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EC-Lab User`s Manual

1. corr corr BB R y Pee dl Prcor B B In10 corr 153 EC Lab Software User s Manual This relationship is commonly named the Stern Rp Fit Geary relationship Sator i l Trace lo vs Ewe For the Rp Fit the user has to select the data points From point 454 oe l ES 0 228 5V and the fit with the Rp fit button as described 0 010 02 m before By clicking on Calculate the software will Topoint 554 automatically find a potential value E on the curve K D177 EW for 0 Two circle markers are set in a 25 mV ie 0 018 28 m Total ponts 101 potential range around E as well as default values for Ba and Be This range and Ba and Be values used for the fit are defined in the Parameters frame EOS The Rp Fit calculates the polarization resistance Rp Pa 120 0 mv and the open circuit potential Ecor by a linear re Po 120 0 mv gression around Ey 25 mV on I vs E plot All the Range i 25 0 mW data points in the potential range are used for the lin Results ear regression Hn 1 856 Ohm Rp is given by the inverse of the linear fit slope and N ies jii Ecorr by the potential value calculated from the linear aa UE Fp equation for 0 i The correlation coefficient shows the accuracy of the linear regression Calculate Copy Save Close It is also possible to determine lcor by adjusting the Tafel coefficients Ba and Be previously determined by F
2. Fig 79 PEIS left and GCPL right selection window for a stack experiment Tips If the user wants to perform impedance measurements on stacks impedance ability is only needed on the master channel With a VMP3 with 16 channels and only 1 with impedance ability impedance measurements can be performed on up to 30 elements assuming that the control voltage of the stack is lower than 20 V 2 10 Batch mode The batch offers the possibility to link a lot of experiments as a series of settings files i e mps files In this configuration the computer is the master of the experiment and sends one mps file after the other when the previous experiment is finished The instrument is not autono mous in this case and a Network communications failure will stop the experiment To display the batch selection window click on Batch in the Tools menu 55 EC Lab Software User s Manual 5 Channel 5 Batch Lo JE meza Batch List 5 5 G C Users electrochimeDesktophy1 0 20 0 ata Samples Battery 1 6650 GIT 71 mpr L Userselectrochime Desktop hl 0 2050 ata amples B atten S650 linked 1 GOCPL 1 cor mpr CL Ueers electrochime Desktop hy 0 2040 ata S amples B atter d S650 linked amp GORL 1 cor mpr C Users electrochime Desktops 0 MD ataS5amplesBatter CP RAGONE mpr LA Lserselectrochimie Desktops 0 MD atarSamples Batter 16650 cuclage GCPL_1 mps Output Folder C Users electrochimiet Desktop m Name Ba
3. AA E ao Zo Zo Tf _ oo aio oy nine Non compacted 0 FOU 1000 1500 000 on times Fig 225 Overlaid compacted and non compacted current curves The variables that can be obtained from compacted files appear when the boxes at the bottom of the process window are ticked keep only values at the end of every open circuit period and or on period 5 1 5 Capacity and energy per cycle and sequence Capacity and energy per Cycle and sequence calculates the capacity energy and capaci tance per cycle for the Galvanostatic Cycling with Potential Limitation GCPL Chronoam perometry Chronocoulometry Chrono l Q Cyclic Voltammetry CV and Potentiodynamic Cycling with Galvanostatic Acceleration PCGA files The values are calculated for both the charge and the discharge The generated file is a compacted file The user can define the frequency for which the data points are recorded every sequence a or every cycle b The cycle definition can be performed automatically or every loop or every charge discharge alter nance 165 EC Lab Software User s Manual Capacity amp Energy per Cycle or Sequence Raw File Experiment Procezzed File Record one point at the end of each Define cycles by Processed file variables epcle number E change A Cycling rate charge Q charge m hi E discharge A Cycling rate discharge A discharge ma h e control mA Close
4. Calculate Copy Save Calculate Copy ae Fig 154 CV Sim window with a single transfer Fig 155 CV Sim window with several transfers For each step the type of reaction and the species characteristics are set in two different frames le Reaction Reduction or oxidation has to be selected by the combo box Z represents the number of electron involved in the electron transfer E is the standard potential of the electron transfer step k is the heterogeneous rate constant atis the charge transfer coefficient in the forward direction 109 2 Species EC Lab Software User s Manual Ca is the concentration of the species A Dg is the diffusion coefficients of the species B The experimental conditions are set in the Setup tab which is divided in five blocks CW SIm Example Mechanism Electrode Geometry Linear Semi intinite A adius 11 cm Surface 3 142 crf Expermental Conditions it Ag ie Ge Temperature Double layer capacity Potential Scan Scan type Linear bl aT Vs E init 05 7 Y Vertex 1 05 a3 Y Number of scans 2 00 Sampling Number of points 11 oo per Car Total number 199 of points Scan rate Vertex 2 80 808 me 8 081 my Sampling time Potential steps Moise Add noise Noise level 1000 000 pu s i 0 000 mi Calculate Copy Save 110 Fig 156 Setup tab of CV Sim e Elect
5. 6 Finally click on Configure to configure the selected channel to record the auxiliary input signal The new selected variables for Analog In1 and Analog In2 are automatically displayed in the Cell characteristics window and activated for recording In the Selector the created varia bles are displayed and can be plotted These auxiliary variables can be used in several proto cols as conditional limits of an experiment Note The parameters set in Analog Ini and Analog In2 to define the linear slope can be inverted to have an opposite variation of the recorded value with the plotted value The configuration of external devices that can be controlled by the potentiostat Ana log output are described in detail in the corresponding sections of the manual A manual control of external devices is also available on the right of the panel When a channel has been configured to control an external device this device can be seen in the global view 6 4 2 Rotating electrodes control The standard instrument equipped with channels delivered since November 2004 with or with out boosters can control a rotating electrode such as a ALS RRDE 3A RRDE Rotating Disk electrode model with the auxiliary input output A specific control panel has been designed to control the rotating speed Note that no measurement of the rotating speed is available This model of rotating electrode is designed to work either one or two working electrod
6. Mass is in mg Molecular weight and the atomic weight are in g mol this is why mass needs to be multiplied by 0 001 F is equal to 26801 mA h mol X quantifies the change of insertion coefficient of the considered ion when a charge of 1 mA h is passed through the cell or disintercalated when a discharge of 1 mA h is passed The charge needed to increase X of 1 is given in the window for Ax 1 AQ 26802 mA h The variable x which is the insertion coefficient of the inserted ion or stoichiometry of the inserted ion in the concerned compound resulting from the charge is calculated using the following formula X Xo X Q Qo x is the sum of xo the initial insertion coefficient and X the change of insertion coefficient during the charge or disintercalated during the discharge Q Qo Q Is the initial state of charge of the battery and is calculated using Xo Finally it is possible to enter the capacity C of the battery in A h or mA h The capacity of the battery is the total charge that can be passed in the battery A capacity of 3 2 A h means that the fully charged battery will be totally discharged if a current of 3 2 A is applied during 1 hour In the techniques dedicated to batteries and especially the GCPL techniques and Modulo Bat technique MB it is possible to define the charge or discharge current as a function of the capacity For instance using a battery of 3 2 A h if the charge is set at C 2 it means that t
7. A 30 amplifier standard 10 4 5 amplifier standard lt None gt standard Fig 83 VSP 300 Virtual mode 2 14 Configuration options Choose the Config Options menu to load the Option window 61 EC Lab Software User s Manual 2 14 1 General Options Options default General Warning Test export Colors References Tool bars menus E Mail Files Save data every i 3 Add channel number to files names LCA Add devices ID to files names _ De LOG files mpl automatic erasing on stop Create automatically saved files Directoy CAECLabiDatas B Prefix Create one folder per day Saved File director dates lt index lt preft mpr Hide processed on line files mppl Manage Reports Ls Stack temporary files 5 mpr automatic erasing on stop Fig 84 Option window General tab The general options window is composed of the following options e Save data every s defines the data transfer rate between the buffer board to the com puter Enter a non zero time value into the edit box The data will be then transferred at this defined time interval e Select the automatic adding of the channel number to the file name e Select the automatic adding of the device ID to the file name Either the last three digits of the IP address if connected through Ethernet or USB if connected through USB Example an experiment created with the channel 3 of a VSP
8. Total points 288 Results Integral 9 09de 3 m4 Calculate Lopy Save Close Fig 138 Integral window Integral Selection Trace l gt vs Ewe From point 2026 me 0 243 2 Y 4 249e 3 m To point 2313 A 1 192 T 0 015 56 m Total points 288 Results Integral 9 899e 3 m Calculate Copy Save Close Fig 139 Integral determination on a trace 100 EC Lab Software User s Manual 4 1 8 Fourier Transform Fourier Transform This mathematical tool FT allows the user to calculate nn E the Discrete Fourier Transform DFT The Fourier Trans A form of a time trace is a representation of this trace in the be De frequency domain The DFT requires a discrete input ie 0 098 58 Y To point 420 The is done following the formula a ells e 0 098 9 Y e o Xk exp 2irr t with Total points 421 Sampling O53 Xi o 1 Xk X t x kdt 2 Hz l P A Parameters When a data point zone is selected click on Calculate Once the zone is selected it is possible to choose the Window Rectange shape of the window In signal processing a window function also known as an apodization function or tampering function is a function rs is zero valued outside of pea chosen dered When FreaMin 0 000 JE a time record is multiplied by a window function the prod Freg Max fi 000 He uct is also zero valued outside the interval This removes Nb Points ig the additional fr
9. Load settings Note Most of the techniques allow the user to add sequences of the same techniques using mouse right click or using the Edit menu On the Parameters Settings tab the CV detailed flow diagram or the column diagram is displayed 21 22 EC Lab Software User s Manual EC Lab V10 36 VMP3 192 109 209 236 channel 2 experiment CV technique Cyclic Voltammetry Experiment Edit View Graph Analysis Tools Config Windows Help G al 1 E 4 5 6 MY e 9 10 11 12 13 14 Ugo Devices Turn to OCW between techniques E Scan E we with dE dt to vertex potential Es Yo vs Measure lt l gt over the last of the step duration Experiment Record lt I gt averaged over N voltage steps 1 0 mW E Range Range Restan Fay Cell Characteristics Bandwidth Advanced Settings External Devices _ Parameters Settings _ Reverse scan towards vertex potential E Y ys O 4000 points per cycle Repeat i time s Reverse scan towards Es Y oys Force E1 E2 End b1 CV 4 VMP3 AL 192 109 209 236 Channel2 Read mode Fig 30 Cyclic Voltammetry detailed flow diagram Experiment Edikt View Graph Analysis Tools Config Windows Help ewi Ms 5 6 7 8 9 wo tt Devices Turn to OCY between techniques 1 ill SetEwe to Ej Wows VMP3 236 Scan Ewe with dEfdt ooo to vertex potential Eq f 000 Yo vs Reverse scan to vertes Ep 1 000 Wo vs Repeat
10. Re Zstack Ohm Fig 77 Stack PEIS measurement with the impedance graph of the whole stack bottom and of each slave channel top GCPL6 mpr El vs time E2vs time E3vs time E4 vs time GCPL6 mpr Estack vs time Estack V 2 000 time s Fig 78 GCPL experiment on a stack of four elements top and on the whole stack bottom 94 EC Lab Software User s Manual On Fig 80 one can see that for stack experiment a Slave selection is available to display all the slave data points in the same graphic window For EIS experiments Nyquist and Bode plots are available both for the whole stack and for the elements Variables Variables Representation Custom ws Bode Impedance Representation di timess J yguist Impedance Rel stac Black Impedance control m Iml stac Fy ys t E stack Re 41 Nyquist stack slave Els ey Am lt 1 Bode stack slave ES F Rel2 Bode Al ES F Im 22 cycle vs time EA F Rejz3freq vs time dg m h Imz 3 Ewel vs freq Py Rep l l vs teq lt i gt ma Ampz4 Ewel Il vs freq Q Go m h Re Z5 Custom A pS Lis dll OS TS NS LENA SSE Im 25J4Dhm v Same selection for all files Frequencies v Same selection for all files stack Hide Additional Variables AAA Hide Additional Variables l i Stack 4 keep previous axes process v keep previous axes process keep previous zoom keep previous zoom Cancel Cancel
11. button to modify the range of data points selected for the Results Polpnomial order fit Pe oe ee The coordinates of the first and last data points used for the E2 2 fit are displayed as well as the number of points used for the 0 249 7 fit in the Selection frame 0 042 05 The results can be copied to the clipboard and be pasted in A the print wndow comment zone or in a text file They can be saved in a text file AMS Error 0 015 8597 E W Fig 132 Polynomial Fit window 4 1 4 Circle Fit a Trace mf ve Rel When the zone to fit is selected click on Calculate in the ada aa circle fit window Fig 133 A part of a circle curve is displayed Y 0 963 5 Ohm as a result of the regression between two green cursors with ee m the Least square method fit Fig 134 y 13 76 Ohm Move the cursors with the mouse by holding the mouse left Total points button to modify the range of data points selected for the fit The new regression is automatically calculated when one of the cursors is moved The coordinates of the first and last data points used for the Results Parameterz Iteratiwe algorithm fit are displayed as well as the number of points used for the od dl a i eMe Y S Z m fit in the Selection frame ano a In the Parameters frame an iterative algorithm allows the Std Deviation 0 629 adjustment of the results using a minimization with the sim Depression 17 plex method Low intercept 46 89
12. or s In the global view above one can see that channels 1 2 3 from the VMP3 are grouped and channels 12 13 14 15 from the VMP3 are synchronized Note one can group or synchronize channels by using keyboard shortcuts 1 To group channels first click on the Modify button and then select the channels while pressing the SHIFT key The grouped channels are colored with the same color 91 EC Lab Software User s Manual a a fefsfofrfofojo s i e stopped grouped To deselect a channel from a group click on the Modify button and deselect the chan nel while pressing the SHIFT key 2 To synchronize channels proceed in the same way as for grouping but with the CTRL key instead of the SHIFT key The synchronized channels are colored with the same color a a e s s 7 al i Eees stopped synchronized 3 Channel with linked experiments can either be grouped or synchronized Tip Loading the same technique with different parameters on many channels Let us say a user wants to perform the same technique on several channels but with slightly different parameters Instead of setting up the techniques individually for each channel the group function can be used to have the same technique on all channels Then if the user ungroups the channels the technique will still appear on each channel The desired param eters can then be set and the channels synchronized 2 9 2 Stack experiments Stack experiments are av
13. 4 6 S percapac ho MENU koera pe A E E A E 148 4 7 COMOSIOM MENU sn oca 148 Aide A A A A A hte tean Meta ant ar 149 AV TAI FEMINACO Wi 150 A A o tech ta culea a N 152 ALAS Minimize ODO sarria ii Id 152 AT Ro Filseteotercoetscle el stepheeentecueitatene a a e 153 Be Te O o 155 4 7 4 Variable Amplitude Sinusoidal microPolarization Fit VASP Fit coocccoo 155 4 7 5 Constant Amplitude Sinusoidal microPolarization Fit CASP Fit 0 156 4 7 6 Electrochemical Noise AnalySIS ccccccssccseceeceeeeeseeeneeeseeeseeeneeeseeeneeeaeeenaes 158 4 7 7 Other corrosion processes ccccccccceseecceeeeeceeeeecceececsegeeessesesseueeesseneessaaeees 159 Data and Tle DIOCES SING posi 160 5 1 Data PrOCESSING visir da AAA AAA AAA 160 SLI Process WINAOW surta do Lali Lario dio 160 512 Additonal processing OPINAS ete seeded reed nee edge ate nae edn peed nee edad ed 162 5 1 3 The derivative process im 163 5 14 TNecompact DIOCESS sis id doc acusa 164 5 1 5 Capacity and energy per cycle ANd SEQUENCE ooocccccocccccnnccnconacoconnncncnnaninennnoos 165 5 1 6 Summary per protocol and cycle occcoccncoccncccccncnncnnoncnnnnncnnnncnnnnnnncnncnnnononos 167 5 1 7 Constant power protocol SUMMAaAry ccoooncncccocnncconcnconononcnnnconononcnnonanononnnranononos 168 5 1 8 Coulombic Efficiency Determination CED Fit ooccccocccccccnccccnnconcnonononcnonnos 169 SLI Polarization RESISTANCE secisetie sees a a acia 171 A
14. 913 925 1995 4 J P Diard B Le Gorrec C Montella Comments Corrosion Science 40 495 1998 WASP Fit Selection Trace Ap ve sin ampl From pont 4 gr4e 3 W We 1979 Ohm To point 19 ie 01 T 858 4 Ohm Total paints 20 Fit Ta Ik R cone 3 a E a 1 co pan Use B and pa Use b and Bo 15 01 79 1 496 7 y 136 4 AI 2612 Iterations 346 Calculate Copy Save Close Minimize Stop Fig 217 VASP Fit window 4 7 5 Constant Amplitude Sinusoidal microPolarization Fit CASP Fit For more information please refer to the Application Note on CASP A sinusoidal potential perturbation AE t E t Ecor 0E sinf2rrfst of a single frequency fs is applied to the sys tem which is considered to be a Tafelian system The frequency is low enough such that the system is considered steady state in which case the current response with time can be de scribed using the Stern equation 156 EC Lab Software User s Manual CorrSim mpr e vs time 0 008 0 006 0 004 0 0027 l mA 0 002 0 004 0 006 0 008 i a i g X E 20 40 60 80 100 time s Fig 218 Output data for CASP simulation The current response can expressed using a Fourier series expansion which results in the following equation 5 6 I t h l sin wt l cos 2wt h sinBwt where the fundamental is 6 and the two first harmonics are 6 2 0 3 respect
15. Ewe Max ooo Y Ewe min 0 00 Ill 0 000 m I Gol 0 00 m h Analog IN 1 max 000 Y Analog IN 2 max oo Y for t gt id o me Do not start on E overload Channel Ultra Low Current Option Floating High speed scan Grounded Definition of high speed value depends on the curent range used Electrode Connections Modify on disconnected cells only standard Miscellaneous Text export T Smooth on 0 points Create one data file per loop linked techniques only Default Fig 51 Advanced settings window for SP 300 technology 35 EC Lab Software User s Manual For SP 200 SP 240 SP 300 VSP 300 and VMP 300 instruments the compliance is not ad justable and is equal to 12 V However for the booster belonging to the SP 300 technology the compliance depends on the booster type For these boosters the compliance is as follows 49 V for the 1A 48V 30V for the 2A 30V 3 14V for the 4A 14V and 0 5V for the 10A 5V booster 2 5 3 4 1 Filtering This option is only available for the SP 300 technology It is possible to filter potential E and current 1 by hardware Three analog filters exist 5 Hz 1 kHz and 50 kHz It is also possible to obtain the raw data by selecting No filter None 2 5 3 4 2 Channel This menu is only available for the SP 300 technology The Channel menu allows the user to select between Grounded and Floating mode for the used channel The Floating
16. If EC Lab is connected to a suitable multichannel the Group Synchronize Stack window accessed using this button will show the Stack option in the drop box cf Fig 77 When clicking on one of these choices the following window appears for channels selection master CH8 CA2 Ref slave CH9 Refi Group Synchronize f Stack Group MP3 237 device channel 8 in shack mode with slave CH9 Ref dace CHS Devices Channels 1 2 4 3 WMP3 237 Pi Ce 9 10 11 12 15 14 15 16 5 6 7 de dd slave CH9 Ref3 slave CH10 Refi Select all channels of VMPS 237 device slave CH10 Ref slave CH10 Select all channels of all devices Stack master 41 8 Number of measured elements in the stack 4 12 AA slave CH10 Ref3 OF Cancel master CHS CA1 Ref3 Ref2 Fig 76 Channel selection window for Stack measurements Using the graphic on the right the user can select the master channel and the slaves The master channel is the channel that is active when the Stack window is open Each slave channel will be able to measure the potentials on two elements using Ref1 Ref2 and Ref3 The potential of the first element is Ref1 Ref2 and the potential of the second ele ment is Ref2 Ref3 As an example with the picture above the master channel is ch8 and the unit has 6 channels to follow the slaves so the total amount of measured elements in the stack is 12 On the slave channels the current wires CA1 and
17. In every technique with potential control and current measurement the user can choose the current recording conditions between an averaged value per potential step for a sweep and an instantaneous value every dt see the Techniques and Applications manual When a technique is loaded in the parameters settings window a small icon is displayed on the left of the flow diagram with the name of the technique and its number rank in the exper iment in case of linked techniques During a run the technique that is being performed is indicated by a black arrow Notes E Range adjustment On the technique the user can define the potential range min and max values to improve the potential resolution from 305 uV 333 uV for SP 300 technology instruments down to 5 uV for VMP3 technology instruments down to 1uV for SP 300 technology instruments Scan rate setting When entering the potential scan rate in mV s the default choice of the system proposes a scan rate as close as possible to the requested one and obtained with the smallest possible step amplitude The scan rate is defined by dE ct Range The current range has to be fixed by the user When the current is a measured value meas ured can be greater than the chosen Range without current overflow error message In this case the potential range is reduced to 9 V instead of 10 V The maximum measurable current is 2 4 l Range For example with Range 10 mA the curre
18. JShow VMP3 236 Set to l S GCPL_C08 mpr for at most ty h fj mn ee ime Limit Ewe lt EM Vv Record every dEy mv or dty Hold Em for tm hfi mn s Cell Characteristics or ldl dt lt di dt Record every dQ or dtg s Limit AQ gt AQA lt gt AX E Range Experiment Advanced Settings External Devices gt 1 GCPL Heston Fata Range Bandwidth 2 Rest fortp fo hfis mn 00000 s Limit dEwe dl lt dEp dt gt min Record every dER o m o dtp 200000 s ftp O ial Aaly goto Fs 5 time s VMP3 2h 192 109 209 236 Channel Read mode a ode 504 b s Fig 70 Repair channel window The user has to change the file name in order to retrieve the rest of data and then unlock le channel by clicking on the unlock button If the user cannot retrieve the data stored in the communication board the only solution is to reset the blocked channel by clicking on the reset button EC Lab 10 36 YMP3 192 109 209 236 channel 8 experiment GCPL technique Galvanostatic Cycling with Potential Limitation G bal IA 7 Ms 10 11 12 13 14 15 16 Devices Turn to OCV between techniques s l E Ja al Q A Ey d a Ml amp E Ewe vs t v JShow VMP3 236 GCPL_C08 mpr x Ewe vs time single channel with one technique Data buffer Experiment E RA Unlock input channel data buffer
19. a 5 4B9e 3 Y de Y 0 043 71 m To point 2234 E x 0 3835V f CV Fe_basique_1 mpr b gt yz Ewe m 0 123 6 m 015 Total points 390 Results Minimum a point 1845 A 5 489e 3 Y T 0 043 71 m Masimum O05 point 2083 mee 0 232 EW Y 0 209 2 m cae Ga lt l gt ma 0 05 0 1 0 15 0 2 0 2 o 0 2 Ewe V us SCE EC Lab Software User s Manual Min Max Selection Trace lo we Ewe From port 1845 a 5 409e 3 Y see 0 043 71 m To point fe eh A 0 2835 W nite 0 123 6 m Total ports 390 Results Minimum point 1845 a 5 409e 3 Y A 0 043 71 m Md asin point 083 me 0 232 by sie 0 09 2 m Calculate Lopy Save Close Fig 128 Min Max fit window 0 4 0 6 Fig 129 Min Max determination on the graph 95 EC Lab Software User s Manual 4 1 2 Linear Fit When the zone to fit is selected click on Calculate inthe Linear Fit linear fit window Fig 130 A straight line is displayed as a result of the linear regression between two green circles aei with the Least Square Method fit Fig 131 oaa E i i rom pomt O Move the cursors with the mouse by holding the mouse se 7 BABS m left button to modify the range of data points selected for Y 0 066 86 mv the fit The new linear regression is automatically calcu Topoint 67 lated when one of the cursors is moved gt 0 130 2 m The coordinates o
20. cma Surface area 10 001 cre Corrozion mate Fig 209 Tafel Fit Window The Tafel graph Fig 210 is displayed in log Il vs Ewe Two linear regressions are automat ically made using the least square method Each linear fit is limited with two circle markers that can be moved log lt I gt vs Ewe x LP_VASP mpr LP_VASP_tafel mpp q A y 72 O 0 3 4 5 0 4 0 2 0 Ew e V Fig 210 Tafel graph The results of the Tafel Fit are recalculated whenever a marker is moved The default positions of the markers are 80 mV and 200 mV around Ecorr Thanks to the intersection of the linear regressions the software calculates the corrosion potential Ecorr the corrosion current value kor and the Tafel constants 8a and fc The Fit accuracy can be estimated with the y or the y V N The Tafel Fit can also be performed on the Ewe vs log I plot 151 EC Lab Software User s Manual Ew e vs log lt I gt x LP_VASP mpr LP_VASP_tafel mpp Ew e V 4 2 0 log lt 1 gt mAj Fig 211 Tafel Fit on the Ewe vs log I graph 4 7 1 2 Corrosion rate Finally the corrosion rate CR is calculated according to the following equation CR Lor K EW d A CR is in millimeter per year mmpy or milliinches per year mpy lcorr corrosion current in A K constant that defines the units of the corrosion rate EW equivalent weight in g equivalent It is defined as the molar mass of
21. 10 V 10 9 V range E Range is located in the setting of each technique TT 10 10 510 OV 10 AY AY OV oy ADY 2 By A Y Fig 247 E Range selection Using the Edit button opens a window to define the potential range manually Entering the required Ewe min and Ewe max the corresponding value of the potential control resolution ap pears For example entering O V and 1 V leads to 20 uV resolution Edit Potential Range E range min BUI Y max i 0 000 Y resolution 305 18 pi peta coe Fig 248 Edit potential range window Application Optimization of the potential resolution is particularly interesting when trying to perform proto cols based on potential scan such as CV in order to approach linear scans as much as pos sible For example after choosing the above 1 V potential window and loading a CV a 20 UV potential step value is automatically proposed when entering a scan speed dE dt as shown in Fig 249 below 182 EC Lab Software User s Manual Fig 249 CV experiment potential scan with 20 uV steps 6 3 Measurement versus control current range Our potentiostats are designed to work either in the potentio static or dynamic mode or in the galvano static or dynamic mode In the potentio mode the potential between the working and the reference electrode is controlled The current resulting from the redox processes at the applied potential is measured On the contrar
22. 109 209 236 Channel6 Read mode 4 384 b s Fig 64 Linked experiments window The linked techniques are displayed on the left of the window with their number in the experi ment Click on the button corresponding to the technique you want to see to display the detailed diagram Once the file name typed the acquisition starts and the program shows the graphic display with the data files During the run the technique in progress can easily be identified by an arrow next to the cor responding button Its number is displayed in the Channel Values box see next figure as Tech The number of loops executed is displayed as Loop As for a single experiment run it is possible to Pause lll Resume IF and Stop a the ex periment The Stop button will terminate the whole experiments acquisition Nevertheless one can stop the current experiment and continue to the next one with the Next Technique button in the tool bar One can also move on to the next sequence using the Next Sequence M button Channel 6 values Fig 65 Linked experiment current values 44 EC Lab Software User s Manual Notes e The bipotentiostat techniques and the manual controls cannot be linked to any other technique e The Polarization Resistance process calculation can be performed on the protocol linker loops separately Linked experiments settings can be saved with Experiment Save As or on the right click menu with Save experim
23. 197 Frequency selection window It is possible to set the surface area and plot a capacitance related to the surface 143 SPEIS _7MHz to 1Hz_ C V_Charact mpr mpr Cs 2 vs lt Ewe gt EC Lab Software User s Manual 1 024 MHz 21 922 kHz 217 576 Hz 3 168 Hz 0 002 0 0015 0 001 Cs 2 pF 2 0 0005 lt Ewe gt V Fig 198 Mott Schottky plot for several frquencies The Mott Schottky Fit isa graphic tool introduced with the SPEIS technique to determine semi conduc tors parameters flatoand potential and donor density based on the Mott Schottky relationship from a Mott Schottky plot Before using this fit a Mott Schottky plot 1 Cs vs Ewe of the experiment must be displayed on the graph This plot shows one trace for each selected frequency Note that only Cs can be used for the fit The Mott Schottky Fit corresponds to a linear fit for each trace one trace for each selected frequency The same potential range is used for every trace When a data point zone is selected click on Calculate A straight line for each trace is displayed as a result of the linear regression betwen two green circles with the Least square method fit Move the circles with the mouse by holding the mouse left button to modify the range of data points selected for the fit The new linear regression is automatically calculated upon moving a circle MMott schottky E Parameters 29 0 C T
24. A Electrochemical Impedance Spectroscopy E Batteries Photovoltaic Fuel Cells supercapacitor amp Corrosion Show Analysis Results TT F FO TY F TUF Fig 126 Analysis menu 4 1 Math Menu The Math menu contains linear polynomial and Circle fits but also the determination of the minimum and the maximum on a curve a Multi Exponential Fit and Sim This Math menu allows also the user to filter the obtained curve to subtract curves to do Integral on parts of the curve or to do a FFT transformation 4 Min Max Shift F1 Y Linear Fit Shift F2 Atl Polynomial Fit Sy Circle Fit Shift F3 Fall Linear Interpolation Shift F5 Subtract Files shift F6 EY Integral Shift F7 Frit Fourier Transform ShiFE FS y Filter Shift F9 Ey Multi Exponential Sim e Multi Exponential Fit Fig 127 Math Menu 94 4 1 1 Min and Max determination On the graphic display select Min Max with the Min Max button or the mouse right click The Min Max analysis window appears Select the zone to fit on the trace and click on Calculate The Min and Max values are automatically detected The Min and Max coordinates are displayed in the Fit window and highlighted in red on the trace Fig 129 The results can be copied to the clipboard and be pasted in the print window comment zone or in a text file They can be saved in a text file Min Max Selection Trace le ve Ewe From point 1845
25. AGS BI Selection ki Trace Pus Ene Selector v Show D From point O 3 1 45 Y LP_PV mpr 0 rial e lt i gt vs Ewe P vs Ewe To point 6299 A 0 815 9e 3 Y Y 0 033 61 miw Total points E300 a at ta i 41 181 m 3 145 129 508 rv 91 069 mw 0 3 Pin 1750 Wen 5 28 500 cme Efficiency 18 3 Calculate Copy Save Close Fig 205 Typical vs E curve for a photovoltaic cell FE E oc PT Fmax FF The resulting V characterization shows a typical vs E and P vs E curves Several parame ters can be drawn from this curve with the Photovoltaic analysis tool Short Circuit Current hc which corresponds to the maximum current when E 0 V l 41 mA in this example the Open Circuit Voltage Eoc which is the potential at which the current is equal to 0 Foc 3 145 V the theoretical power Pr which is defined by the following relationship Pr sc X Eoc Pr 129 mW the maximum power Pmax 91 mW the Fill Factor FF which is Pmax Pr FF 70 3 the efficiency can also be calculated It is assumed that the solar power is equal to 175 W m which gives 499 mW for our photovoltaic cell of 28 5 cm The efficiency of the photovoltaic cell is 91 499 18 4 6 Supercapacitor menu The supercapacitors provides two analysis tools for characterization of supercapacitors These tools are detailed in the batteries section Chapter 5 BE Process Data Cycles
26. At the end of the fit the generated voltam mogram is displayed in the active graphic window of EC Lab Once all the Fit has been finished the values of the parameters with a checked box are dis played a calculated standard deviation parameter lt gives an estimate of the relevancy of the parameter Fit if the dev is very high it means that a great variation of the parameter will not affect very much the quality of the fit X is the global error on the Fit whereas X N is the global error divided by the total data point Example File Mechanizm E E Setup Selection Fit Reaction Reduction A zedH lt E z UA Eo D206 Yo 934e12 ko J Sted cm s 2 03e 12 of IA ES 0 671e 9 Species Ca initial Te2 mol L Cp initial O mol Da Me5 cm i s 10 5e 15 Op B0Be 6 cm ts xxx re 0 693 2e 12 wiv 0 81e 9 Iterations 178 Relative error Duration 00 00 05 Calculate Copy Save Irit quess Minimize Stop Fig 167 Results of CV Fit 119 EC Lab Software User s Manual 4 3 Electrochemical Impedance Spectroscopy menu Impedance analysis is a powerful tool to determine the mechanism involved in an electrochem ical reaction and the values of the kinetic parameters of this mechanism Electrochemical im pedance data analysis allows the user to propose an electrochemical reaction mechanism to define the system The expression of the faradaic impedance of a certain type
27. Batch Mode Repair File Repair Channel Connected PC Tera Term Pro Calculator QA e e Notepad Fig 11 Tools Menu The Tools menu is composed of three frames The first one is for the data file modification Modify Cell Characteris tics Split File Under Sam pling The second frame is related to operations performed on the firmware Channel Calibra tion Repair Channel Down grade or Upgrade the Firm ware or the file Repair File Batch mode The last frame gives access to various tools such as Tera Term Pro used to change the instrument configuration Calculator and Notepad 13 EC Lab Software User s Manual Seep Windows a User Disconnect m Virtual Potentioskat iM Options ShiFE Ckrl 0 Help Ctrl U Fig 12 Config Menu The config menu is dedicated to display username window to access and modify soft ware configuration to access virtual potentiostats All the functions here except the Options are available from the Devices or Experiments boxes 2 3 Tool Bars 2 3 1 Main Tool Bar Main Tool Bar BOXES Pe Sgd4 E Cascade EA Tile w I VMBP3 channel 1 no experiment Fig 13 Windows Menu This menu is used to choose how to display the windows and close them Fig 15 Main Tool Bar grs te HL EC Lab software user s manual EC Lab software techniques and applications T VMP3 installation and configurat
28. Ctrl I ma Insert Technique From File Ctrl F TP Move Technique Before gt Remove Technique J Remove All The Techniques TE Group Synchronize f Stack 2 Accept Ctrl M Pe Cancel Modify Run ChrHR Fig 61 Mouse right click with the insert and remove options The second frame is especially dedicated to linked experiments The Insert New Technique function opens the technique selection window and can insert a new technique into the exper iment The additional technique can be added before or after the activated selected technique using the Insert Technique frame at the bottom left corner of the technique selection window Insert Technique Before le After Fig 62 Insert before after option of the technique selection window If the technique is not in the correct position in the series of experiments the user can easily move it up or down using the Move Technique Before and Move Technique After options respectively Note it is possible with the protocol linker to apply 50 ms OCV period between two protocols reduced to 0 6 ms if the previous protocol is an OCV The user has just to activate Turn to OCV between techniques in the Advanced Settings window If this option is not selected the user will not have the ability to select different current ranges for each linked technique When inserting a technique other options are available Load from default Advanced setting External devices Cell character
29. Duration 00 00 00 Calculate Copy Save Init quess Minimize Stop Fig 161 CV Fit window For each mechanism one or more example of theoretical voltammogram based on simulation tests CV Sim tool are available in CV Fit The user should click on Example button select the mechanism of interest by clicking on Select button The example parameters shown in the parameters section of CV examples window are automatically loaded Fig 162 Before run ning the Fit the user should put the correct sample radius and the scan rate used for experi mental curve It is also strongly recommended to set a parameter near the expected values like standard potential E diffusion coefficient If the value of a parameter is not known Init guess tool proposes a good approximate value of a parameter before the fit start For example 113 EC Lab Software User s Manual an initial value equal to Epa Epc 2 is given to the standard potential where Epa and the Epc are the peak anodic voltage and the peak cathodic voltage of the experimental voltammogram CV Fit a Mechanism E CVsim Examples E Setup Selection Fit Electrode Example Parameters Ss 1 E DLSI Mechanism E Geometry Linear Sem infinite bl 2 E DLSI Rohm Felll Fell E E 3 E DLSI Rohm Cdl Reaction Padu E a 4 E DLSI Rohm Cdl Reduction A ze lt gt B 5 E DSSI z 1 Surface 178 54 rrr 6 EE DLSI El 0 2
30. Fig 226 Capacity and energy per sequence processing window The result of the calculation is a compacted processed file that contains several columns de pending on the selected variables The values can be processed as densities using the elec trode surface area or the characteristic mass Qcharge Q discharge and Energy are calculated by using the following formula Q charge discharge 1 t 3600 A h E charge discharge E i t 3600 A h Cycling rate charge control Q charge Cycling rate discharge I control Q discharge a Efficiency Qdischarge Qcharge Capacity amp Energy per Cycle or Sequence Raw File Experiment Processed File Processed file variables cycle number E changes h C discharge F charge m h E discharge 4e h Efficiency O dicharge m h C charge F Fig 227 Capacity and energy per cycle processing window 166 EC Lab Software User s Manual The capacitance calculation is done as follows C Q AE Farad C 1 1 3600 AE Where AE is the potential difference between the first point of the sequence and the last point of the sequence 5 1 6 Summary per protocol and cycle This process allows the user to analyze CV CA CP GCPL GCPL2 GCPL3 GCPL4 GCPL5 GCPL6 GCPL7 and PCGA linked experiments In calculating Gla dia C sathodic and Xmin and X ma X being lanodic Icathodic for each cycle and linked experiment loop Select this
31. Hold Ep for t Ad d Setti vanced Settings Limit I lt 1 Cell Characteristics or ldl dt lt didi Change Saved File Name New file acr bishe Record every d External Devices E Directory BER Fiets EX ATEST GCPlpbig COS di Limit AQ gt AQ Repair Channel gt 2 jJ Change channel 8 saved file gt 1 GCPL Reset Data buffer will be emptied a 2 Restfortm fo hfi5 mn 00000 s Limit IdEwe dtl lt dER dt 7 om h Record every dEg mV o dtm 1200000 s itp Gor AA i Mtg Gor AG Aay go 2 A time s VMP3 JL 192 109 209 236 Channel Readmode 1 56 3 35 21040b s Channel 8 is locked Fig 71 Retrieve of data and unlocking of a channel board 49 EC Lab Software User s Manual In the case of an experiment where the sampling conditions are not properly set the display of the curve is very slow Sometime the curve display is blocked The current values b a A A A A cee eee eee VSP 300 L 192 109 209 237 Channel6 Readmode a 0 057 2 3 360 21 040 b s Fig 72 Current value tool bar with a full buffer Multi channel selection Grouped Synchronized Stacked or bipoten tiostat experiments 2 9 1 Grouped or synchronized experiments te The button corresponding to the Group Synchronize Stack window is Grouping It is possible to run the same experiment on several channels this is what we call to group channels It is possible to group channels f
32. Impedance Representation YT axis Y2 anis Er hm Phaze deg log 1541 LL gt ES treq Hz log 24 Fig 120 Graph representations window 3 2 10 1 Axis processing As shown previously it is possible to apply a mathematical function on each axis By default standard functions such as log X X X 1 X are proposed Fig 121 Nevertheless it is possible for the user to define his own processing function using the Custom menu Then in the window given Fig 121 the user can define an operation in the Variable box in this example it is the Lx box Mathematical functions are available ticking the box more 89 EC Lab Software User s Manual Graph Representations Niuquist Admittance se Black Admittance EI Phasel4 error Bode Impedance CE Representation Nuquist Impedance CE d Black Impedance CE Hame user 4 Rp vs sin ampl TT anis Y2 arts RI vs t Ewe Ba E stack slave ws t 1 custom Bode stack slave Nyquist stack slave 3 Bode Impedance WE rel Nyquist Impedance wil Tie Black Impedance WE eas vz Q charge vs t time s sqrt Y G discharge vs t 1 sqrt Ye log 2 O charge O discharg spacing q exponential of a number sqr square of a number sqrt square root of a number abs absolute value round round to the nearest integer trunc truncates a real number to an integer AE Ing natural logarithm Mathematical ex
33. Manual Example File Mechanism E E Setup Selection Fit Electrode Geometry Linear Semi infinite Radius 5 mm Surface 178 54 m Experimental Conditions Temperature 25 als AQ a ss Double layer 0 UF soto capacitance Potential Scan Scan rate TS rei as f MEME Fi i TETE MMM Iterations MEM Relative error ses Duration 40 00 00 a Calculate Copy Fig 164 Setup Tab of CV Fit window 4 2 4 3 Selection tab The selection tab displays the selected points on the voltammogram to fit and the total of points selected By default all the points of experimental voltammogram are selected The user has also the possibility to select a part of the experimental curve like the points corresponding to the forward scan or to the reverse scan 116 Example Fe Mechanism E E Setup Selection Fit Trace HHMH From point sans ai HHMH E HHMH Topornt sx a EN n Mm Total points sae A A x Y ri TET MMMH Iterations bat Relative error sexe Duration 00 00 00 Calculate Copy Save EC Lab Software User s Manual File Mechanism E E Setup Selection Fit Trace lve Ewe From point 0 a 0 6 Y DA Topomt 7699 PA 0 598 E Y T 0 383 be 3 4 Total pointe 1600 z 0 706 2e 12 F A 21 01e 9 Iterations 2b Relative error 0 098 39 Duration 00 01 016 Calculate Copy Save Init guess Minimize Stop Fi
34. O MUNTEITHAGSTAUSUCS ana a N 173 5 2 Data File import export functions oocccoccccncncoccnconnconcnonanonnnnonncnnnnnnnnnncnncnnnanennnnss 174 5 2 1 ASCII text file creation and ExPOrtatiON isa a E 174 522 ZOMMPVW IN Ns 175 5 2 3 ASCII text file importation from other electrochemical software 175 5 2 4 FC Lab data files importation coocccconncccncconnoconnnnnnocnnnonancnnnnonannnnnnonnrnnnanonos 177 Advanced feature Siiski a a a aaa a a isis 178 6 1 Maximum current range limitation 2 4 A on the standard channel board 178 6 1 1 Different limialONS esuperanto a 178 6 1 2 Application to the GSM battery testing oocccocccocccconnoccnnconnnconnccnnnnonnnnnnnos 179 6 2 Optimization of the potential control resolution cooonccconcccconcnconcnnnnnnnnoncnnnnoss 181 6 2 1 Potential Control range SPAN ccecccccseeeeeeeeeeeeeeeeeseeeeseeeeeesaneeeeeneeeseaeees 181 6 2 2 Settings of the Working Potential WiNdOW ccoooccccoccnccncncccnnnccncncnonononacnnnnnos 182 6 3 Measurement versus Control current range occcocccocccocccncncncncncncncnnnnnnnnnonnnnnnnnns 183 631 PME potenie MOOS ad iia 183 6392 IMmegalvano MO rra roce iia 184 6 3 3 Particularity of the 1 A current range in the galvano mode ooccocccncccocccocncncnn 184 6 3 4 Multiple current range selection In an experiment oocccocccnncnnoccconcnconcnnnnnnnnonos 185 6 4 External device control and
35. Ohm The results displayed are the parameters of the circle The ed sa eee depression is the angle between X axis and the diameter de c 610926 F fined from low x intercept R is the difference between high x intercept and the low x intercept C is the capacitance deter mined for the experimental point in the selected zone where Im Z is max Rew 1 The results can be copied to the clipboard and be pasted in the print window comment zone or in a text file They can be saved in a text file Fig 133 Circle Fit window 97 EC Lab Software User s Manual PEIS_Fe_basique_1 mpr o miZ ve Reli 100 90 S T 50 40 30 o m Z Ohm 0 2 20 20 40 50 100 150 200 Re Z 0hm Fig 134 Circular Fit on the graph 4 1 5 Linear Interpolation An interpolation tool Es is available with EC Lab The Linear Interpolation raw data file is not changed after this analysis Selection When a data point zone is selected click on Calculate Trace Im 2 vs Rele The linear interpolation allows the user to space out reg From point 2 ularly in time each point of the data file The user can A 130 5 Ohm choose to interpolate data using a defined number of an N points or a regular time between each point Then a pro E En cessed interpolated data file is created with the follow y 108 8 Ohm ing name filename_intpl mpp Total points 12 Sampling 2 954 This tool comes in handy if the user n
36. R QCM mass Hi Capacity amp Energy Per Cycle or Sequence vee CED Fit Fig 206 Supercapacitor menu 4 7 Corrosion menu Several techniques such as Linear Polarization LP Constant Amplitude Sinusoidal microPo larization CASP and Variable Amplitude Sinusoidal microPolarization VASP measurements 148 EC Lab Software User s Manual are used to characterize the corrosion behavior of materials These measurements are used to determine the characteristic parameters such as e the corrosion potential Ecorr e the corrosion current korr e the Tafel constants a anodic coefficient and 6 cathodic coefficient for the anodic and cathodic reactions respectively defined as positive numbers The Tafel constants can be given as ba and be where ba In10 6a and be In10 e The polarization resistance Ap Please note that these techniques are built upon the assumption that the electrochemical sys tems are tafelian i e that the current flowing in the electrode is only limited by the electron transfer and not by mass transport In this case the potential current relationship is described by the Stern or Wagner Traud equation ja exp MOE Econ _ corr b corr EXP b Also please note that all the techniques are valid for a negligible ohmic drop For more infor mation please refer to the application notes on corrosion measurements http www bio logic info electrochemistry ec lab apps literature applicati
37. The advanced settings window includes several hardware parameters and software parame ters divided in four blocks Compliance Safety Limits Electrode Connections and Miscel laneous Cf Fig 43 Note that for SP 50 the compliance is not adjustable 10V 10V Compliance Modify on disconnected cells only Ewe from 10 Y 10 Ece from 10 W LJ 10 More information gt gt Safety Limits Ewe mar 0 00 Y Ewe min Boo y lll 0 000 m B amp o 0 00 m h Analog IN 1 mas y Analog IN 2 max 0 00 y E stack slave max 0 00 y E stack slave mir 0 00 y har t gt 10 me Do not start on E overload Electrode Connections Modify on disconnected cells only standard WE DA ref Eel RE refe Ece refs CE ACAI Miscellaneous Text export Filter u Edit Smooth or 0 paints Create one data file per loop linked techniques only Default Fig 43 Advanced Settings window for VMP3 VSP SP 50 SP 150 instruments 2 5 3 1 1 Compliance The compliance corresponds to the potential range of the Counter Electrode versus the Work ing Electrode potential Ewe Ece This option has to be modified only for electrochemical cells with more than 10 V potential difference between the counter and the working electrode One can change the instrument compliance voltage between the CE and the WE electrodes from 20 V gt 0 V to 0 V gt 20 V by steps of 1 V In all the range
38. To select from the input file To be added if cl nay 10 Go 4m h HE cycle number 0 charge mA h O dischargers h Energy h J Energy charge h let Energy discharge h eae MW cycle times midi step times 4 charge times F discharge time s All All mode cost ned error control changes Ns changes counter inc times 3 a a a al El Procezz Allow Reprocessing Cycles definition auto Esport As Test Compact Count half cycles Process Display Close Fig 222 PCGA Process window This window is separated in 3 parts Inthe first part Input File on the top of the window the user will add the raw data files to process Click on the Load bution to load a raw data file in our example a PCGA file The second part Variables is dedicated to the variable selection generated the pro cessed file The left section is for the variable selection from the native raw file and the right section for those to be added to the processed file calculated into either the firmware such as lt I gt Q Qo or in the computer as processed variables The bottom section is for additional options in the process It is possible to o Allow reprocessing to be able to process again a mpp file o Export as text a batch of data files 161 EC Lab Software User s Manual o Define the cycle as Auto
39. Y E a 7 EE DLSI Rohm O Q Q 2 k le 3 cm s 1 Experimental Conditions 8 EE DLSL Rohm Cdl af 0 5 Temperature HE 9 EEE OLSI Spedes p ae 10 EEE DLSI Rohm Cdl CA initial 0 01 mol L 1 Ra E D KES 11 EEE DLSI Fe I Fe ID Fe D Fe 0 CB initial 0 mol L 1 O 12 EEEE DLSI DA 10e 6 cm2 s 1 Double layer 2 p pF nama 13 EEEEE DLSI DB 5e 6 cm2 s 1 capacitance 14 EC DLSI Setup 15 CE DLSI 16 EE DLSI Geometry Linear Semi nfinite Radius 1 mm Potential Scan Surface 78 54 mm2 Gean rate 100 pra Experimental Conditions mws y Title Temperature 25 deg Rohm 0 Ohm El DLSI i E double layer capacitance 0 uF 2 4 435 Comments x yiya 005265 Iterations 0 Relate eror 01724 Duration 0 00 00 Irit guess Minimize Stop Fig 162 CV Examples window The number of tabs that appear on CV Fit window depends on the selected mechanism One tab for E mechanism two tabs for EE mechanism and so on The EC and CE electrochemical reactions are also available C standing for bulk chemical reaction with no electron transfer The button file allows a user to load parameters contained in a previous fit file mpp file or a mpr file 4 2 4 1 Mechanism tab Like CV Sim mechanism tab CV Fit mechanism tab displays the parameters used by CV Fit algorithm to model the experimental voltammogram Once a mechanism is chosen the user should select the react
40. Z and phase References H W Bode Networks Analysis and feedback Amplifier design Van Nostrand New York 1945 R L Van Meirhaeghe E C Dutoit F Cardon and W P Gomes Electrochim Acta 21 1976 39 D D MacDonald Electrochim Acta 35 1990 39 J P Diard P Landaud J M Le Canut B Le Gorrec and C Montella Electrochim Acta 39 1994 2585 4 4 Batteries menu The Batteries menu is composed of processes allowing the user to add some variables such as insersion coefficient x capacity during charge energy to his file or to calculate for each cycle the capacity and the energy values to summarize all the significant parameters obtained during each cycle Process Data Cycles R QCM mass Ctrl Fl Hi Capacity amp Energy Per Cycle or Sequence summary Per Protocol And Cycle Ctrl F3 Constant Power Protocol Summary Ctri F5 SED CED fit Fig 203 Batteries menu This menu is described in the chapter 5 4 5 Photovoltaic fuel cell menu This menu provides analysis tools for experiments done on photovoltaic components and fuel cells It provides characteristic values of a solar cell Photovoltaic analysis HE Process Data Cycles R QCM mass H Capacity amp Energy Per Cycle or Sequence Fig 204 Photovoltaic fuel cell menu 147 EC Lab Software User s Manual 4 5 1 Photovoltaic analysis Photovoltaic analysis Eal EX Graph 24113290156
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42. always running properly inthe Tera Term Pro window type r or R this will restart the Ethernet connection pro gram that is a part of the instrument firmware WARNING this operation is not a simple task so proceed like this only in case of trouble if the problem persists contact us Effect of computer save options on data recording Electrochemical experiments can often have a long duration more than 24 hours During the experiment the computer should always be able to record the data points If the user enables the power save option for his hard disk data saving can be disabled In order to avoid this we advise the user to remove the power save option from the computer in the settings panel 194 EC Lab Software User s Manual 8 Glossary This glossary is made to help the user understand most of the terms of the EC Lab software and the terms mentioned in the manual The terms are defined in the alphabetical order Absolute value mathematical function that changes the negative values in positive ones Accept button in EC Lab software that switches to Modify when the user clicks on Modify must be displayed to run the experiment Booster current power booster that can be added to each channel individually Apparent resistance Ri conventional term defining the electrolytic resistance in a solid elec trochemical system such as a battery Ri is defined as the ratio dE dl when the potentiostat switches from
43. amplitude Selector window in the graphic display allowing the user to load add or remove a data file from the graph and to choose the axis parameters Specifications characteristics of the instrument such as cell control or current and potential measurement Stern and Geary model model of corroding systems based on the Tafel equation Stop button used to stop the experiment Style graphic function used to define the plot style and color Subtract files this tool allows the subtraction of two curves for example to subtract a back ground from a curve Summary per protocol and cycle off line processing function giving a table off the maximum and minimum charge current and potential value for each cycle or loop both in the anodic and cathodic side Synchronize option used in a multichannel mode to start the same experiment at the same time on all the selected channels Tafel Fit tool available with the graphic display used to determine the corrosion current the corrosion potential and the polarization resistance with a fit Tafel graph off line processing function allowing the user to display on the graph the logarithm of the current Tafel plot Technique builder section of the selection technique window including the tools and tech niques used to create linked experiments Triggers option that allows the instrument to set a trigger out TTL signal at experiment start stop or to wait for an external trigger in to st
44. an open circuit voltage mode to galvanostatic mode and vice versa ASCII file exportation exportation of the raw data files or the processed data files to ASCII text format in order to use them with other software new format mpt Axis graphic function used to define the axis range the logarithmic spacing and the grid lines Bandwidth represents the frequency of the regulation loop of the potentiostat It depends on the electrochemical cell impedance The bandwidth s values go from 1 to 7 with increasing frequency Calibration operation that must be done for each channel in order to reduce the difference between a controlled value for example Ect and the corresponding measured value for ex ample Ewe Capacity per cycle processing function that calculates the capacity per cycle for the gal vanostatic with potential limitation the chronocoulometry chronoamperometry the cyclic volt ammetry and the potentiodynamic cycling with galvanostatic acceleration protocols CASP Fit tool available with the graphic display used to fit a curve obtained with the Constant Amplitude Sinusoidal microPolarization technique This tool is used to determine the current corrosion and the coefficients of corrosion Channels each one of the boards corresponding to an independent potentiostat galvanostat Characteristic mass total mass of the species in the electrochemical cell in most of the cases It is different from the mass of electroactive
45. and 500 mA for SP 300 SP 200 SP 240 VSP 300 and VMP 300 This is especially used for GSM battery testing Please refer to the part 6 1 page 178 for more details Warning the low current board cannot accept more than 400 mA in potentio and in galvano mode We advise the users to be mindful of the maximum current when using low current boards 184 6 4 EC Lab Software User s Manual 6 3 4 Multiple current range selection in an experiment The EC Lab software offers a facility to select different current ranges in either galvano or potentio mode for an experiment The experiment can be made with only one technique but with several sequences in the technique or with linked techniques In both cases the user can choose different current ranges between sequences or between techniques if an OCV period is set between them For example ina GCPL experiment with 10 sequences the user can select 10 different current ranges if the third block of OCV is activated into every sequence Then a warning message is displayed WARNING i Several I ranges found within technique 1 GCPL Ensure that each I range changes follows an OCV period else the changes will have no effect this is not tested by the software Do not show this message again Fig 252 Warning message on different current ranges into a setting Note when several current ranges are selected in a setting the software will not test if some OCV periods are set betwee
46. as the raw data file but with an mpp extension This Filter tool is described in the paragraph dedicated to Analysis tools Method Low pass ha Window Rectangle Cutoff frequency m Hz OK Cancel Fig 48 Filter window Smooth with sliding average For all the protocols the user can smooth all values I Ewe Ece Aux1 with a sliding average To proceed check smooth and enter the smooth window size between 2 and 100 points Create one data file per loop This option offers the possibility to create one data file per loop for each technique of a linked experiment Then the data files will have a prefix number to define the order in the experiment For example an experiment is composed of OCV CA and then a Loop on the OCV for 9 times If the Create one data file per loop box is not ticked the data from the experiment will be stored in two mpr files one for the OCV and one for the CA If the Create one data file per loop is ticked then the data from the experiment will be stored in twenty mpr files one for each OCV and CA of each loop 2 5 3 2 Advanced Settings with HCP 803 HCP 1005 CLB 500 and CLB 2000 For HCP 1005 HCP 803 and CLB 500 the compliance value and the electrode connection are fixed The other limits and functions are the same as in 2 5 3 1 33 EC Lab Software User s Manual Compliance Modify on disconnected cells only Ewe from 10 Y 104 Ece fr
47. available to calculate the amount of a species electro disposed on the quartz To use this process select the process data option in the Analysis menu 193 7 2 7 3 EC Lab Software User s Manual Troubleshooting Data saving Problem Data cannot be saved from a given channel this channel appears in yellow into EC Lab and the program displays an error message while attempting to save data Solution s ensure that the saved file has not be moved destroyed opened by another application if the saved file is on a network drive ensure that you have the right to write data into the same directory create and destroy a text file Else see your network authorizations in EC Lab select Tools Repair Then select the saved file and click on the Repair button ensure that the computer IP Address has not been modified since the beginning of the experiment if the problem persists contact us PC Disconnection Problem The PC is disconnected from the instrument Disconnected is displayed in red on the EC Lab status bar Solution s check the PC instrument connection direct connection verify that the crossed Ethernet cable is plugged from both ends network connection verify that the yellow led is blinking on the instrument front panel and that you can access to your network directories from the PC check that the green LED is blinking this assumes that the multichannel potentiostat is
48. can be created per technique and per loop in a linked technique In the Advanced settings window tick the box corresponding to Create one data file per loop The file name is created as follows Filename __ technique number in link _ technique name _ channel number _ loop mpr 2 7 2 Applications 2 7 2 1 Linked experiments with ElS techniques The following experiment is given as an example of linked experiment This experiment is composed of OCV CA CV PEIS and Loop techniques 43 EC Lab Software User s Manual EC Lab V10 36 VMP3 192 109 209 236 channel 6 experiment battery test technique 3 5 Modulo Bat Experiment Edit View Graph Analysis Tools Config Windows Help G Y 1 MEN a a s W e LOT i2 13 14 15 16 A Devices Turn to OCW between techniques 7 EE Pda 17 a A Ey e K m fi 0 Ewe vs t i Cl Show VMP 300 239 VMP3 236 Ewe vs time battery test_02_GEIS_C06 mpr Constant Current battery test_01_OCW_COB mpr gt Im Z vs Re Z gt battery test_03_MB_CO6 mpr 0 3 312 0 02 Experiment 0 04 gt 331 Advanced Settings Im Z 0hm 0 06 Cell Characteristics 3 308 ae 0 08 External Devices E Range Resolution 100 p Range Allow to set a different IR sequence turn to rest Bandwidth 50 0 0 05 time s Re Z Ohm battery test_04_CV_C06 mpr e lt l gt vs Ewe 0 Ewe mV VMP3 h 192
49. connected through Ethernet with the IP address 192 109 209 207 will be named experiment_D207_C03 e Erase the LOG file automatically on stop The LOG file will still be contained in the mpr file e Create an automatic data saving The user must choose the directory to save the data file The prefix name must be defined and the software will automatically add the date and the index number e By default the on line automatically processed files are hidden to reduce the number of files in directories The on line processed variables are now automatically displayed on the graphic window e Ability to manage reports of the experiment 62 EC Lab Software User s Manual 2 14 2 Warning Options Options default Display warning messages on Pause Stop Modify auta Accept Next technique sequence Remove technique sequence No record Multiple ranges Profile Importation techniques Safety Limits Displaying more than 32 traces on the graph Fig 85 Option window Warning tab Display or hide warning messages when the following functions are used Pause Stop Modify Accept Next technique Remove technique No data points recorded Multiple ranges differ ent current ranges are selected in the different sequences when the Experiment Limits are reached using a Profile Importation technique and finally when 32 traces curves ar
50. correct the settings and continue the run with the Re sume button or stop the experiment To select an experiment limit check the limit and enter a value and a time for example Ewe Max 5 V fort gt 100 ms Then the limit will be reached if Ewe is greater than 5 V during a time longer than 100 ms Once selected an experiment limit is active during the whole exper iment run It is also possible to set an upper or higher limit on the external analog signals Analog IN1 or Analog IN2 E stack slave min allows the user to set a lower limit that will be applied on each individual element slave of a stack of batteries This ensures that no battery is damaged during the experiment E stack slave max allows the user to set an upper limit that will be applied on each individual element slave of a stack of batteries This ensures that no battery is damaged during the experiment Do not start on E overload allows the user to not start an experiment in case of an overload of the potential E It allows also the stop of an experiment in case of a potential overload 31 EC Lab Software User s Manual Warning the safety limits cannot be modified during the experiment run and must be set be fore 2 5 3 1 3 Electrode Connections Standard connection mode VMP3 technology See Fig 42 The working electrode is connected to CA2 Ref1 the reference electrode to Ref2 and the counter electrode to CA1 Ref3 Ref
51. counter electrode potential or on the external parameters These conditional tests force the experiment to go to the next step or to loop to a previous sequence or to end the sequence Standard graphic functions such as re scaling zoom linear and log scales are available The user can also overlay curves to make data analyses peak and wave analysis Tafel Ro linear fits EIS simulation and modeling Post processing is possible using built in options to create variables at the user s convenience such as derivative or integral values etc Raw data and processed data can be exported as standard ASCII text files The aim of this manual is to guide the user in EC Lab software discovery This manual is composed of several chapters The first is an introduction The second and third parts describe the software and give an explanation of the different techniques and protocols offered by EC Lab Finally some advanced features and troubleshooting are described in the two last parts EC Lab Software User s Manual The other supplied manual EC Lab Software Techniques and Applications is aimed at de scribing in detail all the available techniques It is assumed that the user is familiar with Microsoft Windows and knows how to use the mouse and keyboard to access the drop down menus WHEN AN USER RECEIVES A NEW UNIT FROM THE FACTORY THE SOFTWARE AND FIRMWARE ARE INSTALLED AND UPGRADED THE INSTRUMENT IS READY TO
52. dissolution of the metal Once defined these parameters are automatically used to calculate for example the corrosion rate after a Tafel Fit or display the current as a current density It is also possible to modify the electrode surface area or characteristic mass after the experiment by selecting Edit surface and mass in the Graph Tool Bar The window below appears Edit pararneters File LP 12 mpr Parameters Electrode surface area cre Characteristic mass 0 001 g Cosmos Fig 38 Edit surface and mass window 26 EC Lab Software User s Manual Another way is to use the Modify Cell Characteristics in the Tools tab of the main tool bar see 2 2 2 1 2 5 2 1 2 Battery Cell Description frame When the Battery button is pressed additional parameters related to batteries show up Note that these parameters are automatically displayed when a battery testing setting file is loaded The corresponding window is as follows Cell Description Electodemateial OOO OOOO O nitate O tectos O Comments Electrode surface area 10 007 Characteristic mass 10 001 Battery lt lt Mass of active material 7000000 mg atx 1 000 Molecular weight of active material at 0 90 930 gral Atomic weight of intercalated ton 6940 gral Acquisition started at xo 0900 Number of e transfered per intercalated ions To for n theoretical capacity ALI 1916 936 m h Battery cap
53. dl and or charge varia tion dQ 2 onan averaged current value either on a potential step potentiodynamic mode or a time variation potentiostatic mode For techniques with current control the recording conditions are on a time variation dt po tential variation dE and or charge variation dQ Recording conditions are described in the application section for each technique If the user wants to force a periodic recording in time a large value or more simply O must be set in the recording resolution of the variable The box for which the resolution is O has the same color as the background This color code means that this box is not activated and also not taken into account for recording 2 11 4 Data saving Each channel has its own memory buffer to store data points This buffer is rather small around 700 kB The data buffer on the communication board is much larger The memory or number of bytes allocated to each channel depends on the number of used channels The buffer size decreases when the number of channels in the instrument increases The size represented by each data point depends on the technique used Fig 72 gives the minimal amount of stored data points for each buffer board Fig 81 Minimal memory size in data points of the buffer boards Data transfer between the instrument and the PC via the Ethernet line is automatically started when its buffer is 5 full Please note that the user can define the data sav
54. element Ma oocccocccocccnncccnncnnoncnnncnconcnnnnos 126 4 3 1 10 Anomalous diffusion element or Bisquert diffusion element Mg 126 4 3 1 11 GUEriSCher element anna 127 4 3 1 12 Modified Gerischer element 1 Ga ccconccccocnccnncnconcnnonnnnnoncncnnnnnnoncnnnnoos 127 4 3 1 13 Modified Gerischer element 2 Gibb ccconcccconccccnncnconcnnnnnnnnoncnnnnnnnnoncnnnnoos 128 Ares IMAN A eee eee eee ea E ee 129 ALON lt LI WING OW tes tanscees itis tees et eee tt ae arene ie to 129 AS22 Y ES o AA A etl RS aes 131 de 2 2 1 GIRCUMOCSCHOUOM iii elite 131 A PING A A eE E AET EEE 133 Ao EQUIValent cerca o 134 Ao NN yas sataticet tana A ant oeeeteaadaeenmne iuie aitieans ane aedneaecceatia 134 Ao APPUICA MIN 136 4 3 3 4 Fit on successive cycles mito iaa ci cia id 138 4 3 3 4 1 PsSeudo CapacilanCe oocccocnccocnoconccnonocncnonanconnnocnnnnnnnonnnonannonanenaninnons 139 4 33 42 Additional PIOUS usina ni dicen 140 A324 A A 142 4 3 4 1 Mott Schottky relationship and properties of semi conductors 142 EC Lab Software User s Manual 43 42 The Motl Schottky Plot conciso a datevidieaeds 142 4 3 4 3 The MotteSchotky Fltcuioas iniciando 143 4 3 4 4 Saving Fit and analysis results oooncccconncnconononoconcnnnnaronononcnnnnanonononons 145 4 3 5 Kramers Kronig transformation aaa 146 4 4 Batteries MCN asiatica 147 4 5 PHOLOVOIAIC TUE CM te ol 147 45A Photovoltaic ANALYSIS lt ae ui ae 148
55. fit file fit in the same folder as the raw data file When the data file is displayed a function Show Anal ysis Results is available on the right click menu Select this function to display the fit re sults window Analysis Results File SPEIS MHz to1H2_C Y Charactmpr mpr Mott Schotky Anales 04 137 2 15 38 parameters Temperature 5 0 C Dielectric constant 1 000 Surface rea 0 001 cr results File ZAtemporNicolas MASPEIS_7MHzto1Hz2_ CY Characi Range 6 802 10 Frequency 1 024 MHz Flatband potential A Donor denzity 04907818 cm 3 Frequency 21 922 kHz Flatband potential ar55 W Donor denzity 0 418 3e18 cm 3 Frequency 217 576 Hz Flatband potential ade WY Donor density 0 39 1618 cm 3 Pr i E Fig 201 Analysis Results window 145 EC Lab Software User s Manual This text file shows the file name and the analysis performed on the curve with the date and time at the top If several fits were made successively on the curve the user can display every analysis one after the other using the Next button The results can be printed edited to be copied or deleted 4 3 5 Kramers Kronig transformation It is possible to determine the imaginary part of the impedance from the real part and vice versa The system must be causal stable linear and invariant in time and the impedance must be finite when w gt 0 or w gt The Kramers Kronig transformation is sometimes use
56. importation from other electrochemical software EC Lab software allows the user to load every text file generated by other electrochemical software All text formats can be loaded directly from the Load data file function in the Ex periment menu If the software recognizes the data file EC Lab will be able to open it directly If not the user can import the text file with the Import from text function in the Experiment menu This can be done either automatically when it is possible the format is known by the software or manually with a definition by the user of the number of columns and of each vari able 175 EC Lab Software User s Manual In the Experiment menu select Import from text or click on the import icon to dis play the following window lee Input Text File File 18650_cyclage_260504_GCPL_1 mpt Directory C EC Lab Data S amples Size 813 866 bytes J Show Tab and Space 1 lt Tab gt 0 lt Tab gt 0 lt Tab gt 0 lt Tab gt 0 lt Tab gt 0 lt Tab gt 137618 41293 lt Tab gt 135 lt Tab 1 lt Tab gt 0 lt Tab gt 0 lt Tab gt 0 lt Tab gt 0 lt Tab gt 0 lt Tab gt 137738 41295 lt Tab gt 135 lt Tab 1 lt Tab gt 0 lt Tab gt 0 lt Tab gt 0 lt Tab gt 0 lt Tab gt 0 lt Tab gt 137858 41297 lt Tab gt 135 lt Tab 1 lt Tab gt 0 lt Tab gt 0 lt Tab gt 0 lt Tab gt 0 lt Tab gt 0 lt Tab gt 137978 41299 lt Tab gt 135 lt Tab 1 lt Tab gt 0 lt Tab gt 0 lt Tab gt 0 lt Tab gt 0 lt Tab gt 0 lt Tab gt 138098 41301 lt Ta
57. is defined as the spontaneous current fluctuations occurring between two dissimilar or identical electrodes held at the same potential These cur rent fluctuations are due to a galvanic activity between either two dissimilar electrodes or two electrodes of the same material with microstructural differences ECN is usually measured using a Zero Resistance Ammeter ZRA which connects the two working electrodes A refer ence electrode or a pseudoreference electrode of the same material as the working electrodes can be used to measure the potential fluctuations which are called Electrochemical Potential Noise EPN of the pair of electrodes To analyze these fluctuations the tool Electrochemical Noise Analysis Y was introduced This tool is used to calculate the noise resistance of the system Rn Three methods are available to calculate the electrochemical noise Standard deviation With the two standard deviation values Noise Analysis current and potential it is possible to apply the Ohm s law rela Selection Trace vs time y B O Cycle nf tionship and to obtain the parameter Rn R N with oz feat x 2s m AB 7Se 6 m 1 N 1 To point 113 F i i 1114 and so obtained with the formula O gt x x Y 0 019 42 ma N 1 726 Total points 111 where x x is the average aoo Select cycle s Ewe trend removal PSD with DFT It is also possible to calculate the standard de viation from the Power Spect
58. liability claims in the event of injury or mate rial damage are excluded when they are the result of one of the following Improper use of the device Improper installation operation or maintenance of the device Operating the device when the safety and protective de vices are defective and or inoperable Non observance of the instructions in the manual with regard to transport storage installation Unauthorised structural alterations to the device Unauthorised modifications to the system settings Inadequate monitoring of device components subject to wear Improperly executed and unauthorised repairs Unauthorised opening of the device or its components Catastrophic events due to the effect of foreign bodies ONLY QUALIFIED PERSONNEL should operate or ser vice this equipment EC Lab Software User s Manual Table of contents 1 2 equipment instalaste General describo sisenes rin alocado iia Intended use of the QUIM li i ISU UIGUONS TOUS Canaan General safety considerations oocccconcccccnnccncncconnncnnnnnnnnnnonnnnnnoncnonnnnnnonnnnnncnnnnnnoss iv La tgo o 8 071 o q AO EN E 6 EC Lab software settings ina 8 2 1 OE C EaD cs cats PIO O 8 2 2 EG Maim Melina 11 2 3 A a aganls cateneaaagatis bene asonneie 14 2oel Mad VOOM at ad 14 2392 GChanneltool Dal sena heath Nase ees ec Ae hee ea een oe beset ad 15 239 GRAD TOO BAT ri 16 23d DAIS OOD AN usara 16 2 3 0 GUuirent Va
59. loop increment every charge discharge alter nance o Compact file for PCGA to add the dQ variable o Keep only values at the end of every Eoc period or on period for GCPL o Count half cycles Select the variables you want to add and click on the Process bution This will create the processed file with the same name as the raw file but with the addition of letters corresponding to the selected new variables and the mpp extension instead of mpr 5 1 2 Additional processing options At the user s convenience the processed file can contain only a part of the native variables of the raw file In that case the processed file will not be processable again But for a later process of the processed file the Allow Reprocessing box must be ticked on This option will auto matically select all the variables of the native raw file An Export as text option has been added in this window to automatically generate a text file processed file mpt that may be used in other software Different ways exist to define cycles in the processed file in order to plot Q and energy during the charge and discharge steps The cycle for the process can be defined automatically or every loop increment or every charge discharge alternation For the battery applications specific process options Keep only values at the end of every OC period on period and Compact are available for the compacting process for more details see the descrip
60. material This mass is used in the graphic display to represent mass current density or mass charge density Circle Fit tool available with the graphic display used to fit a circular curve Compact mathematical function allowing the user to compress data points from the raw data file Compact functions are available with the GCPL and PCGA protocols All points of each potential step are replaced by their average taken at the end of the potential step The number of points of the compacted data file decreases a lot compared to the raw file Compliance correspond to the potential range of the counter electrode versus the working electrode potential This option is used in molten salt electrochemistry where the potential de creases a lot between the counter and the reference electrode 195 EC Lab Software User s Manual CE to ground connection also called N Stat connection this mode allows the user to lead measurements on eight working electrodes with one or eight reference electrodes and one counter electrode connected to the ground It is a very useful tool for biosensors study This mode can be activated in the Advanced settings window Corr Sim this tool simulates corrosion curves obtained with the linear polarization Constant Amplitude Sinusoidal microPolarization or Variable Amplitude Sinusoidal microPolarization techniques Cycle inside a protocol this term is used to describe a sequence repeated with time Cycle
61. me times Experiment Measure l gt over the last of the step duration Advanced Settings Record l gt averaged over H voltage steps Cell Characteristics E Range o Genta Aig External Devices Range Bandwidth Endscanta Ef Wows dE dt 100 py 5 ms Force El ES JEN 1 0 mi 4000 points per cycle VMP3S ah 192 109 209 236 Channel Y Read mode 0 042 9 4 78e 3 Fig 31 Cyclic Voltammetry detailed column diagram EC Lab Software User s Manual When a technique is loaded on a channel the detailed column diagram is displayed On top of the diagram the Turn to OCV option can be seen as well as the button rl available to show the graph describing the technique and ts variables cf Fig 32 Ewe code Fig 32 CV graphic description The EC Lab software protocols are made of blocks Each block is dedicated to a particular function A block in grey color means it is not active The user has to set parameters in the boxes to activate a block which becomes colored When available the recording function Record can be used with either dEr or dtr resolution or with both Data recording with dEr resolution reduces the number of experimental points without losing any relevant changes in potential If there is no potential change only points according to the dtr value are recorded If there is a steep change in potential the recording rate increases according to dEr
62. mes sage is displayed Warning Is 2000 000 mA Ns 0 The VMP3 is designed to accept a maximum continuous current of 400 m Fig 241 Warning message for the current limitation To go over 400 mA one must respect three limits that depend on the maximum continuous current duration the average current and the power supply 1 The maximum continuous current I is limited to 2 4 A for a maximum duration t of 2 ms and must respect t lt 4 8110 As 7 For example one can apply 2 4 A for only 2 ms and 1 A for 4 8 ms see below Beyond these limits a protection mode sets up in the instrument I A 2 4 Protection mode Lt lt 4 e ns ans E e 0d bates eee 1 oaa 2 one channel limit No limitation 0 2 48 t ms Fig 242 Safe operating area 2 The maximum average current lt l gt recommended during the experiment is 400 mA for one channel For example in the protocol described on the following figure two different 178 EC Lab Software User s Manual currents l and l2 are applied for two durations t and te respectively The average current on a period is defined by Lt l t je Fee Y LFG L l i 0 th t2 t Fig 243 Example of a current pulse protocol 3 The power supply has a limit of 10 A To avoid having the instrument enter the protec tion mode the user must respect the following equation Nb las 10 A 1 where
63. mode must be used when the potentiostat is connected to a grounded cell e g autoclave pipeline etc The potentiostat needs to be floating to prevent current from looping in the cell 2 5 3 4 3 Ultra Low Current Option This option is only available with the SP 300 technology when the Ultra Low Current option is connected to the channel This option is necessary when low current ability at relatively high speed is required What is considered a high speed depends on the magnitude of the meas ured current Lower is the current lower is the high speed Ticking High Speed Scan helps compensate the bias current typically 300 fA which can become not negligible anymore at low currents typically lt 1 nA In these extreme conditions measurements can appear dis torted For instance a loop can show up at the vertex Fig 52 as a result of an asynchronicity of the measured potential and measured current The value of current scan for which the correction must be applied also depends on the intrinsic characteristics of the cell type of electrode distance between electrodes The correction offered in the Advanced Settings window is automatically selected when Ultra Low Current Option is connected 36 EC Lab Software User s Manual Note that if the High Speed Scan box is ticked the data may be noisier especially for ranges below 1 nA Fig 53 It is possible to reduce the noise by numerically filtering the data after t
64. number processing function that allows the user to display on the graphic one or sev eral cycles chosen in the raw file The selected cycles are lightened and the others are hidden Cyclic voltammetry CV this protocol consists of scanning the potential of the working elec trode linearly and measuring the current resulting from oxydoreduction reactions Cyclic volt ammetry provides information on redox processes electron transfer reactions and adsorption processes Default settings settings defined and saved as default by the user and automatically opened when the corresponding protocol is selected Description tab in the experiment selection window which describes the chosen protocol Device EC Lab software window in the Config menu used to add new instrument IP ad dress to be connected to the computer EC Lab software drives the multichannel potentiostats galvanostat Electrochemical Noise Analysis this tool is dedicated to analysis corrosion data and to de termine the electrochemical noise presents on the data Electrode characteristics in the cell characteristics window in EC Lab the user can set all parameters about the electrode Electrode surface area geometric surface of the working electrode It is a value that is used to represent current density or charge density Experiment limits in the advanced settings window these limits can be used in two different ways and concern potential current and c
65. on the link in blue It must be noted that Ewe Ece and the power P are hardware variables and are directly coming from the potentiostat board If the user does not choose to record P it will nonetheless appear as a default variable but will be calculated not by the potentiostat but by the software using the and Ewe values stored in the data file by the software The hardware P is generally more accurate The variable Ewe Ece is calculated by the software Except MPG2 there is no Eee variable with MG 2XX series instruments The Record block gives also the possibility to see the properties of the data file in which the variables will be stored All boxes Acquisition started on host directory and file are filled automatically when the experiment is started Channel i running files Acquisition started on host directory 08 02 2010 192 109 209 146 CAEGC LabliSamples file 2 CV_iron_10 m s mor a Fig 42 Cell characteristics Files window 2 5 3 Advanced Settings tab The advanced settings window includes different hardware and software parameters that de pend on the type of instrument To change the values click on the Modify button enter the new settings and click on the Accept button to send the new settings to the instrument Note the Advanced Settings window is available for all the protocols 29 EC Lab Software User s Manual 2 5 3 1 Advanced Settings with VMP3 VSP SP 50 SP 150
66. per decade 7 In Logarithm spacing sim mpr Equivalent circuit Imi vs Ret 10222 Edit 2 parameter Ohmi F s a 1 Ohm Ohem s 1 2 1 050 A ai Calcuta Com Save Eto Fig 185 Z Sim Circuit Edition window Re Z 0hm 10 To adjust this curve to the experimental one the user must adjust values for each pa rameter as described in the window below and click on Calculate 132 EC Lab Software User s Manual Fx Graph Ee Z Sim Set Frequencies rt ae E i j T F AAA S T es gt xo A i aT from F 100 000 kHz e Es a El AX IES i Ba to Fs 11 000 mHz y Nyquist Impedance How 1 with i O paints per decade Ta Logarithm pacing sim mpr Im ve Reli Equivalent circuit RAT 0Q2 A 2 2 parameter walue F s a 1 Ohm Ohms 1 2 Calculate Copy Save Close Fig 186 Z Sim Circuit Edition window with adjusted parameters Reiz Ohm The results can be copied to the clipboard and saved in a ZSim mpr file The user can modify parameters which will be implemented when clicking on Calculate To store this simulation the user will have to give another name to the data file because by default any simulation results are saved in a ZSim mpr file 4 3 3 Fitting Z Fit When the correct equivalent circuit is defined with Z Sim the user can set it in the Z Fit window to identify paramete
67. possible to increase the grid precision up to 10 digits by the following operations change the Precision value click again on the Process button Note that if the processed files are already calculated this is not necessary to rebuild them respond Cancel when the program asks you to rewrite them Then the grid values will be reloaded from the existing processed files with the new precision The processed files are not deleted after the process and can be displayed in an EC Lab graph or exported one by one into ASCII format 5 1 7 Constant power protocol summary A process called Constant Power technique summary has been especially designed for Ragone plot representation It is associated with the CPW technique in battery applications To use this data process click on process in the graphic window or choose Batteries Con stant Power Protocol Summary in the Analysis menu Then the following processing window will be displayed Constant Power protocol summary Raw File C EC Lab Data Samples CPW_RAGONE mpr times PAN Enerqu W h A Qolm h Ewe intial l m initial Ewes final l r final 1185 7890 8 000 6 760 15 4 0633 1 624 7 3 001 3 2 665 8 20026217 139986 3425 7 1 007 2 3 646 1 096 6 3 001 8 1 332 3526 4195 20021 3 642 6 1 OF 3 293 5 477 93 3 001 4 667 06 4686 4659 1 0007 3 754 4 1113 6 3 171 23 45 3 002 1 333 35 5565 7811 0 497 89 3 820
68. right column The procedure for the configuration of the auxiliary inputs outputs is described below 1 Choose the channel to configure Each channel can be configured for a specific device One channel can control one device and the other one another device 2 Select the Device Type in the list between None Thermostat RDE QCM and other One or several device names are available according to the selected device type 3 Among the available devices some can be controlled with the analog output and some of them can only be used to record values with analog inputs 1 and 2 The user must tick the box to activate the input output 4 Inthe activated frame the user must define the conversion between the input voltage and the variable to plot This is a direct linear conversion in the range defined by the user between the min and the max value 5 The user can also define the name and the unit of the chosen variables Click on Cus tom Variables The figure below is displayed 186 EC Lab Software User s Manual Custom Units custom unit Absorbance U Hame U rit Absorbance AAU Fig 254 Custom Units window to define new variables To create a new variable with its unit click on Add and put the name and the unit of the new variable in the frame Then click on Y to validate The new variable appears in the list in blue as a custom variable and can now be selected as the recorded variable for the analog inputs
69. text file creation and exportation For file exportation to other software Kaleidagraph Origin Excel it is possible to create text files from mpr and mpp files Choose Experiment Export as Text in the EC Lab menu bar This will load the window below Text File Exportation C EC Lab Data Sampless CY Fe basigue 1 mpr Format Options All Files Cycles loops selection Time i EEES Same selection for all files Elapsed Time in 5 Absolute Time mm dd yy hermes sss all Impedance Units Al Fil EC Lab Text Format mpt nits All Files 1 000 Use Default Units CO User s Units m m ster mA hg Cyclic Yolkarninmetry DigiElch Format Export all files into a single txt file Number OF Digits Fig 238 Text File exportation Select one or more files with the Load and Add buttons Note that it is possible to select files from different directories Click on the Export button to export all the selected files into the selected text format The resulting text file s are created in the same folder as the original file and differs only by the mpt extension Several text formats can be created by EC Lab software depending on the importing software For time files one can display the relative time from the beginning of the experiment e g t 0 s for the first point Elapsed Time in s option default or the absolute time in year month day hours minutes and seconds for
70. the max current value determined accord ing to the baseline Height is the current value for the potential Ep always according to the baseline Width 1 2 is the peak potential width determined when it is possible at half the peak height parallel to the baseline Ep Ep is the semi width for the first side of the peak Charge Pos is the charge related to the current above the baseline and Charge Neg is the charge related to the current below the baseline The area for the calculation of this charge is defined by the position of the green markers The results can be copied in the clipboard and pasted anywhere as text They can also be saved in a text file 4 2 1 4 Results of the peak analysis using a polynomial baseline In fact it is often difficult to apply a linear regression baseline to take into account the capacitive part of a curve or remove the beginning of a second current peak A polynomial baseline could lead to a more significant fit On Fig 142 a polynomial baseline has been used to do a peak analysis The oxidation peak of a polypyrrol film is analyzed using a polynomial baseline With this baseline we can avoid taking into account the beginning part of the pyrrol monomer oxi dation The result variables are the same as for the analysis with a straight baseline lt l gt mA pyr4_1_nQd mpp lt l gt vs Ewe cycle 16 0 2 0 0 2 0 4 0 6 06 1 Ewe V Fig 151 Peak analysis on a cyclic voltammetry expe
71. tool in the Gen eral electrochemistry analysis m Summary per protocol and cycle Experiments File List cycle Jexpt Qarn m4 h Ocavm4 h f lan m min lan m mas flcalm min flca m amp max Elan end Eca end GCPL 1263492 1270018 130 000 130 000 130 000 130 000 4 295 2 3923 El CY 0 001 0 001 0 000 0 159 0 001 0 224 2 CY 0 001 0 001 0 000 0 209 0 000 0 221 3 CY 0 001 0 001 0 000 0 208 0 000 0 225 4 CY 0 000 0 000 0 000 0 188 0 001 0 088 Define cycles by auto DONE Precision 3 Fig 228 Summary per protocol window Then select the raw data files that correspond to two experiments with the Load Add Re move and Undo buttons In the example above 18650_GITT_030604 mpr mpr CV_Fe_basique_1 mpr correspond to a GCPL and a CV run with cycles in each technique Click the Process button to start the calculation This will create one processed file per raw file that contains the results in the example 18650 GITT 030604 mpr mpp CV_Fe_basique_1_cnQ mpp and displays the results in the Linked experiment window grid Notice that the linked experiment loops and the electrochemical cycles are both displayed and that the Summary per protocol and cycle window can be resized to full screen to display more values in the grid The grid can be copied to the clipboard and pasted into a spreadsheet with the Copy but ton 167 EC Lab Software User s Manual lf one requires more accuracy it is
72. window To display several graphs on the same window right click on the graphic window select Add Graph and choose the data file to display One graph is active on the window with a red frame in the left bottom corner the other graphs are not In the multigraph mode fits and analysis remain possible on the active trace of the active graph The graph properties can be modified for each graph independently 3 2 9 1 Multi windows When several windows are displayed in the EC Lab software the user can either show win dows in cascade or tile the windows on the screen Choose Windows Tile to display several graphic windows at the same time 87 EC Lab Software User s Manual DB ec Lab v0 4 ooe Experiment Edit View Graph Analysis Tools Config Windows Help BOS GU Hho oa errores Baak fy VMP3 USB channel 1 experiment aj technique Cyclic Kx Graph Devices PJHO AAR BH lt p x am gt A lA DAADA AARE 2 VMP3 USB Nyquist impedance v She 4 1 gt VSP 238 VSP 300 239 18650_linked_4_ZPOT_1 mpr Am Z vs Re Z InZ 0 hm Re Z 0hm AX Graph da 174 s gt gt 388 D0608kKk 0xX5668gr 20 ABRAR Aaka amp Ewe l vs t X gt 4 Y Show cycle 4 1 CPW_RAGONE mpr 0 2 0 Ewe vs time I vs time Y A A v Y oA 0 05 1 0 0 2 04 Ewe V vs SCE Ewe V us SCE 5 000 0 100 000 time s Ewe V vs SCE time s l itatus Stopp
73. 0 32 Graph HX Experiment Edit View Graph Analysis Tools Config Windows Help A es Me Tepe Tee UT PEW ED RA Selector le Show 1 Cv Fe_basique_1 mpr ele ve Ewe oxlred vs Ewe A Ewet us SCE tatus Stopped Time 0 9998 Ewe 0 220 m 0 000 A Buffer 0 Eoc 0 20 mi Q Qo 0 004 h P 0 000 ne D Range opel VMP3 ep USB Channeli AAA a 0 361 0 234 1 06 2 815 bs Fig 98 Graphic window As can be seen the above window Fig 98 displays a loaded Cyclic Voltammetry mpr file To select points use the selection button Select a zone by holding the left mouse button The cursor will draw a rectangle zone around the selected points Then release the mouse button The selected points will be highlighted in bold red The selected zone can be analyzed with fits or hidden from the graph before copying or fitting the graph The user can have every point coordinate with the mouse when holding the SHIFT key of the ul keyboard or clicking in the i gt box This comment box contains the point number in the ex periment and the point coordinates Origin axes can be displayed with another color on the graphic window 73 EC Lab Software User s Manual 3 1 3 Graphic tool bar When the graphic window is displayed the graphic tools bar automatically appears at the top This bar is attached to the graphic window Hei 8 4 AeS x BTR e ea E Fig 99 Graphic tool bar es This tool bar can conta
74. 00 0 0002 14 0 300 A 0 000 m 0 00 0 0100 pass 0 000833 0 00 0 0002 14 Fig 245 Table of the experiments for GSM battery testing The result is represented on the following figure 1600 600 400 200 Fig 246 GSM pulse waveform generated by chronopotentiometric protocol 180 EC Lab Software User s Manual 6 2 Optimization of the potential control resolution 6 2 1 Potential Control range span Our potentiostats galvanostats are digital instruments The potential is applied to the cell via a 16 bit DAC Digital to Analog Converter The DAC delivers a potential in the 10 V range for VMP3 VSP SP 150 and in the 10 9 V range for the SP 300 technology with a resolution equal to its LSB Least Significant Bit that corresponds to the smallest potential step available and is defined as ESB a ane 305 18 uV for VMP3 family 2 1 65535 and as LSB O EA 333 33 uV for SP 300 technology 216 _4 65535 When the user enters in EC Lab a potential value Een the value sent to the DAC is a 16 bits value corresponding to an integer number of LSB i e defined as E NLSBwith N roun Ear LSB where round is the function that returns the nearest integer of the variable Usually experiments do not require 20 V potential ranges So in EC Lab the potential control resolution can be adjusted to the required experimental potential range in order to have potential values as close as possible to th
75. 0064 ae od 00064 14 mk oa AA A AAA ee eS ee bee 6 EA EE Stopped CP Stopped Stopped Stopped Stopped GEIS Stopped GCPL 10 0500 s 5 371 0 000 A 0 0 01 14 0 493 m 0 000 A 0 0 0000 s 0 002 mv 0 000 4 0 0 0000 s 0 0000 s 0 043 m 0 158 my 0 000 A 0 000 A 0 0 9 9998 s 23 754 mv 0 000 A 0 VMP3 236 e S gt e 7 4 yi ii Show window at startup Fig 3 Global View window The global view of the channels shows the following information e On the left the instruments to which the computer is connected The active or selected instrument will appear in a different color e channel number with Z if impedance option is available on the channel If the channels are synchronized grouped or execute a stack a bipotentiostat technique they will appear in a different color A P letter is displayed near the channel number when a linear scan generator is added to a channel board for SP 300 technology A s letter is displayed in the left side of the channel column if a channel is synchronized with other channel A g letter is displayed in the left side of the channel column if a channel is grouped with other channels e an indicative BAR in white if there is no experiment running colored if the channel is running If no pstat board booster or low current board inserted in a slot the corresponding slot number is greyed out and no inf
76. 1 Ref2 Ref3 Ref for reference are used to meas ure the voltage and CA2 and CA1 CA for Current Amplifier to apply the current Electrode Connections Modify on disconnected cells only WE DAZ ref RE ter Ewe f Ens refs CECA Fig 46 Standard connection mode for VMP3 technology CE to Ground connection mode VMP3 technology It is possible to work with several WE several RE and one CE in the same bath Then counter electrodes must be connected together to the Ref1 lead and ground Disconnect the cables from the cell select Electrode connections and CE to ground and reconnect the cell as follows CA1 and Ref3 leads to the working electrode Ref2 lead to the reference electrode GROUND and Ref1 leads to the counter electrode Electrode Connections Modify on disconnected cells only CECA refs E RE fret 42 i Ece ref ground Fig 47 Configuration CE to ground N Stat for VMP3 technology 2 5 3 1 4 Miscellaneous Text export This option allows the user to export data automatically in text format during the experiment on line exportation A new file is created with the same name as the raw data file but with an mpt extension Filter 32 EC Lab Software User s Manual This option allows the user to filter by the mean of the software the data just after the run by ticking this box before running the experiment A new file is created with the same name
77. 50 or 60 Hz frequency signal coming from the electrical grid The Filter tool available in EC Lab software allows the user to remove this additional undesirable signal Several filtering methods can be chosen e Moving average method the window size must be de fined e Savitzky Golay method it is based on a polynomial cal culation in a defined window The window size and the polynomial order must be defined e Low high pass or band pass reject methods These methods are based on Fourier Transform The window Rectangle Barlett Hann Hamming Blackman Welch and the cutoff frequency ies must be defined please refer to the Fourier transform part above for more de tails 102 Filter Selection Trace Ente ve time From point O mi Os Y 0 609 8 To point 150164 ie 1 556 Y 0 613 5 W Total points 150165 Parameters Method Band reject Freg min 1 627 Hz Freg max 0 271 2 Hz Window Rectangle frequency band 50 000 Hz mir 60 000 Hz max Progression Method Founer Transhorm Calculate Stop Close Fig 142 Fourier Transform window EC Lab Software User s Manual The results can be copied in the clipboard and pasted anywhere as text They can also be saved in a text file lt l gt vs time cv noise _cycle6 filter mpp cv noise_cycle6 mpr 0 94 TTA 0 92 98 98 5 time s Fig 143 Filter re
78. 6 Cannot retrieve channel E data 1217413102070 YMPS 236 The channel will be locked and you will have to go into Tools Repair Channel to T unlock it Show window on emor Fig 69 Warning message stating the lock of a channel As stated in the error message the user should go to tools menus and click on repair chan nel tool The user has to check the following points The controlling computer and the instrument have to be maintained connected by the same way USB or Ethernet Before opening the repair channel window the user has to select the blocked win dow Incase of synchronized or grouped channels the repair channel is applied on all synchronized grouped channels when the procedure is done on one channel The user can realize easily that the level of the buffer located in the status bar is full In case of a multichannel system the memory of the communication board is shared between all the channels Before unlocking the channel the user has to retrieve the data stored in the communication board buffer Fig 71 48 EC Lab Software User s Manual EC Lab V10 36 VMP3 192 109 209 236 channel 8 experiment GCPL technique Galvanostatic Cycling with Potential Limitation Experiment Edit view Graph Analysis Tools Config Windows Help as ds ah a al aia 9 a0 di 12 13 14 15 J6 Devices Tum to OCY between techniques s l z da a Q a Q YE Es ie a s0e oE Ewe vs t v
79. 7 Lod YSP 300 239 Fig 24 Multi device connection box lf more details are needed about the connection of the instrument please refer to the corre sponding Installation and configuration manual 17 EC Lab Software User s Manual 2 5 Experiments box By default the highlighted tab in the Experiments box is the Parameters Settings tab Four tabs allow the user to switch between three settings associated to the protocol the Advanced Settings the Cell Characteristics External Device and the Parameters Settings 2 5 1 Parameters Settings Tab When no technique or application is loaded in the Experiments box a small text is displayed indicating how to proceed No experiment loaded on current channel To create an experiment please selects one of the following actions New Load Settings New Stack if connected to a multichannel Load Stack Settings if connected to a multichannel m The column will contain the techniques of a linked experiment The settings of each technique will be available by clicking on the icon of the technique The Turn to OCV between techniques option offers the possibility to add an OCV period between linked techniques This OCV period allows the instrument to change its current ranging Tum to OC Y between techniques 7 Fig 25 Top row in the Parameters Settings window The button is available to show the graph describing the technique an
80. 9 11355 3 097 6 88 968 3 001 4 165 88 6457 3199 0 250 27 3 862 8 11494 3 056 1 18 914 3 001 7 03 376 77146683 0 124 41 3 993 7 1 159 6 3 036 7 17 24 3 002 2 41 44 DONE Process Copy Close Fig 229 CPW process window This process window is made of a table containing the characteristic variables of each power step such as the time the energy and charge of the end of the step the working electrode potential and the current that crossed the cell at the beginning and the end of the step The Copy tab allows the user to paste the values of the table in graphic software in order to have a Ragone plot see figure below 168 EC Lab Software User s Manual Power W 3 Energy W h Fig 230 Ragone plot for a Li ion cell 1 35 A h 5 1 8 Coulombic Efficiency Determination Fit CED Fit CED Fit tool is used to fit the coulombic efficiency vs cycle number curve by a 2 order poly nomial function The polynomial function coefficients ao ai a2 are determined The difference between the experimental curve and the modelled curve RMSE is also determined CED fit Selection Trace Fromm point a i To point a ie Total points A A A A A A A A Number of hidden points 4 1 b For unselected points only Results z y x a 0 x a x Tn BEEN Gy BEEK ay An RAMS Error sxx Calculate Lopy Save Fig 231 CED Fit Window 169 Efficiency
81. A 83 32 GODY ODUONS carril dida 85 32 7 1 Standard CODY OPUONS vena 85 9 2 7 2 Advanced Copy ODUONS misstiiica dd 85 3210 ai PIMP ODUONS S rias aaa 85 3 2 9 Multi graphs in a WINKOW cccceccceeeceeeceeeseeesaeeeeeeeeeeseeeteetseeseeeeseeteeeseeeseeees 87 S294 MUL WINGOWS aai ersatn iana E te cesta dice E eset csutten casio teenie nett daca 87 3 2 10 Graph Representation MENU cccccsecccseccececseecceecceusecseessusecsusesseessueenaess 88 3 2 10 1 AXIS PPOCESSINO sesgos 89 3 2 10 2 How to create your own graph representation for a specific technique 90 32 109 Howtocreatea Graph SWE 2 ss iii a ile ale alaba 91 ANAIS SO O OO o Ocio 94 EC Lab Software User s Manual 4 1 Mat DOV TN agate ae ee o ateo 94 4 1 1 Min and Max determination coocccccncccncccncccnccononononononononanonanonanonanonanenanenanenanes 95 Ad A 96 Aiko UUW LO MMA ers We iieiea a E E AE acoiaa soundly 97 A Mt 97 Ao ElmearImerpola ON ia 98 AO a A O IN A eT 99 Al A e O RO RO bina een tot obo ean on tot on annem cae 100 4 18 Fourier Transiorm x22 cerenetenenargennisaendunnsand Aaa 101 o E E eee er et er et ee eee meee Pon eee et 102 4 1 10 Multi Exponential SIM Pla do 103 4 2 General Electrochemistry Menu ccccccecccceeeeceeceeseeeeceeeeeseeeeseesesseeeeseeessaees 104 Aa Rear AMAL SIS cuina via iva abla bla 104 4 2 1 1 Baseline Selecionar dia ia 105 dele Peak analysis TOS Sia de dci 106 4 2 1 3 Results of the p
82. B P Flannery Numerical Recipes in C The Art of the Scientific Computing Cambridge University Press Cambridge UK 2 Edition 1992 E Walter and L Pronzato Identification of Parametric Models from experimental data Springer 2006 J P Diard B Le Gorrec C Montella Cin tique lectrochimique Hermann 1996 E Barsoukov and J Ross Macdonald Impedance Spectroscopy Theory Experiment and applications Wiley interscience 2 Edition 2005 4 3 3 4 1 Pseudo capacitance ZFit calculates the pseudo capacitance associated with a CPE This value can be calculated only for an equivalent circuit R1 R Q This calculation corresponds to the determination of a capacitance value C at a frequency fo corresponding to the maximum imaginary part on the Nyquist circle obtained by fitting with the equivalent circuit R1 R Q This value is the solution of the following equation 1 1 2rr RQ 2nRC With a and Q the CPE parameters Considering the previous example from the first frequency down to 20 Hz the equivalent circuit could be R1 R2 Q2 Imi Z vs Re Z SPOT Fe basique 1 mpr POT Fe basique 1 zfitmpp BO a0 100 120 Re Z Ohm Fig 192 Fit results with an R1 R2 Q2 circuit 139 EC Lab Software User s Manual Fit AE s Results Equivalent circuit Al 2A2 Ohm 0 4227 29 47e6 F s a 1 5 A0be 6 0 820 4 0 549 80 9 Ohm 2 124 Pseudocapacitance Equivalent circuit Al
83. BE USED IT DOES NOT NEED TO BE UP GRADED WE ADVISE THE USERS TO READ AT LEAST THE SECOND AND THIRD CHAPTERS BEFORE STARTING AN EXPERIMENT 2 1 EC Lab Software User s Manual EC Lab software settings At this point the installation manual of your instrument has been carefully read and the user knows how to connect his her instrument to the potentiostat The several steps of the connection will not be described in this manual but in the installation manual of the instrument Starting EC Lab Double click on the EC Lab icon on the desktop EC Lab opens and connects to an instru ment See the Instrument s Manuals for more details about the instruments connection Once an instrument is connected to EC Lab the main window will be displayed le Lo g EC Lab V10 38 VMP3 channel 1 no experiment c mco Experiment Edit View Graph Analysis Tools Config Windows Help 8 DACE a a a y AN PN ET E E S E E 1 ee E ES Daes a Prnaagle v Bo gt ennas 3 7 i fit No device selected Selector y Show 41 b Before starting an experiment please connect a device Newsletter a Add Device a Virtual Mode Your Feedback on EC Lab software Experiment Advanced Settings Cell Characteristics External Devices improvement process to devel the most user friendly and powerful systems Please fill the quick survey less than 2 minutes to provide us with
84. CA2 are not used Most of the techniques and applica tions can be used and linked in Stack mode When the user clicks on the OK button the Techniques selection window is automatically displayed The user can create the experiment with one or more techniques Fig 78 shows an example of an impedance measurement performed on a stack of batteries The technique used was PEIS for more information please refer to the Techniques and Ap plications Manual In this example the master channel controls the potential of a stack of 10 elements and measures the current flowing through the whole stack The impedance of the whole stack is shown in the bottom part of the graph and the impedance graphs of each ele ment in the top part of the graph Only 6 channels are necessary one for the master channel and 5 for the slave channels Fig 79 shows an example of a GCPL measurement for more information please refer to the Techniques and Applications Manual performed on a stack of four elements 93 EC Lab Software User s Manual EsJLo Jasa peis 5 with R mpr Im Z1 vs Re Z1 Im Z2 vs Re Z2 Im Z3 vs Re Z3 Im Z4 vs Re Z4 Im Z5 vs Re Z5 Im Z6 vs Re Z6 Im Z7 vs Re Z7 Im Z3 vs Re Z8 Im Z9 vs Re Z9 Im Z10 vs Re Z10 DS r z E Ss N T Re Z10 Ohm peis 5 with R mpr Im Zstack vs Re Zstack Im Zstack 0 hm
85. Cancel Fig 28 Techniques selection window The techniques available with EC Lab software are divided in two different sections Electro chemical Techniques and Electrochemical Applications Electrochemical Techniques folder includes voltamperometric techniques electrochemical im pedance spectroscopy pulsed techniques a tool to build complex experiments manual con trol ohmic drop determination techniques and also Bipotentiostat techniques for multichannel instruments Electrochemical Applications folder includes battery testing supercapacitor pho tovoltaic fuel cell testing corrosion measurements custom applications and special applica tions At the bottom of this window different options can be selected when a protocol is loaded In the case of linked techniques the user can insert the technique either before or after the tech nique already loaded in the Experiments Box This option will be described in detail in the Linked Techniques section part 2 7 The technique can be loaded with or without the Cell Characteristics and the Advanced Settings of the default setting file The experiment can be saved as a custom application see Custom Applications section in the Techniques and Applications manual For example choose the cyclic voltammetry technique and click OK or double click On the right frame a picture and description is available for each protocol 20 EC Lab Software User s Manual Cycle v
86. E RRDE or RADIOMETER CTV101 electrodes rotator For these devices the calibration param eters are factory set Other external systems can be used but are not available They will be added to the list upon request Note that calibration parameters for an already selected device are not available Nevertheless if you select another device it is possible in the Analog OUT window to define the control parameters Click on the Apply button to validate the settings Note that this menu can be activated without any rotating electrode unit but will only have effects for the electrochemical instruments equipped with a rotating system In order to use two potentiostat galvanostat channels and some rotating ring disk electrode with two working electrodes it would be useful for the user to synchronize both channels together in order to start the experiment on both channels at the same time Report to the corresponding part in the manual for more information about the synchronize option 190 EC Lab Software User s Manual aes HEF3 and CA1 AEFI and Ground REF2 IS electrochemical cell Focus on the rear panel Analog Out Trigger Out 6 4 3 Temperature control Temperature control is possible with the auxiliary inputs outputs of our potentiostats with a voltage control Several thermostats have already been configured such as Julabo series and Haake Phoenix series Device Type Device Hame Haake Phoenix series w Analog O
87. EC Lab Software User s Manual Version 10 38 August 2014 V BioLogic Science Instruments Equipment installation WARNING The instrument is safety ground to the Earth through the protective con ductor of the AC power cable Use only the power cord supplied with the instrument and designed for the good current rating 10 Amax and be sure to connect it to a power source provided with protective earth contact Any interruption of the protective earth grounding conductor outside the instrument could result in personal injury Please consult the installation manual for details on the installation of the instrument General description The equipment described in this manual has been designed in accordance with EN61010 and EN61326 and has been supplied in a safe condition The equipment is intended for electrical measurements only It should be used for no other purpose Intended use of the equipment This equipment is an electrical laboratory equipment intended for professional and intended to be used in laboratories commercial and light industrial environments Instrumentation and ac cessories shall not be connected to humans Instructions for use To avoid injury to an operator the safety precautions given below and throughout the manual must be strictly adhered to whenever the equipment is operated Only advanced user can use the instrument Bio Logic SAS accepts no responsibility for accidents or damage result
88. EC Lab Software User s Manual The columbic efficiency vs cycle number plot is fitted with a second order polynomial function where the formula is shown on the Fig 231 The CED Fit windows is made of three blocks selection number of hidden points and results block The selection block displays the selected point s coordinates and the total points The user can hide a number of points Usually the first charge discharge cycle is bad For battery caracher ization at least the first fourth points should be hided for CED Fit The Fig 231 below shows CEF Fit results obtained with one hided point 18650_cyclage_GCPL_i mpr Ewe ws time CED fit Selection 42 oe 4 Ft fa N Fh Trace Efficiency we cycle number 7 4 F fF amp F t FA J From point 1729 T i 4 k j k k3 F A 5 nie 39 85 2 J d To point 6901 i E a E e 99 94 3 4 Total points Y 42 Humber of hidden points For unselected 3 h points orly 0 100 000 200 000 300 000 time s Results S 4 Y x a t a xt a x Efficiency vs cycle number 0 al d 0 0137 43 2 249e 3 AMS Error 229 67 ppm Calculate Copy Save 0 1 2 3 4 5 6 T cycle number Fig 232 CED Fit Window After clicking on the calculate button an mpp file is created The mpp file corresponds to the curve coulombic efficiency vs cycle number green plot shown in the Fig 232 The results block contains the results of the fit of the coulombic eff
89. Nb is the number of channels used simultaneously in the experiment and linst Is the current measured for each of those channels For example the number of channels used simultaneously in a 2 4 A current pulse protocol is limited to 4 It can increase to five if the maximum current is 2 A for the instruments sold after April 2004 For the others the limit is 250 mA for the instruments sold after April 2004 For the others the limit is 2 4 10 A s Note that the same principle is applied on all the Range values except the 1 A range of SP 200 SP 240 SP 300 VSP 300 and VMP 300 6 1 2 Application to the GSM battery testing A specific current pulse profile is used for GSM battery testing The GSM pulse protocol see next figure consists of applying a current pulse l between 1 and 2 A for a short time t lt 1 ms followed by a step to a lower current l2 for a longer period tz I h Fig 244 Theoretical GSM pulse waveform 179 EC Lab Software User s Manual This theoretical pulse waveform can be easily programmed into EC Lab with the chronopo tentiometric protocol The sequences are presented in the table below e Ns 0 OCV e Ns 1 apply 1 4 A for 1 ms e Ns 2 apply 0 3 A for 10 ms The sequence is repeated few times The period is 11 ms and lt I gt never exceed 400 mA dE mi 0 000 m 0 000 m 0 00 0 0000 pass 0 000000 0 00 0 0000 14 1 400 A 0 000 m 0 00 0 0010 pass 0 000389 0
90. Ring Chronoamperometry Run on channel 2 SW 13947 Bipotentiostat channels 1l 2 User CE vs WE compliance from 10 to 10 Y Automatically adjustable compliance Electrode connection CE to ground Ewe ctrl range min 0 00 Y max 10 00 Y Acquisition started on le e24 20le 12 56 34 saved on File bip CO0 lt mpr Directory C Documents and Settings aymeric pellissiertDesEtop Host 192 109 209 146 Device YMPS 5N 06660666 4 Disk Channel Ring Channel Fig 115 Experiment history window for a bipotentiostat technique ring channel 84 EC Lab Software User s Manual 3 2 Copy options On the graphic display several copy options are available When the user right click on the mouse the following copy options can be found in the Copy menu options size as Bitmap a as JPEG Colors Default Fer as Metafile id Copy Graph Alt G as PCX as PRs 4 Copy Data A lt D as PostScript as SVG Preview Copy Graph Advanced amp Copy EIT Data Condecon Fig 116 Copy option and copy graph advanced menu 3 2 7 1 Standard copy options On the top of the copy options menu two standard options allow to copy either the graph or the data The Copy Graph option will copy the graph to the clipboard as displayed on the com puter screen in an enhanced metafile format emf The user can paste the file in The Copy Data option will copy the d
91. Sequences within a technique If the user wants to perform an experiment composed of the same technique but with different parameters the sequences can be used These sequences are accessible in two different ways depending on the type of diagram used Column Mode Below the Turn to OCV line and buttons can be seen Fig 34 2 Tum to OC between technigues 1 do 1H Apply ly 150 000 m vs lt Mone gt forts 0 h o mn 100000 imita E we gt EM pass y AG gt AQm 138 889 n h A is Fig 34 The and buttons to add sequences m Clicking on the button will add a sequence with the same parameters as the previous se quence Clicking on the sequence will remove the sequence Up to 99 sequences can be added Note that only one data file will be created and that you can only add sequences of the same technique Flow Chart Mode 24 EC Lab Software User s Manual In the flow diagram mode a table appears automatically One row of the table is a sequence of the experiment The experiment parameters can be reached and modified in the table cells as well as in the flow diagram of the parameter settings window O 0 00 2 0000 0 0 0 00 1 0000 0 350 Mone gt 00 1 0 0000 0 000 1 0 01 0 0000 0 0 0 00 0 1000 0 300 None gt 0 01 0 0000 0 000 0 7000 0 300 None gt 0 01 0 0000 0 000 Fig 35 EC Lab table shown in Flow Chart mode During
92. UT Convert 400 I 0 00 o 10 0 Analog IM 1 100 E 400 F Analog IM 2 comen EV with 0 lo mas o Y D min Fig 258 Haake Phoenix series thermostat control configuration with a VMP3 191 EC Lab Software User s Manual The user can configure other thermostats to only record temperatures Analog in or both con trol Analog Out and record Analog In temperature 6 4 4 Electrochemical Quartz Crystal Microbalance coupling The SEIKO EG amp G QCM 922 quartz crystal microbalance has been coupled with our potenti ostat galvanostat to record both the frequency variation and the resistance variation The con figuration for the EQCM coupling is described in the figure below Device Type Device Name SEIKO EG amp G QCM922 v Analog OUT E E E E 0 0 Analog IN 1 i 0 1200 Ma 200 Af range 200 Hz yt Analog IN 2 AR range Fig 259 SEIKO EG amp G QCM 922 configuration window One can see that both frequency and resistance variations are recorded on the potentiostat Analog inputs The user must define both the frequency range and the resistance range The results of this experiment are displayed below Fig 260 192 EC Lab Software User s Manual 20004 4 000 H 6 000 Frequency Hz 5 000 H SWU aJU y 10 000 12 000 H time s Fig 260 Frequency and resistance variations recorded from the analog inputs for a VMP3 coupled with a SEIKO EG amp G QCM 922 A process is also
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94. a aoe be a eater yttaadee ee 163 BA cant eer emt re eet cme een em eee een cme een em A 77 EXOOKE dS TC acess aaa aaa acts 163 NS cette de tae A ete ts cee 175 LOODS APPO ee A 17 MaS Sinn icda 194 A i O 162 Polarization estaa 172 AO on E seeds cadens nee OS 163 FAC DFOCCS SING cuina did 163 Summary POP CV CIS incre oros 168 o eat age ise eich sia aa tas asa ase tas ge tah aie goat 58 Process A E E A ere N AEN ere NEEE oe er ce AATE Ee eR ee ee Cee ee ee ann eee 77 Process File DENVAIVE GUNE is AAA S A E A E A 164 OMT ii ii ii ii 193 Record ANACO IA a a ne eae ena 30 Eos A A E E EA O S O E 23 60 O E E E E E ean eee aces 30 ad OA 2 PCI O ET Onn et a a et eee 30 RETSr nce Elecro Vencida A eee 29 AO tana ele CU OCS Ste eat et ac aot ae ee a 188 190 SAIS is 32 A a o nn eee ee ee 23 e 75 Addi PP OA 76 CC OA OO EE ith tas nts oath asta anaes tag aa ia O PE ts tases het ara al 76 LO AC ieieni ardent eadncuntondan nuadwcint T 76 FER STO VS esas ach ea A A hah cla aut cide 76 Do nn A e PC Ts eer eR A TTT enn RP e NNT To Pen 76 oe APA onto acareeeaatondrecesaeacw E e 24 Settings POPU MENU msi a 18 A aden seasaanatbaadeg cua aeaateaadensceancensteaedeesceaceen tenance ranteaseesteasee 34 aie els Sz cols ee ere nen eee ae eee reece ee nee are etre ne eee ee eee eae ee eee a eee ee eee 151 Tool Bars 204 EC Lab Software User s Manual Channel Selecione eee 15 COnNgUra oR asi 15 67 C ren Valss at 16 Fast GrapaDISPla
95. acity C 0 000 Fig 39 Cell description window for a battery experiment or when the battery button is pressed In addition to the parameters described above this window allows the user to enter the physi cal characteristics corresponding to the intercalation material This makes on line monitoring of the redox processes possible in terms of normalized units Let us review all the parameters The mass of active material in the cell has to be set with a given insertion coefficient xmass in the compound of interest for example xmass 1 for LiCoOz These two parameters mass and xmass are actually related to the battery itself This mass is dif ferent from the characteristic mass lt is only used to calculate the insertion rate x and not the massic variables I Q P C Energy unit of mass The molecular weight of the active material is the molecular weight of the active mate rial substracted by the atomic weight of the intercalated ion The atomic weight of the intercalated ion is set in a separate box For example for LiCoOz the molecular weight 2 EC Lab Software User s Manual of CoO is 90 93 g mol and the atomic weight of the intercalated Lithium Li is 6 94 g mol e The initial insertion rate xo e neis the number of electrons transferred per mole of intercalated ion An intermediate variable X is calculated using the following formula molecular weight xmass X atomic weight ne X mass X 0 001 x F Xp
96. ailable with our multichannel potentiostat with VMP3 technology i e VMP3 VSP and even Bi Stat In EC Lab a stack is composed of several cells batteries fuel cells photovoltaic cells connected in series The current of the full stack and the current flow ing through each element of the stack are the same The voltage of the whole stack is the sum of the voltage of each element The master channel controls the current flowing through the whole stack and the slave channels are used to measure the voltage of each element De pending of the potential difference between the beginning and the end of the stack and the current needed it might be necessary to couple a current booster or a load box to the master channel Using our accessory SAM 50 which is a voltage sense adapter from 10 V to 50 V in addition with a 50 V load box CLB 2000 the user can easily study stacks of fuel cells up to 50 V Please refer to the Technical Note 27 for more details about SAM 50 There are two ways to access the stack mode 1 When launching the EC Lab software if a multichannel system is detected the open ing window will propose to create a New Stack experiment or to Load Stack Set tings Mo experment loaded on current channel To create an esperment please select one of the following actions a Hew a Load Settings wm New Stack wm Load Stack Settings Fig 75 Experiment selection 92 EC Lab Software User s Manual 2
97. all channels of WMP virtual device Select all channels of all devices Start grouped channels at averaged potential Fig 73 Group Synchronize Stack Bipotentiostat window Channels belonging to the same group or being synchronized appear with the same colour To know if the channels are grouped or synchronized the user can show the global view Global View IZ I EA user status Reduction tech GEIS cable straight standard standard standard amplifier B 2430 time 0 03 24 3 339 Y WMP 300 239 Ewe Ece 122 9 user MS status Reduction tech MONA amplifier y N wo N ok N a zZ g 62 AZ 9 Zz g 102 12 N wo pan a vv _ n Stopped Stopped Oxidation Oxidation Stopped Stopped CP CP GEIS GEIS ocy Stopped ocy 0 05 15 0 0522 s 0 10 17 0 10 17 0 0000 s 0 01 15 3 309 13 563 3 545 Y 10 527 m 0 224 mv 0 022 mi 0 000 4 0 000 4 0 091 m 0 000 4 0 000 4 0 0 0 0 0 0 07 20 0 024 Y 0 000 4 0 0 000 4 0 127 mv 2 048 mv 0 135 mv 0 0 101 mv 1 647 mv 3 310 13 561 Y 3 545 Y 10 390 m 0 325 mv 1 669 mi control ROJOOSinAN 0 022 Y 1 955 mv Show window at startup Fig 74 Global view to show the grouped and synchronized channels HOE Hil HET M HN BRL HEAT Ai Grouped channels are marked with a g in the channels global view window and synchronized channels are marked with an s The active channel has an highlighted g
98. ance of the CPE decreases when the frequency increases 123 EC Lab Software User s Manual 4 3 1 6 Warburg element for semi infinite diffusion W The Warburg element can be used to simulate a semi infinite linear diffusion that is unrestricted diffusion to a large planar electrode Description Warburg Wy Impedance Zif e 4 Za Nyquist Diagram rn 2 vs Reli Fig 174 Warburg diffusion element description The Warburg impedance is an example of a constant phase element for which the phase angle is constant Tr 4 and independent of frequency The Warburg is unique because absolute val ues of the real and imaginary components are equal at all frequencies 4 3 1 7 Warburg element for convective diffusion Wa The Warburg element for a convective diffusion is an approximation mainly used in case of diffusion on a Rotating Disk Electrode in a finite length The mass transport is supposed to happen only by diffusion in the Nernst diffusion layer and the solution is considered homoge neous outside this layer The impedance when a species diffuses through the Nernst Diffusion Layer is described by Wa 124 EC Lab Software User s Manual Description Diffusion convection Impedance lr 20 Ty lem ZII Fay Muquist Diagram Imi vs Reli Fig 175 Warburg element for convective diffusion The Warburg element for convective diffusion is equivalent to the Warburg element in the high
99. arizes several parameters of the experiment Click on Yes to accept the settings and start the experiment The settings can be set as default settings for the current technique Right click on the mouse and select Set settings as Default The parameter set tings can be saved as an mps file in Experiment save as or right click on Save Experi lel 2 6 2 Running an experiment gt ment or click on Click on the Run button A filename selection window will appear 40 2 EC Lab Software User s Manual Save Data File As G a gt v10 20 Data gt Rechercher dans Data p Organiser v Nouveau dossier izom 2 Nom i Modifi le T Bibliothe a EN ee Ji Samples 15 03 2012 12 04 C Documents y 2 CorrSim mpr 23 12 10 27 E Im A M a CorrSim_filter mpp 23 03 2012 10 29 E 4 5 A 2 CVsim mp 16 50 E Zsim mp 2 11 05 E E Ordinateur amp os c G bio logic bio logic loc Z hi R seau Nom du fichier 1_C05 mpr gt Type EC Lab data files MPR MPP MPT x a Cacher les dossiers Enregistrer Annuler Fig 60 Filename selection window The default folder to save the data is called Data The user can choose and create another folder to save his data files Type the filename Note the filenames can be forced to end with the channel number using the Config Op tion General This option is always fixed for grouped channels Clicking Sav
100. arker Options S Draw only lines over M Undersample traces over 25000 points graphic windows Scroll graph over 20000 pointa Hide OLY Points 10000 points Mote common The Traces window al lows the user to define all the properties of the se lected traces Select the trace you wish to modify in the Traces Name frame The available trace prop erties are the plot style Line Line Markers Markers z the line properties solid dash color and size E Blue 2g the marker properties rectangle circle color and size An undersampling option is available when the re sults are plotted as lines parameters for all Lemoa Fig 108 Traces window In the Options frame it is possible to choose to hide OCV points or to draw only lines over a number of points or to undersample traces over a number of points Note that the two last possibilities should be the same for all the traces Note When several traces are plotted on the same graph the user can change the active trace with a left click on the desired trace It is also poraa to select between four predefined graph styles Line style only blue solid line Line Markers style blue line circle markers XY prop style blue line circle markers and proportionality between X and Y axes Monochromatic black line The other curves in this style will be in black with dash or dot lines This style is specially dedicated to sc
101. art or stop the run Units graphic function used to modify the axis units 199 200 EC Lab Software User s Manual VASP Fit tool available with the graphic display used to fit a curve obtained with the Variable Amplitude Sinusoidal microPolarization technique This tool is used to determine the current corrosion and the coefficients of corrosion Wave analysis graphic tool used on curves obtained in a convective regime and returning the limit current and the half wave potential ZsimpWin software delivered by PAR and used to fit impedance curves with electrical circuits EC Lab Software User s Manual Index Accepi Modity SCTINGS airis 19 41 48 ANA o E 30 ll AA tica a S 24 BAGA aei 56 Ba tery Characteristic Soie iia eh A 28 BISGUEFL DINUSION Elmer 127 GelSharactenstes cti 25 26 EhnaracteriStic Masacran 27 83 Colors COnng uta ON eiii id cido tic 65 SONI OC So ea 21 CO a ds in alae ida ls alado duda Daa 78 79 A E A A etn ence tents 31 37 O eter een ene se een See ee ee eee S 72 86 LE A eh PAN UU o ucts ek eee cnt ocat eo tite O eee ee eae 78 86 EIT Data GONG SCO e os eo e e etl oi 86 E A A em rer oe 86 co no o 86 A o tae eee ree Peer 86 Corrosion CASP Fl aio beelta cee gtaeetisen 157 Elecir cn mical NOISE ANAIS Sid ais 159 Noise Resistance e a a a a 159 RolariZatlon mesitas li 154 A onsite E AA E AE TE E 154 Stern or Wagner Traud Equation ccccccsscccsseecceseeceuseceeeeecese
102. ata selected on the graph if data points are selected or data as they are displayed on the screen in a text format in two columns with X and Y only Data can directly be pasted in spreadsheet software 3 2 2 Advanced copy options Three advanced copy options are also available The Copy Graph Advanced option offers eight different file formats for the graph copied enhanced metafile Bitmap SVG Post Script PCX GIF PNG and JPG with a possibility to choose the size of the picture in pixels The Copy Z Data ZSimpWin option is a gateway to ZSimpWin software This copy option is only available with impedance data files Three data rows frequency Re Z and Im Z are copied in the ZSimpWin format and can be pasted by the user in this software If the impedance experiment is repeated several times only the displayed cycle is copied The Copy EIT Data Condecon option is a gateway to Condecon software This copy option is available only with data files including potential current and time Three data rows are copied to the clipboard in the following order E I and t this option only copies the data points corresponding to the displayed points on the graph 3 2 8 Print options Print displays the print window The user can print only the graph The log file and some com ments added by the user in the comments tab can also be printed on the same paper page The printer setup is also available with the setup b
103. ation Tafel Graph On a linear polarization trace select the Tafel Fit with the Tafel Fit button X or the mouse right click and the data points for which the fit will be performed A warning message pops up to switch to the log I versus Ewe graph representation in case it was not the selected repre sentation Cannot perform tafel fit with the representation selected Switch the representation to log l ws Ewe Fig 208 Tafel Fit warning message to switch the graph representation Answer Yes to the previous message The Tafel Fit analysis window appears The fit can be minimized with a Simplex method The results can be copied to the clipboard to be pasted in the print window comment zone or a text file They can also be saved in a text file Note One can manually select the log I versus E representation In Graph Proper ties Axis Axis Processing select log 1 for Y1 The equivalent weight the density and the surface area used for the corrosion rate calculation can be defined before the beginning of the experiment in the Cell Charac teristics window see part 2 5 2 150 EC Lab Software User s Manual Tafel Fit Stop Minimize On 11 e 20 relative error 11000 iterations Default Results Trace log xl ve Ewe wf Ecorr 203 080 ri RE corr 16 538 p 4 a 182 4 ry E e 498 6 ri 2 X 5 081 48 KIN 0 079 848 3 Equivalent weight 0 000 gen Density 0 000 g
104. atus Bar or warning Messages EC Lab Software User s Manual Graph Analysis Tools Config Tools Config Windows Help Plot af Mouse Mode XE Autoscale Representations Hide OCV Points Hide Selected Points Show All Points i Load Files Alt O E Add Files A Remove Trace Alt R LOG History EF Edit Surface and Mass Load Settings On Channel po Active Trace TA Add Graph H Remove Graph This menu includes all the Graph tools zoom in and out points selection auto scale and Graph Properties and the graph representation menu This menu also al lows the user to load or add new files to the graph This menu is equivalent to the Right Click menu on the Graph window Alt P Graph Properties Fig 9 Graph Menu Yo Math a General Electrochemistry Electrochemical Impedance Spectroscopy d Batteries Photovoltaic Fuel Cells Supercapacitor Corrosion Show Analysis Results Fig 10 Analysis Menu The Analysis menu contains various Analysis tools sorted Math General EIS Bat Photovoltaic Fuel Cells supercapacitors and Corrosion More details will be by themes Electrochemistry teries given in Chapter 4 a Tools Config Windows Help Modify Cell Characteristics 6 Extract Cycles Loops Split file oe Under Sampling Channels Calibration gt Firmware Upgrade Downgrade Retrieve Data From The Instrument
105. authorized only if the present User Name corresponds to the owner of that channel even from another computer If another user wants to modify parameters on a channel that belongs to My Name the following message appears Warning channel X belongs to My Name By accepting modification you will replace current owner Do you want to continue The command User in the Config menu allows you to change the User Name at any time You can also double click on the User section in the bottom of the EC Lab software window to change the User Name The user can specify a personal configuration color display tool bar buttons and position default settings which is linked to the User Name If it is not selected the default configuration is used For the user s convenience it is also possible to hide this window when EC Lab soft ware is starting Once your instruments are connected you can have all the details about the experiments that are run and on which channels of which instruments they are run by accessing the Global View There are several ways to access the Global View window 1 It automatically appears once the User Name is set the first time EC Lab is opened 2 In the Devices box click on E 3 Press Ctrl W 4 Go to View Global View EC Lab Software User s Manual Global View IZ 5 IZ 102 oo Reduction an N Ta m i E 5 OO EL A A ae are 11 12 13 NE Reduction GCP 0 06 13 3307 0
106. ay not be properly applied Note with CE to ground connection CE vs WE compliance is set to 12 V The CE to ground option is not available with the ZRA protocol Zero Resistance Ammeter 48 V control mode This connexion mode is available with the SP 300 VSP 300 VMP 300 when a 1 A 48 V booster connected to the standard channel board Electrode Connections Disconnect the cables from the cell select Electrode Modify on disconnected cells only connections 48 V control and reconnect the cell as ome P2 and S3 lead to the working electrode P2 S2 leads to the reference electrode 33 P1 and S1 lead to the counter electrode 52 51 F1 Fig 56 48 V control mode for SP 300 technology Refer to the Installation and configuration manual of your instrument for more details on the 48 V control connection mode 30 V control mode This connexion mode is available with the SP 300 VSP 300 VMP 300 when a 2A 30 V booster connected to the standard channel board Electrode Connections Disconnect the cables from the cell select Electrode Badnera oone tede eeo connections 30 V control and reconnect the cell as follows 30 control P2 and S3 lead to the working electrode S2 leads to the reference electrode P1 and S1 lead to the counter electrode Fig 57 30 V control mode for SP 300 technology Refer to the Installation and configuration manual of your inst
107. b gt 135 lt Tab _ 4 p Importation Parameters Text file format FC Lab z Columns Separator Tab v Colums J Automatic detection Number of columns 1 Columns type Column 1 Variable Time s Input file current polarity convention Positive oxidation standard IUPAC convention Positive reduction inverted convention Importation Imported File s Text file format FE La Chi CONDECOR CONDECY Ever 18 Cie ZV IEN FC Lab FE Lab log FRA Garry GPES GPES Cy VA Ewen A GPES CM Time s 15 GPES PSA Ewes dttdE 42 Timers GPES ECHN Timers Ewe rA Powersuite PowerCorr 18 Ewen Powerly Ewes 1 8 PowerPulse 144 E we Powersine Rel Ohm Imi Ohm PowerStep T imes 174 Voltarnaster Fig 240 Text file importation into EC Lab and available importation file formats To proceed to text file importation click on the Load button and select the file to import Now the file name directory and size are displayed near the top of the window in the Input Text File frame The second frame defines the parameters for importation In order to select the good separa tor click in the Show tab and space box to display separators in the file You can try with an automatic detection In most of the cases the user will have to use a manual detection while 176 EC Lab Software User s Manual unchecking the box Then define the number of columns and for each of
108. ch apply this process The selection of the Graph Style can be done on the Advanced menu as shown in Fig 122 As mentioned in the Graph properties part the user can choose amongst four available Graph Styles or define himself a Graph Style that can be associated with defined techniques This can be done selecting the Edit menu see following paragraph for more details about the Graph Style creation Clicking on the second Edit button does the technique selection Once the selection done techniques are displayed in the selected techniques box as shown in the Fig 122 Techniques selection 4 gt Electrochemical Techniques 4 gt Voltamperometric Techniques C Open Circuit Voltage OCV C Cyclic Voltammetry CY Cyclic Yoltammetry Advanced CVA C Linear Sweep Voltammetry LSY Chronoamperometry Chronocoulometry CA C Chronopotentiometry CP V Staircase Voltammetry SW C Large Amplitude Sinusoidal Voltammetry LA SY C AC Voltammetry ACV Graph Representations mm fas Pulsed Techniques ag Technique Builder Nyquist Admittance a Name Tri Manual Control o Black Admittance t Ohmic Drop Determination El PhaselZ error cad l Electrochemical Applications Bode Impedance CE Nyquist Impedance CE Representation Advanced Black Impedance CE Graphic style association Rp vs sin ampl Ri vs t Style nn E stack slave vs t lt None gt Technique Line style Line Markers style Nyquist sta
109. ck slave Select XY prop style Bode Impedance WE Monochromatic style Nyquist Impedance Wl Black Impedance WE Q charge vs t Q discharge vs t Q charge Q discharg Clear user 1 Edit Bode stack slave a Add Remove OK fea OK Cancel lt Graph Representations re N yquist Admittance Black Admittance 2 Phase Z error Bode Impedance CE Nyquist Impedance CE Black Impedance CE Graphic style association Rp vs sin ampl Ai ys t Style lt None gt v Edit E stack slave vs t Bode stack slave Technique s association Nyquist stack slave Selected techniques Bode Impedance WE Ey Nyquist Impedance wl CA Black Impedance WE SY Q charge vs t Q discharge vs t Q charge Q discharg Clear user 1 7 Name user 1 Representation Advanced Edit Add l l Remove OK Cancel Fig 122 Graph Style and technique selection Note this graph representation will only be available if the variables to display are recorded in the current mpr file for which the representation will be applied 3 2 10 3 How to create a Graph Style It is often convenient to display the obtained data with the same way same trace color same markers same units For this it is possible with EC Lab to create a Graph Style In the Graph tab select the Representations menu The Graph Represe
110. cseeeseusesseeeeseasessaeeess 150 SlerM Geary GIAO asset desta da did 155 ELA ER E ee re A y eee ee eee ee ee ee ce eee eee ee 150 A eee cakaa an cot en eae eet eae aaa a tne 156 MUO GU o Cea cesta ce teeta tite ce tee eet E 23 A e PEE RUE eee eee eee ee er ee ene eer eee eee ere ee ee 185 A A O a a 185 Messi 184 GUS IO IMA ICO el lo aecea tes 42 A nn A ke a S 109 EXAMI o atcect pani dan nian iectpanueci nica tect A ce ning Mined Rea saay E 113 DO LUD E a p PP sashes auieenaaanamananaseeenneausle 111 OYCIOS Suite tt titoricardo 176 OO a 17 O meee ee 75 A A A A 139 Data A AA O O a 95 COO SION AA II A A II A eee 149 A Pee eC ne Ce ee eee ee 103 FOUnEr ansiosa e a a a a 102 o AA E A II O ena ear re SNE E em 121 MSC AO o e O SO 0 A 101 Mii eE E E NE EER AAN 99 T a a te Pane nn een ane ne ane ae eat cna nee nT ae ree Re ee eee a 96 NIG SCA o ees ca 143 201 EC Lab Software User s Manual MOTE SCROUKY Plis acid 145 MOT SCHOUKY Pl bisnietos 143 BS AI AIL YSIS Ad 105 ES CIN PP oo O II A ein uae wanna aruae ies 106 PIC SWIG atu A ee ee Ne O ee sett Cee eee ee et 106 A o A 146 SUDAR St acia 100 AO AN POCO REO OO E ees ae ae as ee a T T 108 File Na eee ee nee ee ee 63 PUGS selected PONG ives pce sees cress reese cerns e eid eats 78 Kole errr re ee er eer ee eer ere er ee er ee eee ere re 73 A e 71 75 SN ig eis ig eri ascites ig esting cave igen goes igs g aan isang one state non one enone 61 e212 1 fee ome eer oe
111. curve at the extremities of the zone of selected points In the Regression mode the baseline is determined with the least square method Data points used for the regression are automatically selected within the first quarter of the total number of points between the be ginning of the selected zone and the point correspond ing to the max current value Baseline Peak Baseline Ho Linear Manual Polynornial Resulta From point o mt Y To point me T3 P Total points 2 Slope 2 0416 3 mary Offset 3 314e 3 m Correlation 1 Polyrorne Calculate Copy Save Lloze Fig 148 Baseline selection tab e lf the user selects Polynomial a polynomial baseline is plotted between the two cur sors using two data zones for the polynomial fit twenty first points and twenty last points of the selected data zone The polynomial used to plot the baseline is the following y ax bx cx d The results of the fit are automatically updated when a cursor is moved The Results box displays the baseline equation and the data point zone used for the regres sion 105 EC Lab Software User s Manual 4 2 1 2 Peak analysis results Peak Analysis When the baseline type is selected click on Calculate The Baseline Peak software will automatically find the max current value in the se Selection lected zone according to the baseline Data points used for the ea peak analysis a
112. d DIS Mo ALS 126 semi Intinite DITUSI N Wisin E eensvaeiants 125 Equivalent Circuit Syntax asasi ai ae i a AE SEa aaa ES 132 Kramers ON caras a N 147 A RR 54 A a a e is OAE AE RES ee ia AE 134 lalo AAA N 136 RAandoOMIZa UoN sata 136 WES Uvas con to od eee ee eee Te 137 139 x 137 O o eT ee ee ee ee 130 MPA NOM seca retire haeeitedet in aceite ian aa 74 176 o e Een eR ea eon eee ee 177 AP eE Eo 28 IM Slate oa 32 UIAKEA LECANIQUES ise 42 AE cote gat eho eete tate ete ta hele ek ernie ee erate ee cat alae 84 EP ze 34 42 77 176 Man Menu Barras T A T 11 A O O OPE e OC In a 96 EC Lab Software User s Manual Multi Channel Selection O A eee ee eee 51 e e e eee AEE ern me 51 53 SV MGI OMIZC A POOo 5o 5ZP A e 51 M li Device CON ao e dea e ee DS 17 MUECA natalie 88 Ohmie Drop GOMpPCNSallON ue css id Oe ated Aaa Ae ected 46 Paramet o VULNS ea ee cfr ced setae need acl ae lab peed os ect ead a eset 21 Parameters SSNS xia daciiiesarctieaerecie E end eae eelaaeeee reas 18 PON GOOrdIN ASS cscs A o needa eee nee ea 74 Potential Range PA eno adeudeaaenenedauadetdaastwensasuadels 182 CONTO PPP oo E A ion cotta asin ing ial espe Is ocd aie das ooh 182 A 86 TOC SS o do 161 Capacity and Energy Per Cycle occcccccncccccnccccncccnononocnnnnnnnonncnonnnnnonnnnnnnnnononcnonnnnnnnanoss 166 COMPactiaiianaai da a id 163 165 Gonstant Power Protocol SUMMANY diurna date tegen 169 DEINE CVCE seana a Siadd const
113. d Red species of a redox system 4 3 2 1 Z Sim window 1 step To simulate a curve with the same shape as the previous experimental results click on ZSim icon Ay or right click on the graph and select AnalysisiZSim Then the ZSim selection win dow appears with the corresponding graphic window This window shows the simulated graph of the circuit with the values selected 129 EC Lab Software User s Manual Sim Set Frequencies from F 100 000 kHz 50 to E 1 000 mHz with 10 o points per decade Zsim mpr Im Z vs Re Z 40 Ir Logarithm spacing E 30 Equivalent circuit A1 01 F2 C3 F3 Edit O p N 20 parameter value E Ohm 1 10 F s a 1 10 1 000 1 050 1 100 Re Z Ohm Calculate Copy Save Close Fig 183 ZSim menu and the graph corresponding to the selected circuit Note the simulation circuit opened by default is the one used in the previous simulation 2 step In the frequency frame set the frequency range between 500 kHz and 10 uHz with the num ber of points per decade and the spacing logarithmic or linear Select an equivalent circuit in the list If the required circuit is not in the list then the user can create a new circuit in the Edit window Click on Edit to display this window Equivalent Circuit Edition Circuit 991 35 Description R1 01 A2 C3 A3 Add Display Circuits With F m Teva Modify RC Elements All C
114. d in elec trochemistry for the validation of experimental results The impedance imaginary part can be calculated from the real part or conversely with the equation _ 2 f Re 4 x Re Z w TT gt x w The Kramers Kronig transformation can also be verified in an admittance plot If we consider the previous data file ZPOT Fe Basique mpr the Kramers Kronig transformation applied to the whole point series gives the following results IM 2x 00 ax lt PEIS Fe_basique_1 mpr Im Z vs freq log spacing lt PEIS Fe_basique_1_kk mpp Im Z vs freq log spacing gt PEIS Fe basique_1_kk mpp Delta Im Z vs freq log spacing 20 1 D O Im Z 0hm 00 O Z W e119 0 10 O 120 E 140 0 1 1 10 100 1 000 10000 100 000 freq Hz log spacing Fig 202 Result of the Kramers Kronig criterion applied to the data points with the ex perimental Im Z part the calculated one and the relative error One can see that the system does not fulfill the Kramers Kronig conditions because in the low frequency range the impedance does not tend towards 0 For the high frequency range the imaginary part tends to 0 so the precisions given below are not significant 146 EC Lab Software User s Manual Kramers Kronig Results A Reli Sai A Imi 24 Sb E lt A El 3 04 lt A PhaselZ gt E e The results of this test are displayed as an averaged relative error for each parameter Re Im
115. d its variables 2 5 1 1 Right click on the Parameters Settings tab EC Lab software contains a context menu Right click on the main EC Lab window to display all the command available on the mouse right click Commands on the mouse right click de pend on the displayed window Other commands are available with the mouse right click on the graphic display EC Lab Software User s Manual Advanced Settings Cell Characteristics w Parameters Settings Channel 13 Load Settings Ctrl L Leal Save Settings 45 Chrl 5 Print Experiment Reset Settings To Default Fie Set Settings 4s Default os Group E Add Sequence Ef Reset Sequence Copy Sequence Ctrl EJ Paste Sequence Ctrl V 2 Modify Ctrl M b Run Ctrl F Fig 26 Mouse right click on the main window of EC Lab software Most of the commands are available with the right click They are separated into 6 frames The first frame concerns the available setting tabs the second one is for the experiment from build ing to printing The third frame is for the modification of an experiment actions on techniques and the creation of linked experiments The fourth one is dedicated to sequences addition removal and the fifth one to the controls during the run The sixth and seventh frames are additional functions described above and the last frame is a direct access to the Options tab 2 5 1 2 Selecting a technique First select a channel on the channel bar The
116. dditional Variables is checked by default Unchecking the option will add the state byte variables to the file selection window lt is also possible to keep some previous processes or zooms by ticking the boxes Keep previous axes process and Keep previous zoom Several commands are available to use files e Load replace all files by others e Add add file s to the list in order to overlay curves Remove remove the selected file from the list Undo undo the last operation done Clear remove all files from the window X Y1 and Y2 represent the X axis and two different Y axes left and right EC Lab users are able to plot data in X Y1 coordinates or in X Y1 amp Y2 coordinates Select the variables to be displayed on a given axis by clicking the corresponding box click again to deselect Select Same selection for all files to get the same axis display for several files A shortcut scroll menu allows a quick selection of the graph plot 19 EC Lab Software User s Manual 3 2 Graphic tools 3 2 1 Cycles Loops visualization The cycles in the CV Cyclic Voltammetry CVA Cyclic Voltammetry Advanced and SV Stair case Voltammetry techniques are automatically generated without any additional action from the user For experiments made with an older version the user will have to process the cycle number according to the procedure described below to display each cycle separately If the selected file contains loops or several cyc
117. dified Gerischer element Ga The expression of the imped ance of the modified Gerischer Gp is given below Description Modified Genscher 2 Lb Impedance Ay ZI 1 171 oi ta Muquist Diagram lm 2 vs Rek Fig 181 Modified Gerischer diffusion element 2 128 EC Lab Software User s Manual 4 3 2 Simulation Z Sim In order to define the equivalent circuit after an impedance experiment the user can create an electrical circuit and plot the corresponding Nyquist impedance diagram in a given frequency range To illustrate the capabilities of this tool let us consider the ZPOT_Fe_basique mpr data file that the user can find in the sample folder C ECLab Data Samples The aim of this sec tion is to define the appropriate circuit for the fit The data file that will be used in the simulation section and the fitting section has been made from an iron solution on a gold disc working electrode in a pure diffusion regime in the potentio mode at the open circuit potential Open the PEIS_Fe_basique mpr data file using the Ex periment menu Load data file The following window will be displayed PEIS Fe_basique_1 mpr Im Z vs Re Z 100 80 60 Im Z 0hm 40 20 100 200 Re Z Ohm Fig 182 Experimental Nyquist impedance data file This is a typical impedance data file performed in a pure diffusion regime in a solution contain ing both Ox an
118. dow 3 3 2 6 LOG History file The log file summarizes all parameters used for an experiment with the possible modifications on line Log Note common parameters for all graphic windows O K in Cancel EC Lab Software User s Manual The user can show or hide the graph legend The position the font name style and size the background color and the trans parency of this background can be defined The legend includes the file name Note When several traces are plotted on agraph the user can select the active trace by clicking on the cor responding legend A title can be added to the graph to describe the experiment The text must be typed in the box The user can choose the title s format font font style size and color To improve contrast and legibility for a presen tation for example the user can change the color of the graph background This window allows the user to se lect the current polarity conven tions to display data files The standard current convention from IUPAC with a positive value for the oxidation current The inverted Current convention with a positive value for the reduction current It is also possible to adjust the graph size to the monitor format displays the history of the experiment from its beginning 83 EC Lab Software User s Manual i peis3_05 mpr LOG a File pels3_05 mpr rE points 10 031 bytes Potentio Electrochemical Impedance Spectrosc
119. e lvs time ve time EwelV 2s 58 9e 6 m 113 111 4 0 019 42 m Total ponte 111 yu Parameters Select all s cycle s CA R 100mHz_01_ena_psd mpp Ewel vs freq I vs freq Ewe trend removal 0 02 trend removal PSD with DFT se MEM order Results Ewe average 2 448e 3 W average 0 473 56 6 A o Ewe 0 935 ve 3 W ol 0 184 9e 6 A Ar 5 061 Ohm Fig 221 Electrochemical Noise Analysis on system with a 100 mHz electrochemical noise time s Ewel V o na wri freq Hz References Bertocci U Frydman J Gabrielli C Huet F and Keddam M Journal of Electrochemical Society 145 1998 2780 2786 Mansfeld F Sun Z and Hsu C H Electrochim Acta 46 2001 3651 3664 Lee C C and Mansfeld F Corrosion Science 40 issue 6 1998 959 962 4 7 7 Other corrosion processes Two additional processes are available with the corrosion techniques Polarization Re sistance and Multi Pitting Statistics They are both described in the section below 159 5 1 EC Lab Software User s Manual Data and file processing General variables can be processed with the process data function From the EC Lab menu choose the Analysis menu and for each of the analysis category a list of processing functions can be applied to raw mpr data files Hereafter are summarized all the processes Process Data Capacity and energy pe
120. e Q for a discharge cycle reinitialized every cycle Qdischarge mA h x normalized charge X Apparent resistance R O Cycle number cycle number Power in CPW calculated by E P W Differential current over time for potentio technique only dl dt mA s Energy in CPW calculated by E l t Energy W h Energy charge E l t for I gt 0 E charge W h Energy discharge E l t for I lt 0 E discharge W h Cycle time time elapsed during each cycle cycle time s Step time time elapsed step time s Discharge time time elapsed during each discharge l lt 0 reset to O at discharge time s the end of each charge Charge time time elapsed during each charge I gt 0 reset to O at the charge time s end of each discharge Incremental or differential capacity over the potential dE during d Q Qo dE mAh V charge or discharge Rp polarization resistance in corrosimetry R O Icorr corrosion current resulting from Rp calculation Icorr A Ecorr corrosion potential resulting from Rp calculation Ecorr W C Inverse of square capacitance for Mott Schottky plot Care C Capacitance for Mott Schottky plot C F Frequency freq Hz Ewe module of Ew Ewel V I module of N A Phase of Z Phase Z deg 1Z module of Z IZQ Re Z real part of Z Re Z O Im Z imaginary part of Z Im Z 0 lt Ewe gt averaged Ewe value for each frequency lt E gt V lt l gt averaged value for each frequency lt l gt A Range current range Range Capacitance calculated usin
121. e bath One computer or eventually several for multichannel instruments connected to the instrument can monitor the system The computer can be connected to the instrument through an Ethernet connection or with an USB connection With the Ethernet connection each one of the users is able to monitor his own channel from his computer More than multipotentiostats our instru ments are modular versatile and flexible multi user instruments Additionally thanks to the multiconnection several instruments can be controlled by one computer with only one EC Lab session open Once the protocols have been loaded and started from the PC the experiments are entirely controlled by the on board firmware of the instrument Data are temporarily buffered in the instrument and regularly transferred to the PC which is used for data storage on line visuali zation and off line data analysis and display This architecture ensures very safe operations since a shutdown of the monitoring PC does not affect the experiments in progress The application software package provides useful protocols for general electrochemistry cor rosion batteries super capacitors fuel cells and custom applications Usual electrochemical techniques such as Cyclic Voltammetry Chronopotentiometry etc are obtained by associ ations of elementary sequences Conditional tests can be performed at various levels of any sequence on the working electrode potential or current on the
122. e or pressing lt ENTER gt will start the experiment and the Run button turns into the Stop button One file is created when running the experiment a binary raw data file with an mpr extension automatically added that contains all the information for the experiment usually contained in the Log file the selected protocol initial settings instrument IP and channel N files director The user can choose to separately save the Log file using the Config Options General menu Linking techniques 2 1 Description and settings It is possible to link different protocols within the same run This allows the user to create and build complex experiments composed of up to 20 techniques When created the linked exper iment settings can be saved either as an mps file or as a Custom Application In the first case the settings can be loaded from the initial folder and in the second case they appear in the applications and can be reloaded whenever necessary Linked experiments can be made using the Technique Builder in the technique window The WAIT and LOOP options have been designed especially for linked experiments Building linked experiments is very easy with settings on the right click menu When the user right clicks on the parameter settings window the following menu pops up 41 EC Lab Software User s Manual E Mew Experiment Ctrl Mew Stack Experiment lal Save Settings 45 Chrl4 s Insert New Technique
123. e plotted on one single graph 63 EC Lab Software User s Manual 2 14 3 Text Export Options Options default General Warming Test esport Colors References Tool bars menus E Mail Text file exportation format Time Elapsed Time in 2 Absolute Time mm dd yy hhi mmss s28 Fig 86 Option window Text export tab The time recording format for the exported files can be chosen 2 14 4 Color Options Options default General Warning Text export Colors References Tool bars menus E Mail Grid lines color Curent Values Color Ewe Flow chart colors Time Ns my Chart 1 ms El Display the nest variables in bold Iex E m Applicaton background i Color Back Theme Sky Blue wt Fig 87 Option window Colors tab 64 EC Lab Software User s Manual e The grid line color of the grid lines for the multi line parameters settings see the GCPL protocol can be chosen e The background of the flow chart and text color can be chosen The custom buttons allow the user to define additional colors that appear at the end of each drop box The default color theme is Sky Blue 2 14 5 References Options e Displays all the reference electrodes registered in EC Lab The default reference elec trodes are in black Options default Soe A General Warning Test export Colors References Tool bars menus References Electrodes Electrode Name unspec
124. e set values and in potential sweeps to be as close as possible to a linear sweep with the smallest potential step This is obtained by adjusting of the DAC output from 10 V 10 9 V to the required potential range through a programmable attenuator and a programmable offset This optimization is available in the Parameters Settings window see below Given the Emax and Emin limits the potential range is reduced to Emax Emin and the potential resolution becomes Ena Emin 0 2 65535 Adding the 0 2 V value is a hardware constraint to allow reaching Emax and Emin Thus the theoretical maximum resolution is 3 uV 200 mV 65535 In EC Lab we have chosen to have a set of fixed resolution values adjusted to the potential range in a 1 2 5 10 scale This leads to the table below for the maximum potential range values at which the resolution changes 181 EC Lab Software User s Manual 20 305 18 or 333 33 19 46 300 12 9 200 6 3 100 3 0 90 1 1 20 0 4 10 0 12 9 Table 1 Resolution values according to the Ewe potential range Note that the potential control resolution is available with low current boards delivered from 1 June 2004 For the other low current boards delivered before 1 June 2004 a technical mod ification is necessary 6 2 2 Settings of the Working Potential window If no experiment limits are defined the potential resolution is 305 18 uV or 333 33 uV corre sponding to the
125. e the section below 3 1 4 Data file and plot selection window Right click on the mouse and select Plot select Selector in EC Lab Graph menu or click on the Selector button to open the selection window The following window will be displayed 74 EC Lab Software User s Manual File Selection Files Variables Co ACY platinum 10 cycles n mpp Representation ves Ewe as TL YE times control E wer lt l gt 4m cycle number Pr 4 Same selection for all files v Hide Additional Varnables v keep previous axes process keep previous zoom Load Add Remove Undo Clear Cancel Fig 101 File selection window The user can choose to plot other variables as the predefined ones The loaded file contains the recording of the following variables the time time s the working electrode controlled po tential control V the working electrode measured potential Ewe V the average current av erage values on every potential steps lt l gt mA and the state byte Other variables such as cycle number may be displayed depending on the protocol of the experiment The state byte includes the variables mode ox red error control changes and counter inc cycle increment that indicates different status of the experiment Most of the time the user may not be inter ested in showing the state byte that is more dedicated to internal files processing The option Hide A
126. eak analysis using a linear regression baseline 106 4 2 1 4 Results of the peak analysis using a polynomial baseline 107 A 2 2 WAVE ana SIS ariadna 108 A223 OV SIM rep EES 108 Ae OV OPC POE T Re Ea a aa 113 Aza WECIANISINMAD ia co ici 114 4242 SUP TAD capes erase a a a agers teat ies ae ee 115 4243 Selection t b oesi n a a aicuaten accu bee aa aa a i 116 4244 E E E o A EEE O A A ai 117 4 245 GV FICDOMOM DUTONS ent eea a a i 118 A246 OVARIOS US iccinron inina ate aicacguebiednsticatdanutnnicaeaicenatens 119 4 3 Electrochemical Impedance Spectroscopy MENU ccccceeeeseeeeeeeeseeeseeesaeeens 120 4 3 1 Z Fit Electrical equivalent elements ccccccseccseeceeeeneeeneeeneeeneeeneeeneeeneeenees 120 ASS Val Resistor R uissusactassnuacuassndaciacebasendenmamensanitncndnmemeisasitnendmmanraniincndnmaneaad 121 Beles WNOUCIOR iz cyi peice tice lorie asset EN 121 431 3 AVIOOINIEGINGUCION a ii 122 AA GADACKOR o O e Sa eee aes ec ses 123 4 3 1 5 Constant Phase Element Q occccccccncccccnnoconcnnononnnonononnnnononononnnnnnonononeness 123 4 3 1 6 Warburg element for semi infinite diffusion W ooocionccconinoninoncnanonnno 124 4 3 1 7 Warburg element for convective diffusion Wg ooocconnionnccnniconicanonono 124 4 3 1 8 Restricted diffusion element M occcnnncnccncccnccncnncnnnnnonocnnnonannnnnnonnnnnons 125 4 3 1 9 Modified restricted diffusion
127. ection of the curve with the median between both linear regressions la is defined as the current value for E E1 2 on the anodic linear regression and is defined as the current value for E E1 2 on the cathodic linear regression 4 2 3 CV Sim 108 EC Lab Software User s Manual CV Sim is a tool designed for the simulation of cyclic voltammetry curves resulting from a voltammetry experiment It is a useful tool to elucidate the mechanism of an electrochemical reaction involving from one electron E to five electrons EEEEE To perform the simulation it is assumed that the Initial current is equal to zero The user needs to define the number of electron transfer steps that are involved in the mech anisms via the combo box E represents a mechanism with one electron transfer E and so on up to 5 electron transfer EEEEE Depending on the number of electron transfers selected the corresponding number of tabs appears The EC and CE electrochemical reactions are also available C standing for bulk chemical reaction with no electron transfer CY Sit CY Sir Example Example Mechanism E Mechanism EEEEE Reaction Reduction Arze d E Reaction Reduction A ze4 E z 11 E0 TA i y ko 10 001 cms Y 10 001 cms Gh f 0 5 10 5 Species Ca initial fet mol L Cg intial Oo mol L Da deb cm fs Dg Se 6 cits Species Ca initial et mol L Cg intial jo mol L Da fe 5 ones Dg Feb cm
128. ed Time 0 9998 s Ewe 0 220 mV 0 0004 Buffer 0 Eoc 0 220 mv 000 0004h P o000w ne 0 Range open p VMP3 R USB Channel S EENEN a 1 29 0 063 4 2 789 b s Fig 119 Multi windows This can lead to a very complex displaying mode that may be very useful for multichannel display 3 2 10 Graph Representation menu It is possible for the user to define fast graphic displaying modes with the Representation tool in the Graph menu The Graph Representations window already offers some standard representations For each representation a scheme of the axes is given For example in the Fig 120 the Bode imped ance representation is given This representation is defined as the frequency value on the X axis This value is processed with the log spacing function the IZI value on the Y1 axis This value is processed with the log function the Phase Z value on the Y2 axis It is possible to display the two Y axes on the same graph or to separate them selecting the Separate traces box 88 EC Lab Software User s Manual Graph Representations Ewe vs eee Ece vs t Bode Impedance wa t Ewe vs t Representation Advanced Ewe vs 3 lve Ewe delta vs Estep YT axis Ye axis loglll vs Ewe lO him Phase 4 deg Ewe vs logll L log l ri a E separate traces Power vs t Energy vs t Ap ws t aes Bode Impedance freqHz Myquist Impedance log Black Impedance Mame Bode
129. ed on the graphic tool bar to select the cycle to display 76 EC Lab Software User s Manual vs Ewe v Show cycle 7 q p al vs Ewe CY _Fe_1_n mpp lt gt m 0 2 02 0 4 0 6 Ewe lV Fig 103 Cycle selection on a processed file The user can see either all cycles or a selected cycle chosen with the scroll box This option is very useful for peak analysis on a given cycle especially in analytical electrochemistry Note If the user wants to copy data mouse right click and paste in a spreadsheet software only data corresponding to the displayed cycle will be copied A title can be added to the data file and appear at the top of the graphic window Right click Select Graph properties and choose the Title tab 3 2 2 Show Hide points The EC Lab software is equipped with a show hide option on the right click menu Abnormal points can now be hidden on the graph in order to perform data fitting without any troubling points The hidden data points are not removed from the data file They are only graphically hidden for better fitting The data points must be selected with the selection mouse mode i i before being hidden Then click on Hide Selected Points to reject points 3 2 3 Add comments on the graph The graphic package allows the user to add comment zones on the graph The number of comments zones that can be added on the graph is unlimited 11 EC Lab Software User s Manual menta a
130. eeds to subtract 4 3 13 two data files as the subtraction between two files is only possible when the interval between each point is the Quput file same for both files Nb Points ho Sampling Mes 3 Calculate Copy Save Close Fig 135 Linear interpolation window 98 EC Lab Software User s Manual 4 1 6 Subtract Files Subtract Files A tool for subtracting curves is available with selection EC Lab The raw data files are not changed after this analysis The Subtract Files tool is available in the olution Math menu or via the right click of the mouse jez The two files to subtract are selected as File 1 and File 2 Then the resulting file File 1 File 2 is displayed 5 The sampling rate of the resulting file in _filter mpp for mat is defined by e the sampling rate of file 1 or and file 2 O Same as File 1 e the total number of the points of the resulting curve File 1 File 2 The spacing can be de fined in a linear or logarithmic spacing O Same as File 1 and File 2 e aconstant time step foo points The results can be copied in the clipboard to be pasted i in the print window comment zone or in a text file They can be saved in a text file ir spacing O Exem 0 001 0 Y Fig 136 Substract files win dow File 1 File 2 sampling Same as File 2 lt l gt vs Ewe z CV_1nA_10Vs_solution mpr cycle 2 z CV_1nA_10Vs_background mpr cycle 2
131. emperature Dielectric constant 1 000 0 001 co Surface area Results Hlatband potential 3 375 W E Donor density 0 490 71e18 cr Frequency 21 922 kHz Hlatband potential 3 455 Donor density 0 418 3e16 cr Frequency 217 576 Hz Flatband potential 3 492 Donor density 0 397 12618 cr Frequency 3 168 Hz Flatband potential 3 508 W Donor density 0 451 be18 cr F mr F Calculate Cony Save Ciose Fig 199 Mott Schottky results window The potential range used for the analysis is shown in the Results frame For each selected frequency the flat band potential is determined by extrapolation of the linear regression to C 0 The donor density is calculated from the slope of the linear regression at 25 C according to the dielectric constant of the material and the surface area of the semi conductor defined in the Parameters frame 144 EC Lab Software User s Manual SPEIS_7MHz to 1Hz__C _V_Charact mpr mpr Cs 2 vs lt Ew e gt gt 1 024 MHz 21 922 kHz 217 576 Hz 3 168 Hz 0 002 0 0015 0 001 Cs 2 pF 2 0 0005 lt Ewe gt V Fig 200 Mott Schottky Fit The results of the fit flatoand potential donor density can be copied to the clipboard to be pasted in the print window comment zone or a text file They can be saved in a text file 4 3 4 4 Saving Fit and analysis results All the fits described above can be saved in a text file Click on save to create a
132. ent and reloaded with Experiment Load settings or with the right click menu Load settings Linked experiments settings files are text files with the mps extension like the standard set tings files Please be aware that the recording of auxiliary signals from Analog In1 or Analog In2 and power are disabled with an impedance technique No external data points will be recorded during the EIS measurement period If the user accepts such settings the following warning message appears A Warning itis not possible to record analog inputs and the power with the impedance techniques Selecting these recordings will have no effect for the impedance techniques Fig 66 Warning message on external signals recorded with ElS techniques 2 7 2 2 Application of linked experiments with ohmic drop compensation The following experiment is given as an example of linked techniques but also to show how to use the Ohmic drop compensation techniques This experiment is composed of CA CV PEIS and Loop techniques This series of linked techniques illustrates the effect of the ohmic drop compensation Indeed to compensate the ohmic drop during an experiment the ZIR technique has to be set before the techniques for which the compensation is done To illustrate this the Fig 67 is given as an example In the left side of the figure the series PEIS CV ZIR CV is defined On the right side of the figure the second graph shows the superimpositio
133. equencies that appear if the time record is not periodic with the input which is the case in Fig 133 The 6 windows possibilities are described below the rela Calculate Copy Save tionships are only valid within the interval 1 1 and 0 out gt Frequency range Auto side Rectangle ka Rectangle w t 1 B arlet Barlett w t 1 t HA Hann w t 0 5 0 5cos Trt Blackman Hamming w t 0 54 0 46cos rrt Welch Blackman w t 0 42 0 5cos mt 0 08cos 2Tit Welch w t 1 t 2 Fig 140 Fourier Transform window The processed DFT data file is created with the following name filename_dft mpp This tool is very useful to determine if the measurement is affected by environmental noise like 50 or 60 Hz 101 EC Lab Software User s Manual CA R 100mHz_01 mpr Ewe vs time vs time 0 1 gt AAAA A AAAA 2 0 0 1 0 02 AY i 20 02 0 50 100 time s CA R 100mHz_01_dft mpp Fourier Transform limA vs freq E Selection Trace vs time From point O 0 003 A Os nha O m lt i To point Wie 0 002 gc 111 4s ite 0 019 42 m Total points 114 0 001 Sampling Parameters 0 986 1 s 1 014 H2 Window Blackman Y freqiHz Y Auto Frequency range Freq Min Hz Freq Max Hz Nb Points 55 Fig 141 Fourier transform analysis 4 1 9 Filter Data may be distorted by external perturbation for instance in our example the
134. er values 136 EC Lab Software User s Manual ma cn Selecon Poesia EA A A pa H Equrralert orou Aber 0gak AxSOGR RoGAR2 W2 cals Hepa impediret S hc E Bi p de a E Ohm 0 3437 Arz we Rect aa 17 0906 Felei 316706 ml ws Pot PES Fe benga zim A 03e Ja TOS Ohm 0 7798 wa BB FF Ohne 1 2 UEG i r E e z Fil E Select qurent F iiki 7 Method Flandomas Simplex Rebre bi ock ony Shop andorra on 10000 berabor Stopfton 5000 tertio waga 1 q 25 42 se PA BOTA Restore S000 5 mole Cycle Pea Retz ohm pa Mirarczo Eseudol Copy zave e Fig 189 Fit results with a combination Randomize Simplex The randomization was stopped after 10000 iterations and the fit after 5000 iterations In that case the yx value is related to a weight 1 for each point The more points are selected for the fit the higher the x value will be In case of a weight Z the results are as follows Ez Grapt bola E i Sedin Aesi tea de T i E al i HR AN Mer Equrvaient ciz A AS mh oF AMAIA dl A A E OSAR Edi B Hypiimpniee Show q b pom weljugeijwalos ura de a Al AT Dit 03551 imi va Redz sk F a ar De ell PHs Fe birga i oo Az 1 Olen ORI7E 120 E 54 56 Dimi 0 3961 100 4 E T E 5 EN Fa 3 a Select cunerd cycle Tog E Method andornuzn Sampii Radome frit cock ork ad i Shopiandomine o
135. error mode Pink Impedance mode Blue Pause mode White stopped mode 15 EC Lab Software User s Manual 2 3 3 Graph Tool Bar The Graph Tool Bar with shortcut buttons including zoom rescale analyses and graph prop erties is attached to the graph Report to the graphics tools part for more details Fig 19 Graph Tool Bar Also attached to the Graph window is the Fast Graph Selection Tool Bar that can be used to rapidly plot certain variables and choose the cycles loop to be displayed Ewe vs t x v Show loop 4d 4 p Fig 20 Fast Graph Selection Tool Bar and cycle loop filter 2 3 4 Status Tool Bar At the bottom of the main window the Status Tool Bar can be seen VMP3 h 192 109 209 237 Channeli Read mode My Name 0 0 3 010b s Fig 21 Status Tool Bar for a VMP3 The following informations are displayed the connected device the instrument s IP internet protocol address if the instrument is connected to the com puter through an Ethernet connection or USB for an USB connection For multichannel potentiostat galvanostat or for measurements that require a fast sampling rate the use of the Ethernet connexion is strongly recommended the selected channel alock showing the Modify Accept mode Read mode or Modify mode the remote status received or disconnected For VMP2 and for SP 300 technology instru ment Warm up autocalibration is displayed when the instrument perf
136. es EEEE CUSTOM DC 3e 6 em2 s 1 ES Comments Reaction Reduction ze lt gt D z 1 EO 0 2 Y KO 0 1 cm s 1 a 05 Add Remove Select Fig 160 CV Sim examples window EC Lab Software User s Manual 13 predefined examples are available in this window The corresponding parameters are dis played on the right column Custom reactions can be added by the user by clicking on the Add button The custom parameters must be entered in the parameters window then needs to be added to the custom example by clicking on Replace 4 2 4 CV Fit CV Fit is an analytical tool dedicated to fit cyclic voltammetry curves consisting of at least of one cycle It determines the kinetic parameters of a cyclic voltammogram like the rate constant k charge transfer coefficient o diffusion coefficient To fit an experimental voltammogram the user has to open the experimental voltammogram and select CV Fit tool available in General Electrochemistry section of Analysis menu According to the nature of electrochemical specifies available in the solution the user has to choose between seven mechanisms E EE EC CE EEE EEEE or EEEEE mechanism Example File Mechanism EEE E segs P Fit Reaction EC CE A ia E EEEE i EEEEE Y 0 172 Y 1 05e 3 cms 4 B5 Species Ca initial de2 moll Cg intial F mol L 7 Feb cms 7 e6 scr fatata y Y i TETE HHNH lterations ERRE Relative error see
137. es ring disk electrodes A bipotentiostat is necessary for the measurement of the working electrode po tential of both electrodes The VMP3 using two channels VSP SP 300 VSP 300 or the VMP 300 are appropriate instruments for this kind of experiment 187 EC Lab Software User s Manual Fig 255 RRDE Rotating Disk electrode ALS RRDE 3A 188 EC Lab Software User s Manual 6 4 2 1 Control panel Before running any experiment with a rotating electrode one must first choose the rotating unit Click on External devices tab Device type RDE in the EC Lab experiment tab Devices Device Type Device Name Analog OUT SP 150 255 8 VSP 300 238 E E E E 0 0 Experiment Analog IN 1 Advanced Settings Cell Charactenstics p 0 E E Parameters Settings EEE om ae i 1 EW RCA E 10 Fig 256 Menu to choose for rotating electrode control Note this menu is available only if channels designed to drive a RDE are connected with the RDE electrode rotator Then the following window is displayed 189 EC Lab Software User s Manual Device Type Device Mame Analog OUT 6000 le E E 0 0 Analog IN 1 Convert EM to DeltafFreql H2 e with o Wo E Hz mas 0 Y D Hz min Analog IN 2 C Convert EM to DeltalA Ohm with 10 Y 10 Ohm mas D Wo D Ohm mn Fig 257 Rotating electrode control configuration Under Speed control unit one can select the standard supplied ALS RRDE 3A or PIN
138. es Loops 4 6 Cancel Modify E St Split File F a Insert Technique From File E Sye Under Sampling E W Remove All the techniques E 194 Calibration E Reset Settings To Default PS Retrieve Data From The Instrumen dl wi j 4 Lock Toolbars Ass 42 aboia afia rarigi e cama Cancel Fig 16 Main Tool Bar menu to choose the icons to be displayed 2 3 2 Channel tool bar You can see below 16 buttons depending on the instrument and on the number of channels that can be inserted into the chassis These buttons correspond to the actual slots They are not displayed if the slot is unused or if there is a booster board or low current board inserted in it Fig 18 The channel number is always the slot number o Bo il Fig 17 Channel Selection Tool Bar of a multichannel fully loaded If no channel board inserted into a slot or if a booster low current board inserted into a slot the corresponding slot is not displayed in the channel selection tool bar O E Fig 18 Channel Selection Tool Bar of a multichannel partially loaded By clicking on the button the user can select the current channel s Clicking on one of the buttons enables the user to see the channel status The corresponding bars give the on off status of the channels white if there is no experiment running or colored if the channel is running Yellow charge mode Green discharge mode Turquoise OCV mode Red
139. experiments example with ohmic drop compensation technique 2 8 Available commands during the run During the experiment several commands remain active Most of the settings can be changed while the experiment is running These changes appear in the log file 2 8 1 Stop and Pause Clicking on the Stop button J will display a message asking for confirmation Clicking OK stops the measurement At that time a binary version of the mpl file is appended to the mpr file A raw data file mpr is then obtained which contains all the information on the experiment while the mpl file is erased The Log file can be kept as a separate file by checking the corre sponding in Config Options Clicking on the Pause button il will lead to a pause in the progress of the protocol and in the measurement recordings The cell will be disconnected from the current generator but not from the potential measurements Then the Pause button switches to the Resume button I and clicking on this button continues the experiment with a gap corresponding to the pause time 2 8 2 Next Technique Next Sequence It is possible during an experiment to move on to the Next Technique using the button N or to the Next Sequence using the button 46 EC Lab Software User s Manual 2 8 3 Modifying an experiment in progress The Modify button enables the user to modify most of the parameter settings while the experiment is running PE The new set of
140. f the current versus time Click on Display to automatically display the processed variable on the graph The ex ample below shows the Current derivative curve plotted versus the potential overlaid with the native cyclic voltammetry 163 EC Lab Software User s Manual C EC Lab Data Samples CV Fe_basique_ 1 nd mpp lt li gt ve Ewe cycle 2 dict vs Ewe cycle 2 A gt mA S YUI IP Ewe V ws SCE Fig 224 Overlay Cyclic voltammetry with derivative curve All the graphic tools and fits can be applied to the derivative curve 5 1 4 The compact process The Compact function or Keep only values at the end of every OC period on period function can be used in GCPL and PCGA protocols In the GCPL protocol this function results in the determination of the apparent resistance Ri of the material studied see the next section about GCPL In the PCGA protocol this function results in the determination of one average value of the variables for each potential step Selecting Compact compresses the data result ing from the raw data file All the points of each potential step are replaced by their average current potential x or Q taken at the end of the potential step One consequence is an im portant decrease in the number of points in the compacted file compared to the raw file The figure below shows the effect of the compact function on the current plot 164 EC Lab Software User s Manual Toba HAARAA m
141. f the first and last data points used for o 1231 me the fit are displayed as well as the number of points used Total points 44 for the fit in the Selection frame The results can be copied to the clipboard and be pasted Results Slope 99 99 rer red Offset 0 047 01 mu Correlation 1 in the print wndow comment zone or in a text file They can be saved in a text file Copy Save Close Fig 130 Linear Fit window PEIS Fe basique 1 mpr Linear Fit En Im Z ws Re Z Selection 110 Trace mid ve Rel es From point 29 a 100 s 136 2 Ohm Y 20 93 Ohm 90 To point 35 Ki 24 8 Ohm ii y 108 8 Ohm Total points 10 si Results e E Slope 0 987 6 Obim0D hm fo 5 Y Offset 114 Ohm vA rm Correlation 0 999 9 a 50 40 Calculate Copy Save Close 30 A 20 10 0 50 100 150 Re Z Ohm Fig 131 Linear Fit on the graph 96 EC Lab Software User s Manual 4 1 3 Polynomial Fit Polynomial Fit The polynomial Fit is a new mathematical tool available in trace cue ve tame EC Lab EC Lab 10 36 version and later This tool allows e a user to fit a curve by a polynomial The polynomial fitting w 2 432 W can be performed using the Polynomial Fit tool and by se epom Jo lecting the polynomial order e A When the zone of the curve to fit is selected click on Cal culate in the polynomial fit window 132 Move the cursors with the mouse by holding the mouse left 1i
142. fied restricted diffusion element Ma This element is also called Bisquert element The expression of its impedance is given below Description Anomalous diffusion May Mg Impedance E cothls eds Fyfe ra ls Sail Myquist Diagram l Im vs Rel Fig 178 Anomalous Diffusion element 126 EC Lab Software User s Manual 4 3 1 11 Gerischer element G The Gerischer circuit element arises when an electroactive species undergoes a chemical re action in the bulk A Gerischer element has also been used to model a porous electrode Description Genscher hy 3 Impedance a P 41 21715 1 Nyguist Diagram Im vs Rel Fig 179 Gerischer Diffusion element At high frequency the G circuit element presents a 45 line on the Nyquist plot 4 3 1 12 Modified Gerischer element 1 Ga The expression of the modified Gerischer circuit element derived from that of the Gerischer diffusion element expression by adding the parameter a The expression of the impedance of the modified Gerischer is given below 127 EC Lab Software User s Manual Description Modified Genscher 1 EEF ja Impedance Fy 4 1 nza Nyquist Diagram mf vs Rell Zif Fig 180 Modified Gerischer diffusion element 1 4 3 1 13 Modified Gerischer element 2 Gp A second modified Gerischer circuit element Gp has been used for models that do not match the Gerischer element G nor the mo
143. frequency range f 2 54 2TTT41 4 3 1 8 Restricted diffusion element M This diffusion element is used for finite length linear diffusion for example in the case of inser tion reactions Description Linear diffusion May t Impedance cothlYryizaf Yiyin Nyquist Diagram m vs Rel Zi Fay Fig 176 Restricted Diffusion element The restricted diffusion element is equivalent to the Warburg element in the high frequency range f 3 88 211Tg1 and to an R and C in series circuit in the low frequency range 125 EC Lab Software User s Manual 4 3 1 9 Modified restricted diffusion element M This diffusion element is used for finite length linear diffusion for example in the case of inser tion reactions for which the element M is not suitable Description Modified restricted diffusion May kal a Impedance coth s art 72 20 Nyquist Diagram Ir vs Rel Zit Fy Fig 177 Modified Restricted Diffusion element The modified restricted diffusion element is equivalent to the Warburg element in the high fre quency range f gt gt 3 88 2T1Ta1 see element M but in the low frequencies instead of being a vertical straight line it has a phase of a1T1 2 4 3 1 10 Anomalous diffusion element or Bisquert diffusion element M A second modified diffusion element My has been used for models that do not match the re stricted diffusion element M nor the modi
144. ftware User s Manual A ere Ne tee ee ee Meat er Pee eee ee eaten eae mee ce Tee Seca gee Ree Tee eee nee Cee ee Pe eee ee ee eee ee ee 37 Fitting Tools CAS oo 157 A o O E O O ee 98 O A EE E E EN 97 MUtexponentlal IM Fla le arteries ea 104 A aan cher icetcteape tens egmee sateape geserachranet a psaesceenanessreeneaeseeemneemseepesaese 154 UAV let cee cscs A IINA AE ET Cheeta Sete O A a EN 151 VAS ee ene en A EE AE EAE One eee eee eee ee ee ee 156 FA E E EOI ee ee eee eee ener 134 Floating Grounded A acetates tha ciate 37 FOW GKHanS MOS ene aime eet a ge enn Se 21 O VIEW scria a a es a 9 A O I eine ere ron terrae 70 A 80 Graph Menu Ec E E POE O mic aaa maaiane aie taceae es 89 aranh POUD MEN eee een ee ence ote ene o eE nee eee ee 70 Graph PEONES 1 o ea oo 72 81 DEl A A EE 70 HON Speed Scala 37 PIN anain A 24 io A oa mo OO i meee one en eee eee eee ee eee ee 121 Data Analysis G2 02 6 0 y AA RR een men mC eee Persie Mtn Mecsas eet ch Oe ae me ra Oa 124 e o E o eee tet eee ar genet caecen eueet eae 122 WOGINIEGINGUGTOR LA tii o eo ace 123 Electrical E ivalent Elements cs 121 Anomalous DNUS Mira a aia 127 Constant Phase E Seceen ciate deena celta edna eceae eas 125 CONVECTION DiffUSION WA aa de dead cnet 125 Genscher OO 128 Modified Restricted Diffusion Ma ccooccccocnccccnoconocncnocacnononononnnnannnnnnonnnnonannonaninannnnons 127 Tac 18 0 oe CADA CHANCO d 140 FA SIS ONE se gare teh A 122 Restricte
145. g 165 Selection Tab of CV Fit window before left and after right fitting 4 2 4 4 Fit tab Fit tab specifies the fitting conditions set for fitting procedure number of iterations relative error and fit duration The user can customize these parameters and set them by default by clicking on the default button CV Fit uses the Simplex method also called Downhill Simplex A minimisation method is per formed by minimizing the criterion X N x Y Fmosa Fi simil Eo 5 param i Where Imeas Ei is the current value at the potential E of the experimental voltammogram Isimu Ei param is the simulated current which is function of the chosen mechanism 117 EC Lab Software User s Manual The setting and fitted parameters are stored in the mpp file filename_cvfit mpp created by CV Fit tool This file can be loaded by clicking on file button each time the user wants use the same parameters Example File Mechanism E E Setup Selection Fit Stop fit or 11 000 Iterations 10 1 Relative error o hi mig Default of 0 706 2e 12 INN 21 01e 3 Iterations 2b Relative eror 0 098 39 Duration 00 00 06 Calculate Copy Save Irit guess Minimize Stop Fig 166 Fit Tab of CV Fit window Before starting the Fit make sure that all the experimental parameters are set in the mecha nism and setup tabs radius sample initial concentration scan rate The pa
146. g an R C series equivalent circuit Cs F Capacitance calculated using an R C parallel equivalent circuit Cp F Y Admittance magnitude in Q Y Q Admittance phase in degrees Phase Y deg Re Y real part of Y in O Re Yy 0 Im Y imaginary part of Y in Q Im Y Q 2 11 3 Data recording In all the technique sequences the user is able to define different modes for data recording The main mode is to fix the recording resolution of the measured variable potential dE current dl charge dQ with at least a recording every predetermined time interval dt from 0 1 to 9999 s The time interval condition helps in having a minimum amount of recorded points in case the variation of the observed variable is less than the chosen resolution for a long period of time potential close to equilibrium process leading to a potential plateau etc 99 EC Lab Software User s Manual On the contrary if the system is very unstable or noisy and the chosen variable interval condi tion is too small the amount of recorded points can be very high which can lead to a saturation of the buffer For open circuit period OCV nothing is controlled and only the potential is recorded The recording conditions for OCV periods are in time variation dt and or in potential variation dE For techniques with potential control two different recording conditions are now available 1 on a time variation and or an instantaneous current variation
147. harge The first one is to protect the cell against damages These limits must be higher than the limits set in the experiment The second way to use these limits is the control potential resolution It corresponds to smallest potential step that can be made according to the full potential range File Export as text function that converts the raw data file mpr to a text format file mpt The new created file is located in the same directory as the raw file File Import as text function that converts an ASCII file txt created by other software into an EC Lab raw data file mpr The new created file is located in the same directory as the text file File Load the load function allows the user to load a data file mpr a settings file mps a linked experiment settings file mpls or a report file 196 EC Lab Software User s Manual Filter this filter can be used as off line filter many times after the experiment but also just after the recording of the data by ticking a box on the Advanced Setting window Many methods and windows are available Fit graphic tool used to determine kinetic or experimental parameters Fourier Transform tool used to apply a Fourier transform to recorded data many windows are available Global view EC Lab software window where all the channels are shown with the user the experiment the state relax oxidation reduction and the booster or low current board Group option used
148. he battery will be charged with a current of 1 6 A The time of the charge is defined elsewhere in the technique see EC Lab Software Techniques and Applications 2 5 2 2 Reference electrode It is possible to set the reference electrode used in the experiment either chosen in the list or added while clicking on the corresponding tab The common reference electrodes are availa ble If unspecified is entered then the potential will be given in absolute value Note that it is possible to add a custom reference electrode and that the Reference electrode menu is also available in ConfiglOptions Reference Reference electrode SCE Saturated Calomel Electrode hi Offset potential vs Normal Hydrogen Electrode 0 241 Y Fig 40 The Reference electrode block 28 EC Lab Software User s Manual 2 5 2 3 Record Record Eces WE CA2 Pl Paw rer E 1 Analog IN 1 Se pa Ue Analog IN 2 4 Eas Record external devices on 4nalog INF ref CECA Fig 41 The Record block In addition to the variables recorded by default mainly Ewe Ref1 Ref2 or S1 52 and other variables depending on the chosen techniques the user can choose to record e the counter electrode potential Ec Ref3 Ref2 or S3 S2 e the power P Ene computed by the hardware e analog external signals pH T P using auxiliary inputs 1 Analog In1 and 2 Analog In2 These signals must be configured using the window opened by clicking
149. he curve that you want to zoom Zoom Back is very useful when you have zoomed an undesired zone It is not limited in the number of actions The Autoscale is made of different autoscaling functions according to each axis 3D is used to displaying the graph in a 3D mode e The second block contains the Analysis tools More information on Analysis are given in part 4 e The third block is dedicated to the addition of comments or notes on the graph with the possibility to Add and delete a comment zone and paste a comment from the clipboard The graphic parameters of the comment background size font and color etc can be edited by double clicking on the comment e The fourth block is to show or hide OCV points and abnormal artefact data points that the user wants to remove before an analysis or a print 70 EC Lab Software User s Manual e The fifth block is more dedicated to file selection with Load files Add files Selec tor LOG history The selector will be described in a following section e The sixth block is about the graphic display with the Active trace Add graph and Remove graph Ewe vs time faj_03 mpr This option shows the active trace that can switch o gt Tvs time faj_O4 mpr to the one of the other trace with a click e The seventh block can be used to start stop pause or go to the next technique of the experiment e The eighth block Copy and Print includes interesting tools Mal C
150. he displayed variables are the same for all the chan nels and all the instruments Double clicking on any of the channel window will replace the global view by the specific view of the selected channel Double click on a channel of the global view to select it You will get the following window EC Lab Software User s Manual r rea EC Lab V10 38 VMP3 192 109 209 237 channel 1 no experiment Experiment Edit View Graph Analysis Tools Config Windows Help X 048 a a a A P E T T shld fP maagg R H Be E No experiment loaded on current channel To create an experiment please select one of the following SP 300 236 actions YMP 300 235 N VMP3 237 a YSP 300 239 Selector y Show 1 a Load Settings wm New Stack a Load Stack Settings Experiment Advanced Settings Cell Characteristics External Devices oP O Status Stopped Time 0 0000s Ewe 3355Y 0 0004 Buffer 0 Eoc 3 355 Y 0 00 0 004h Range open VMP3 192 109 209 237 Chammell Ej Read mode pol 0 0 20 194 b s Fig 4 Main window for experiment setting This window shows at the very top in the blue title bar the software version the connected instrument the IP address if connected through a LAN the active channel the name of the experiment i e name of the data file and the selected technique if any 2 2 EC Lab Main Menu T Experiment Edit View Graph A
151. he final rest potentials and the pitting potentials obtained from all the channels used in the experiment N Stat connection mode used to work with several working electrodes one counter and one reference electrode in the same electrochemical cell This mode must be used with special connections see the user s manual N Stat box accessory provided for measurement in the N Stat mode This box has been de signed for multielectrode cell applications to simplify the potentiostat to cell connection Open Circuit Voltage OCV protocol that consists in a period during which no potential or current is applied to the working electrode The cell is disconnected and only the potential measurement is available Option EC Lab software window in the Config menu used to choose general parameters of the software such as automatic data saving or warning messages Pause button of the EC Lab main window that leads to a suspension of the progress of the protocol and the measurement recording The cell is disconnected OCV period The Pause button switches to Resume when clicked Peak analysis graphic tool used on an I E curve to determine the peak current the peak potential exchanged charge quantity and several other parameters Preconditioning previous part of the electrochemical experiment that consists of the equilib rium state establishment deaeration period accumulation of electroactive species on the elec trode surface or pret
152. he real ones A randomization is added before the fitting to select the most suitable set of parameter values The most suitable set of parameter values are the values that yield the lower x value x gives an estimation of the distance between the real data and the simulated data Its expression is BZ D Z E aram X 7 reaal simi p i 1 O l with Z a i is the measured impedance at the fi frequency Zu f param S a function of the chosen model S fis the frequency i param is the model parameters ex R1 R2 C1 Q1 a is the standard deviation Considering that for each frequency the impedance has the same standard deviation then o is equal to o In this case minimizing x is the same as minimizing x o Hence the expression of the x criterion as it is used in Zfit is x iZ 1 L simu tis param i 1 In this case the unit of x is Ohm If the user chooses to weigh the data points with Z the impedance modulus then the expres sion of x is i F y Zeus Less N param y E 4 The available minimization algorithms are the following gt Randomize if this is selected the software picks random values for all the parameters calculate the x and keep for each parameter the value that yielded the lowest x It should be mostly used to provide suitable initial values for a further minimization but can also be used as a minimization tool only slower and less powerful than the
153. heir acquisition the numerical filtering is available in the Math menu of the Analysis tab lt l gt vs Ewe UME_5Vs_sans compensation_1nA mpr cycle 3 UME_5Vs_avec compensation_1nA mpr cycle 3 Ewe V vs SCE Fig 52 CV carried out with an Ultra Microelectrode of 10 um in a solution of ferrocene in EtOH with TBAP as a supporting salt The range of current is 1 nA and scan rate is 5 V s Zoom at the vertex Blue line no compensation Red line High Speed Scan com pensation lt I gt vs Ewe CV_THF_Fc_1Vs_100pA_avec toutes corrections mpr cycle 3 CV_THF_Fc_1Vs_100pA_sans correction mpr cycle 2 Ewe V Fig 53 CV carried out with Ultra Microelectrode of 10 um in a solution of ferrocene in THF without any supporting salt The range of current is 100 pA and scan rate is 1 V s Blue line no compensation Red line High Speed Scan compensation 3 7 EC Lab Software User s Manual 2 5 3 4 4 Electrode Connections Standard connection See Fig 49 The working electrode is connected to P1 S1 the reference electrode to S2 and the counter electrode to P2 S3 S1 S2 S3 S for Sense are used to measure the voltage and P1 and P2 P for Power to apply and measure the current To set the standard connection proceed in the same way disconnect first S1 S2 and S3 from the cell and only after disconnect P1 and P2 select Electrode connections standard and set the next connectio
154. hoose the variables to display An example of the Bode diagram ob tained with the 3D representation tool is given Fig 106 E O E ae SS A 3 LEED ee a i eycle number log freq Hz MAGI y Sigs Cp gi Lm ofr LL ee he 3 S JAEN IV E 0 A Y IF 4 2 cycle number E TA ral A 2 ARA me TA a o Io NS log freq Hz Fig 106 Bode diagram obtained with the 3D representation Once on the 3D representation it is possible to reach the 3D menu by right clicking on the graph Fig 107 Thanks to this menu it is possible to come back to the 2D representation or to display simultaneously 2D and 3D graphs Similarly to the 2D representation it is possible to Copy and Print the graph as explained in section O page 84 The Graph properties menu for the 3D representation is the same as the Graph properties menu for the 2D graph detailed in the following paragraph 79 EC Lab Software User s Manual 3 2 5 Graph properties O wD 0 30 Copy E Print Ctrl P Graph Properties Fig 107 3D menu On the graphic window right click on the mouse and select Graph properties This Graph properties window is divided into 5 themes Traces Axes Units Graph and Options Each of them allows the user to define properties of the graphic display Graph properties Predefined Graph Style Line style Custom Graph Style Traces Ames Units Graph Options Lines M
155. i timers Ewe m cycle number CA mol L 1 CB mol L 1 CC mol L 1 ooo0o a0 0 88000 Same selection for all files Hide Additional Variables keep Previous axes process keep previous zoom Load Add Remove Undo Clear OF Cancel yl Fig 158 Variable selection window to display concentrations 111 EC Lab Software User s Manual CVsim mpr lvs Ewe CA vs Ewe CBvs Ewe CCvs EweH 1 gt WN O 5 000 f 6 a 10 000 4 15 000 2 20 000 0 0 5 Ewe V Fig 159 Interfacial concentration variation versus electrode potential Several examples are available in the CV Sim window To display an example one has to click on the Example button on the top of the CV Sim menu Then CV Sim examples win dow 112 appears to select the mechanism of interest Csin Examples Example Parameters E BLSI Mechanism EEEE El DLSI Rohm Felll Fell El DLSI Rohm Cdl Reaction El DLSI Rohm Col Reduction 4 ze lt gt B El DSS z 1 EE BLSI EO 0 Y EE DLSI Rohm O 0 102 kO 0 222 cm s 1 EE DLSI Rohm Cdl af 0 5 EEE DLSI Species 10 EEE DLSI Rohm Cdl 240 0 01 mol L 1 11 EEE DLSI Feilin Fein Fei I Feo CBO 0 mal L 1 12 EEEE OLSI DA 10e 6 cm2 s 1 13 T DLSI DE 3e 6 cmz s 1 Es Reaction Reduction B ze lt gt C O Co Ch cn E lp re Title Speci
156. i1 being the potential and the average cur li i 4i i5 rent without excluded points on the potential step AE 2 i2 on 2AE 3 i3 on AE or 3AE according to the selected method and 4 i4 2AE Note if there are several loops n gt 0 then the en In values are averaged on the different loops before the calculus 5 1 10 Multi Pitting Statistics Multi Pitting Statistics is a process which can be applied to Multi Pitting experiment files It gives the mean value lt E gt and the mean quadratic deviations o of the final open circuit poten tials Eoc and pitting potentials Ep of a set of electrodes or of a set of selected files Note that the Ep value corresponds to the potential measured for lp Multi Prtting Statistics Files C UserselectrochimesDesktop4y1 0 2040 ataSamples Corosion MP_concrete_in_ Nall mpr C Usersselectrochime Desktop 0 2040 ata amples Corrosion hMPP_ OS mpr C UsersselectrochimesDesktopy1 0 2040 ata S amples Corosion MPP O04 mpr CAU ser electrochimieDezktop 10 20 Data S amples Corrosion MPP 12 mor Load Add Bemove Undo Statistics channel E imit v 1 566 1 353 1 429 E oc w 1163 E Ept 0 0 0 714 0713 E inite SE init 0 420 E ocy gt S ae 0 322 V Print Settings Copy Print Close Fig 237 Multi pitting statistics window 173 EC Lab Software User s Manual 5 2 Data File import export functions 5 2 1 ASCII
157. ication Modify Cell Characteristics Geen Print C Export As Text i Settings In Columa With Floweharts C Import From Test F ris Error Messages C Extract Cycles Loops C F Cancel Modify C Se Split File F a Insert Technique From File C 3g Under Sampling SX Remove All the techniques C 194 Calibration 2 Reset Settings To Default C ne Retrieve Data From The Inestrame lt i Lock Tool bars de Spore erecta de one Fig 90 Options window Tool bars tab The tool bar option can be used to select the icons wanted in the main tool bar and the graph tool bar from all icons available in EC Lab software Both tool bars can be locked or unlocked This is effective only when the software is restarted It is also possible to select the functions available on the graphic right click menu Graphic Popup Menu and on the settings window right click menu Settings Popup Menu 66 EC Lab Software User s Manual 2 14 7 E mail menus Options Options default General Warning Text export Colors References Tool bars menus E Mail SMTP Configuration SMTP Host 192 109 210 211 User Mame fC Password fe From E mail 83 name domaincom 0 Port Cancel Fig 91 E mail tab SMTP server settings for sending mail and data from EC Lab The E mail tab is a new section available in option window of EC Lab software This option enables EC Lab to communicate wi
158. ices on Analog INH refs CECA gt Fig 36 Cell Characteristics tab standard connection with VMP3 technology 25 EC Lab Software User s Manual 2 5 2 1 Cell Description This window has a standard configuration and the battery configuration can be activated by clicking on the Battery button 2 5 2 1 1 Standard Cell Description frame Cell Description Electo material OOOO O O S O Comments Electrode surface area 10 001 Charactenstic mass 10 001 Battery gt Equivalent eight 10 000 greq Density 10 000 g cm Fig 37 Standard Cell Description frame You can either fill the blank boxes manually entering comments and values or load them from a mps setting file or a mpr raw file using Load Settings on the right click menu This win dow allows the user to e add information about the electrochemical cell material initial state electrolyte and com ments e set the electrode surface area the characteristic mass the equivalent weight and the den sity of the studied material The surface area is the area of the sample used as a working electrode and ex posed to the electrolyte The characteristic mass is needed if the user needs to express any variable per unit of mass It can be the mass of a whole battery or the mass of a sample The equivalent weight is the characteristic mass divided by the number of electrons exchanged during the electrochemical reaction in most cases the
159. iciency by a 2 order poly nomial function The RMS error is also calculated The Fig 233 below shows the CED Fit results obtained from 10 cycles charge discharge of a battery with a current rate of 135 mA 170 EC Lab Software User s Manual CED fit Selection Trace Efficiency ws cycle number From point 1729 Ai T 39 85 To paint 6901 k f E 39 04 lt Total points 7 Number of hidden points 4h b For unselected points only Results y x ay tax a x dy 39 05 0 013 7 2 249e 3 AMS Error 229 67 ppr Calculate Copy Save Fig 2333 CED Fit results 5 1 9 Polarization Resistance Polarization Resistance determines the Rp and Icor values from a Polarization Resistance files Select Analysis Corrosion Polarization Resistance to load the following window Click on the Load button to select a polarization resistance file Then a summary of the parameters will be displayed into the settings frame Note that it is possible to modify the elec trode surface area value for Rp in Q cm calculus here 171 EC Lab Software User s Manual Polarization Resistance Process File C manips lA echem Nicolas M4120326_1p41_C05 mpr Settings n 5 AE 50 mi n 10 Apply a second set of potential stepe s with reverse sign on AE electrode surface area 10 001 cme Options 3ponte AE AE 34E Method peinte 1 4ponts AE 2AE AE 24E point i to point 10 Calculate lt l gt for all the po
160. icted linear diffusion Mg anomalous diffusion G Gerischer element Ga modified Gerischer element 1 Gp modified Gerischer element 2 120 EC Lab Software User s Manual 4 3 1 1 Resistor R Description Resistor Impedance ei A Myquist Diagram Imi vs Rel a Fig 169 Resistor element description The resistor element is defined as a passive component with a constant value when frequency varies Fig 169 describes the resistor with its symbol its faradic impedance and a view of its Nyquist representation The resistor element is characterized by a constant value that can be measured in the Nyquist diagram by the Real part Re Z for an imaginary part equal to zero Im Z 0 4 3 1 2 Inductor L Description Inductor Ly PPP Impedance f L j2af Nyquist Diagram m7 vs Reli 0 D Fig 170 Inductor element description The inductive element has impedance with a frequency dependency as shown on the faradic impedance equation The Nyquist plot of an inductance is a vertical straight line in the imagi nary negative part Im Z lt 0 or phase 17 2 121 EC Lab Software User s Manual 4 3 1 3 Modified Inductor L Description Modified inductor Lay Impedance ZI L4 201 Noguist Diagram rd vs Reli IZ fl Li Zat Fig 171 Modified inductor element description The modified inductance La is an electric component defined on based o
161. idden file including the graphic properties of the corresponding raw mpr file As with the mgr file the mgp file is hidden and includes the graphic prop erties of the processed file mpp During the experiment e Data from measurement results are appended to the mpr file e Possible modifications of the parameter settings are updated in the mpl file and replaced in the header of the mpr file The mpl file is then the Log of the experiment During the experiment this file can be read with a text editor but users should not try to write in this file or to save it because any modification will make it unusable by the EC Lab software 2 11 2 Variables description Several variables are standard and common to any technique of the software Every data file contains state bytes that can be hidden in the selector Several additional variables are de pendent of the technique used Cf Additional variables Depending on the techniques some processed variables can be created either automatically or by the user For ElS techniques the variables are related to Z and admittance variables can be obtained by processing 57 EC Lab Software User s Manual Variables description Variable name unit Time time s current mA Ewe WE potential versus REF Ewe V dq charge increment between two recorded values dq mA h Ect potential control control V len Current control control mA Ectri lotri potential or current control co
162. ience Selecting all cycles for the fit and randomization on only the first cycle will lead to an automatic fit When the Minimization is launched a new graph is added in the bottom right corner This graph will display the equivalent circuit parameters obtained by the fit in this case R1 R2 R3 C2 C3 versus potential or time The user can have a time evolution or a potential evolution of the desired parameter E a Selection Fanar Equrvaleri cious RATALNA ACRAS Ed 5 pram pel sn ads uml dey es a E A Ri Oe L7 ha 03755 SPE Tesi Box 3 Circa Simp E SPER _ Teri Box 3 Creu S_1 A rap ctia 2l E DAE TeS F 14 323 E fa i 1014 Ohm 187 ct Re 521306 F 0 114 36 R3 Z qt 2748 Chinn 1 854 O Re z Ohm IO SPE Test Box 3 Circuit 3 7Miparsmonpp Comtubite iO vs Ep CoP vs Eres 8 Fit Select al gri a i E a a Method Rarndomza Smiles A aretas feel cic he ony T E a 5 She aae te 10000 del abr A Sp os S000 aair height Fl y Z 56 yx iv U begues 500 Sinis Cycki 21 imme Feud Copy Sawe Chas Fig 191 Successive fits on cycles with randomization on the first cycle We can see the evolution with the DC potential of the resistance R3 and the capacitance C2 The parameters of the equivalent circuit components are stored for each cycle in the File name_Zfitparam mpp file 138 EC Lab Software User s Manual References W H Press S A Teukolsky W T Vetterling
163. ientific articles Nevertheless the user can define his own style defined with all the functions of the Graph Properties window Traces Axes Units Graph Options 80 EC Lab Software User s Manual Creation of a new graph style is possible with the recorded automatically Graph properties Predefined Graph Style Line style Custom Graph Style Traces SES Wlaxis Y 2 amis Title Units Graph Ewe vs SCE Seale 2 79896 e 001 gt 1 22564 7e 000 Options Scientific Motation Process 4 Invert Axis J Grid Silver Options 01 Proportional Shift axes Origin A Custom k Font o Fig 109 Axes window ce button This new graph style will be All the Axes properties can be changed in this tab Select the axis you want to modify in the in dex tabs It is possible to change the title of the axis but also to adjust the axis range to the user s con venience The user can also change the notation to scientific mode or in vert the axis positive val ues on the left and nega tive values on the right The grids can be hidden while deselecting the box The user can choose the color and the style of the grid In the Options part the user can choose to display his data with the X and Y axes propor tional generally used for Nyquist representation and to differentiate from the rest of the grid the axis origin color style or line size The fon
164. ifed 0 000 AgfAgll KCI 3 5M Ag AgCI KCI sat d Ag AgCl Nall sat d Hg Hg2504 E2504 sat d NHE Normal Hydrogen Electrode SCE Saturated Calomel Electrode SSCE Sodium Saturated Calomel Electrode Fig 88 Option window references tab e Allows the user to add edit or remove his own reference electrode and its potential vs NHE Then the following window appears Reference Electrode Mame Voltage Home made Ag AgCl 0 250 W Fig 89 Reference Electrode window The new reference electrode will now be displayed in blue characters in the table The standard potentials of reference electrodes have been extracted from the following refer ences 65 EC Lab Software User s Manual Electrochemical Methods A J Bard amp L R Faulkner Wiley New York 1980 Electrochemistry for Chemists D T Sawyer A Sobkowiak J L Roberts Jr 2 Ed Wiley New York 1995 Handbook of Analytical Chemistry L Meites Ed McGraw Hill New York 1963 2 14 6 Tool bars menus Options Options default General Warning Text export Colors References Tool bars menuz E Mail Select the tems that are displayed into Hain Tool Bar we 2 New Experiment E Set Settings As Default d Load Settings C ETS Group Synch Stack Bipot F HA Import Settings From Text C Ef Reset Sequence da Load Data File C Copy Sequence lel Save As C Ed Faste Sequence F We Save Experiment As Custom Appl
165. ified staff will be glad to help you Please keep information on the following at hand Description of the error the error message mpr file picture of setting or any other useful information and of the context in which the error occurred Try to remember all steps you had performed immediately before the error oc curred The more information on the actual situation you can provide the easier it is to track the problem The serial number of the device located on the rear panel device Bio Logic SAS Model VMP3 s n 0001 Power 110 240 Vac 50 60 Hz Fuses 10 AF Pmax 650 W www bio logic info CAUTION CE DO NOT OPEN ATTENTION RISQUE DE CHOC ELECTRIQUE NE PAS OUVRIR The software and hardware version you are currently using On the Help menu click About The displayed dialog box shows the version numbers The operating system on the connected computer The connection mode Ethernet LAN USB between computer and instru ment G eneral safety considerations Y Class The instrument is safety ground to the Earth through the protective conductor of the AC power cable Use only the power cord supplied with the instrument and designed for the good current rating 10 A max and be sure to connect it to a power source provided with protective earth contact Any interruption of the protective earth grounding conductor outside the instrument could result in per sonal injury Guarantee and
166. ig 213 Rp Fit window the Tafel Fit The results can be copied to the clipboard to be pasted in the print window comment zone or in a text file They can also be saved in a text file LP_VASP mpr ale ys Ewe 0 06 0 04 0 02 lt gt mA 0 02 0 04 0 06 0 22 0 2 018 Ewet Fig 214 Linear polarization curve of an iron electrode in H2SQ 0 1 M Note The user can adjust the Ap Fit by grabbing and moving markers The fit result is auto matically updated 154 EC Lab Software User s Manual One could use the Linear fit to get the same results but the Ro fit is more convenient for the Rp calculation 4 7 3 Corr Sim The Corr Sim tool allows the user to simulate data in the same way as Z Sim see 4 3 2 According to the parameters contained in the Stern or Wagner Traus equation i e Ecorr korr Ba Bc CorrSim generates the response corresponding to the technique chosen in the Output LP VASP or CASP see Fig below Clicking on the Calculate button gives the simulated curve according to the parameters set The ouptut plot depends on the type of the techniques used The results can be copied in the clipboard to be pasted in the print window comment zone or in a text file They can be saved in a text file Corr Sim Parameters Ecor 200 rr loom a pA Use P and p a Use b and b b mooo eo Output Technique Llp ALE Ecord A E Ecor Er e Ecor 11 00 000
167. in a multichannel mode to start different experiments on the selected chan nels at the same time Hint small box appearing under the box pointed by the mouse It indicates the min and the max values accepted in the box range current range used in the experiment It is related to the current resolution Impedance defined by the ratio E I Info tab in the graphic display that gives the number of points and the size of the raw data file Integral tool available with the graphic display used to integrate curves IR compensation in the electrochemical cell the resistance between the working and the reference electrode produces a potential drop that keeps the working electrode from being at the controlled potential IR compensation allows the user to set a resistance value to compen sate the solution resistance Limits in the advanced settings window the experiment limits are used in two ways first to protect the electrochemical cell from damages during the experiment and second for the po tential control resolution Linear Fit tool available with the graphic display used to fit a curve as a straight line Linear Interpolation the linear interpolation allows the user to space out regularly each point of the data file The user can select to interpolate data by a defined number of points or a regular time between each point Linked experiments EC Lab offers the ability to link up to ten different experiments with the protocol l
168. in all commands usable on the graphic window The five first buttons are for the different mouse modes The four buttons in the second frame concern rescaling Data transfer from the instrument to the PC leads to immediate display in an automatic scaling A mode The graphic window is always rescaled These buttons allow rescaling on X axis Y1 axis Ee Y2 axis A and every axes a at the same time All the Analysis tools are Y Math General Electrochemistry Electrochemical Impedance Spectroscopy El Batteries Photovoltaic Fuel Cells a e F o T AS Corrosion Show Analysis Results available using a drop box The icon of the last used analysis is displayed in the graph tool bar The analysis can be per formed as many times as needed just by clicking on the icon Another tool bar is available with EC Lab graphic window On the left a scroll menu allows to choose among several predefined representations the desired one The available plots are dynamic and depend on the file type time evolution or frequency evolution vs Ewe 7 Show cycle 4 1 p Fig 100 Fast selection plot tool bar At the end of this menu the user can find a Custom option that opens the File selection window for further graphic visualization On the right part of the tool bar a Show option makes possible to the user to show only one cycle or one loop The user can define his own fast graphic displaying mode To do that se
169. ing frequency in the Option General menu see section 2 14 1 page 62 In the same menu the user can also define an automatic creation of the data file name 2 12 Changing the channel owner Click on Config User and enter your username in the following window l User Name Uzer name Use personal options Show window at startup Cancel Fig 82 User name window 60 EC Lab Software User s Manual In the case where the new user replaces the current user of a channel e g MyName EC Lab software displays a warning message WARNING channel x belongs to MyName By accepting the modification you will replace the current owner Do you want to con tinue lt is not possible to change the user name of a channel when an experiment is running Chang ing a channel owner is only possible when the channel is stopped 2 13 Virtual potentiostat If there is no instrument connected to the computer it is nonetheless possible to setup an experiment in the virtual mode including boosters and options for the instrument When the instrument is selected the corresponding number of available channels is displayed with addi tional choice for amplifiers and cables for SP 300 technology if required In this mode the user can create a setup and save it as an mps file Virtual Potentiostat Instrument Channels Amplifier Cable l lt None gt standard lt None gt low current 14 48 amplifier standard
170. ing from any failure to comply with these precautions GROUNDING To minimize the hazard of electrical shock it is essential that the equipment be connected to a protective ground through the AC supply cable The continuity of the ground connection should be checked periodically ATMOSPHERE You must never operate the equipment in corrosive atmosphere Moreover if the equipment is exposed to a highly corrosive atmosphere the components and the metallic parts can be cor roded and can involve malfunction of the instrument The user must also be careful that the ventilation grids are not obstructed An external cleaning can be made with a vacuum cleaner if necessary Please consult our specialists to discuss the best location in your lab for the instrument avoid glove box hood chemical products AVOID UNSAFE EQUIPMENT The equipment may be unsafe if any of the following statements apply Equipment shows visible damage Equipment has failed to perform an intended operation Equipment has been stored in unfavourable conditions Equipment has been subjected to physical stress In case of doubt as to the serviceability of the equipment don t use it Get it properly checked out by a qualified service technician LIVE CONDUCTORS When the equipment is connected to its measurement inputs or supply the opening of covers or removal of parts could expose live conductors Only qualified personnel who should refer to the releva
171. inker Linked experiment settings the user can save the settings of linked experiments as a mpls file This allows the user to easily load all the experiment settings LOG function of the graphic display that opens the log file mpl containing details and set tings of the experiment but no data points Loop protocol available in the linked experiments and used to repeat one or more experi ments It is different from the cycle in an experiment Low current option providing a sub pA resolution that can be added to each channel 197 EC Lab Software User s Manual This option extends the current range down to 1 nA This option can be added both to standard and Z option channel boards Min Max graphic tool to determine the min and max values on a selected zone of the curve Modify button of the EC Lab main window allowing the user to select a protocol change the experiment parameters before or during the experiment This button switches to Accept when the user clicks on Mott Schottky graphic display of 1 C vs Ewe curve and corresponding linear fit to determine slope and offset MultiExponetial Sim this tool can be used to simulate curves with multiexponential functions MultiExponetial Fit this tool can be used to analyze curves with multiexponential functions Multi pitting statistics off line processing function of the MPP and MPSP protocols that gives the mean values and the mean quadratic deviations of t
172. ints a Cac Calculate Ro In Cl Outputs Linear Polarization resistance Bn anodic F Ob 22 Rp cathodic 5 070 68 z Rp averaged 5 066 45 Number of digits 6 leon 4 386 Ede 3 Close Fig 234 Polarization Resistance process Then according to the experiment type it is possible to select the 4 points or the 3 points methods that both correspond to specific settings gt Fig 235 4 points method Fig 236 3 points method n 2 reverse steps n 3 do not reverse steps The 4 points method gives more accuracy so it is proposed by default Nevertheless it is not always possible to make a reduction after an oxidation so then chose the 3 points method Note one can perform more than the 4 points and 3 points method with the Polarization Re sistance technique but the process here accepts only these two 172 EC Lab Software User s Manual If several points have been recorded per potential steps n gt 1 it is possible to exclude some points for the calculus For example selecting Calculate lt I gt for point 3 to 10 will exclude the first two points Choose the Rp unit Q cm or A and click on Compute to calculate the next values e 4 Panodic P cathodic Panodic 7 me Raat gt 7 aa and o i al L Z 1 L L l 3 points method Ion with 7 and r 2 l l 4r o 1 Li l l l l 4 points method IT gt with e1
173. ion manual Getting Started Homepage Check for Updates HOR Newsletter PF About Fig 14 Help Menu The Help menu contains pdf files of the Software the In strument installation and configuration Manuals and several quickstarts This menu provides also a direct link to the Bio Logic website and a way to check for software Up dates It is also possible to access to the Newsletter au tomatically displayed when the software is installed for the first time on the computer and for each upgrade E galg The user can change the buttons displayed in the tool bar To do that the user can either click on Config Options Tool bars menus Main Tool Bar and select or deselect the desired but tons see part 2 14 6 page 66 for more details or right click with the mouse on the Main Tool Bar and choose Options EC Lab Software User s Manual Options default Genera Waring Ton expat Tool bars nenus EMail Select the tems that are displayed into Main Tool B Main Tool Ba E ta New Experment Graph Tool efault Fi O Load Settings Settings Popup Menu Stack Bipot T HA Import Settings From Text Graph Popup Mena I pel Load Data File E Copy Sequence El la Save Ag EJ Ej Paste Sequence F Fal Save Experiment 4 Custom Application E Modify Cell Characteristics Print E Export As Text 52 Do Settings In Column With Flowcharts E Import From Test E PN Error Messages EJ Extract Cycl
174. ion type reduction or oxidation if the experimental curve is obtained by a cathodic sweep an anodic sweep respectively The number of mechanism tab displayed depends on the chosen mechanism 1 tab for E mecha nism two tabs for EE mechanism and so on The higher the number of parameters to fit difficult is the fitting procedure 114 Example File Mechanism FE a EC Lab Software User s Manual El E2 Setup Selection Fit Reaction Reduction Ar ze d 6 a se W 0 206 Y ka w 9 1e 4 of Species Cg intial D4 Ca Initial Me 2 des m 3 06e 6 15392812 31 55e 9 Iterations 1000 Relative eror Duration 00 00 26 Calculate Copp Save Init guess Minimize Stop cm z 11 15be 3 3 2208 12 1 0e 3 16e 15 32 be 15 Fig 163 CV Fit window with two Tabs for EE mechanism 4 2 4 2 Setup tab In the Setup tab three blocks are available Electrode experimental conditions and potential scan In the Electrode block select the geometry of your sample Linear semi infinite or hemi spherical semi infinite and enter the radius of the sample The sample surface is automatically calculated In the Experimental Conditions block the user enter the temperature used for the experi mental CV The Ohmic drop electrolyte resistance Ra and the double layer capacitance can also be entered if they are known by the user 115 EC Lab Software User s
175. ircuits Remove Hove Up RIHAR ACSA ed i R1 C2 R2 C3 R Aw dd eean R1T C2A 2M3 5 A1 C2 R2 03 A3 04 R4 R1 C2 R2 W3 FAl le Redal Alt 4 R2 C2A3 C3 A4 44 C05A5 AltO1A2 C2 AS L4 A4 C5 F5 R1 01 7AR2 C3 R3 R1 01 AA 240 AAAR aCA 4 Fig 184 Z Sim Z Fit Equivalent Circuit Edition window The circuit base contains more than 130 circuits The user can create new circuits to be added in blue to the list The most usual circuits are described and explained on the right side of the 130 EC Lab Software User s Manual window This description contains the circuit scheme the faradaic impedance expression and the impedance Nyquist diagram 4 3 2 2 Circuit selection The user can pick a circuit in a list containing all the circuits or only some circuits according the number and type of elements desired in the circuit To refine the list the boxes Gal J E lement s l a la 13 Elements and is must be checked Please note that in the example above all the circuits with 4 elements containing at east 1 R and 1 C will be displayed which means the displayed circuits might contain L or W elements 4 3 2 2 1 Circuit description If the required circuit does not appear in the list the user can create it The new circuit can be written in the first frame top with several rules 1 For elements in series the used sign is For example for R in series with C the equivalent circuit will be R1 C1 2 For eleme
176. istics Fig 63 Loading options of the technique selection window If the boxes are checked it means that the default advanced settings cell characteristics and external devices settings will be associated with the inserted technique regardless of any change that was made Note that the Advanced Settings Cell Characteristics and External devices are the same for all the linked techniques If these boxes are unchecked it means that the parameters set in the existing techniques will be kept 42 EC Lab Software User s Manual This option is useful if you need very specific parameters that you do not want to be erased and replaced by the default parameters Note that more than one loop can be added to a linked experiment When the user clicks the Run button the program asks for a file name that will be used for all the linked experiments with the following rules experiment file name user file name _ experiment number _ experiment short name _ channel number mpr For example the file name MyFileName will be used to generate these files Experiment 1 no file name for the Trigger In option Experiment 2 MyFileName_2 MP_01 mpr Experiment 3 MyFileName_3 WAIT _01 mpr Experiment 4 no file name for the protocol linker loop Each of these files will store the corresponding data points for all the loops Note 1 It is possible to synchronize linked experiments on several channels 2 One data file
177. ively 3 3 5 5 CASP Fit Olt heor ba bc 5E Dal Do ss F Da be ps Pinus Selection 8 8 Trace lve time E b E b b iy HELL s l2 bof OEP E ee oe el y 07 95 n 48 To point 1465 ba bo ba bc oe Ol3 Icon ee ee oe Peery 3 OA 384 Total points 1466 It is assumed that the harmonics superior to 3 are not signifi cant so they are neglected in the calculation of lcorr Ba and Bc To validate the fit h l and h are given in the window This method leads to valid results only if h is positive h positive or equal to O and h negative The corrosion current is then fet 6h 3013 4 3 Jol 201 5h 3013 Input potential EE y Hs sil ATE Auto detect Wa i 0 000 rei fs 10 01 F Hz Outputs 611 1 053 m Bl2 2 023e 3 m la 0 868 5e 3 m Icom 3731 p 2 V34 l 2013 l 3013 Ol a Lisa NT TE E be 2 V8 5b 261 5h 301 l2 enor 0 2091 E Oh 30 3 The error gives an information about the quality of the cho sen amplitude and the quality of the fit Calculate Copy Save Close Fig 219 CASP Fit window 5 L M szaros G M szaros B Lengyel J Electrochem Soc 141 8 1994 157 EC Lab Software User s Manual 6 J P Diard B Le Gorrec C Montella Comments J Electrochem Soc 142 3612 1995 4 7 6 Electrochemical Noise Analysis The Electrochemical Current Noise ECN
178. le Ae Calculate Ohm i 7 _a5fe 6 F Select al cycles Method Randomize Simplex Randomize First cycle only Stop randomize on 10000 iterations stop fton 5000 iterations ll weight al ey 1 727e 3 yi 8 666e 3 Iterations 5000 Simples Cycle HHNH Minimize Pseudaol Copy Save Close Fig 193 Fit results and pseudo capacitance calculation The results can be copied and pasted in another document 4 3 3 4 2 Additional plots C EC Lab Data Samples ZPOT_Fe basique_ 1 zfit mpp Delta PhaselZN vs fred log spacing Detalh vs freq log spacing Delta Phase 7 deg wizened 0 1 1 10 100 1 000 10 000 100 000 lfreq Hz log spacing Fig 194 Plot of the relative error on Z and phase vs frequency log spacing 140 EC Lab Software User s Manual The equations used for this calculation are described below The same error plot exists for the real part and the imaginary part of the impedance The error is calculated for each frequency i AZ Z meas E A x 1 00 Ao 0 calc meas meas zZ Re Z eas E Rel ARe Z L a 100 Im 2 Im 2 Alm Z ass eao e eae 100 Right click on the graph to see the menu and select Selector to display the following window offering the possibility to display the relative errors The same window can be accessed from the rapid graphic selection ba
179. les then one can display specific loops or cycles To access the Cycle Loop selection the user needs to make sure the cycle number variable is contained in the data file either recorded automatically or through processing In EC Lab Analysis menu select General Electrochemistry Process data After loading the data file select Cycle Number and Process The following window appears Process Data Input Files CAUserstelectrochimiesDesktops5 amples Fundamental ElectrochemistysCy Fe basig Technique Cycle Voltamnmetry Processed File C Users electrochime Desktops amples Fundamental Electrochemistry Load Add Remove Clear Varnables To select from the input file To be added mode osred error cycle number 0 0 m O chargem4 h A discharge m h dldtm z cycle timers step times charge timers discharge times control changes counter Inc timers controls Enel m e e 1 All Process Average o steps 4 Allow Reprocessing Cycles definition auto Export As Text Count half cycles Process Display Fig 102 Loops cycles process Check the variables you need to have These will be more detailed in part 5 At the end of this operation DONE is displayed and a processed file mpp is generated in the same folder as the raw data file mpr Click on the Display button to automatically display the processed file A cycle selection tool is now activat
180. lles Tool Baca did 16 2 4 A A ee 17 2 5 EXPenmentS DOX acatar oia 18 2 5 1 Parameters Settings TaD errira da 18 2 5 1 1 Right click on the Parameters Settings tab oocccocccocccococococononoronnnonons 18 2 0 Le SCICCTING a E e hos 19 2 5 1 3 Changing the parameters of a technique ooocccccocccccncccccnnncnconnnencnnacincnnnons 21 2 5 2 Cell Characteristics Tacita 25 20 21 Gell DESCIOTOMN sn 26 2 5 2 1 1 Standard Cell Description frame oocoocoocconconconiocnoniconoonconnonoononnnnnos 26 2 5 2 1 2 Battery Cell Description frame occoccconccccconcconconocanoonocanonnocanonnonanonos 27 25 22 E a a 28 R ROCO a ROT 29 2 0509 Adyanced Setas a laibis 29 2 5 3 1 Advanced Settings with VMP3 VSP SP 50 SP 150 ooccocccccccccccncocnccononos 30 ad Sra al DOM MAN o lod do 30 Ae NS ei is 31 2 0 9 129 Electrode LON AS aos 32 2 5 3 1 4 MIISCCNAMCOUS rat veia ladies 32 2 5 3 2 Advanced Settings with HCP 803 HCP 1005 CLB 500 and CLB 2000 33 2 5 3 3 Advanced Settings with MPG 2XX oooccccoccccccconococnccncnnnonnnonncnnnnnnnonrnnnnnnnos 34 2 5 3 4 Advanced Settings for SP 200 SP 240 SP 300 VSP 300 VMP 300 35 o RIEAN A aac annceah arate canis canine aacanetasceawGcas 36 29942 Ne 36 2 5 3 4 3 Ultra Low Current Option ooccccocncccccnccccnncnonnconnnnnonnnnnnnnnnnnnnonanonnnannos 36 2 5 3 4 4 Electrode CONNECTIONS ooccccccccccocncoconnnonnncononnnnnnnnonnnnnnannnnnnnnnnannnn
181. lue of a parameter at an iteration and at an iteration i 1 The relative error is normalized so that it can be applied to any type of parameter R C L and so on Weight if Z is chosen more importance are given during the minimization process to the points with a high impedance modulus In this case x is divided by Z If 1 is chosen the same importance is given to all the data points and the expression of x is the same as defined above y was defined above and is the criterion that needs to be minimized The lower it is the better the fit is x N with N the number of points is a normalized expression of x whose value is independent on the number of points It is equivalent to an error During the fitting process the iteration number as well as the cycle number are displayed at the bottom of the window Fit Select current cpcle s Method Randomize Simplex ll Randomize Li ___ _E EE AAA Simples Randomize first cycle only Levenberg Marguardt o Randomize Simplex Stop randomize on I agi iterations Randomize Levenberg Marquardi Stopfiton 5000 iterations weight El gt y 0 029 97 AAA 0 0306 Iterations 5000 Simples Cycle Fig 188 Fitting method selection To perform the calculation click on Minimize 4 3 3 3 Application Considering the previous example ZPOT_Fe basique mpr the following result may be ob tained using the Randomize Simplex option with the default paramet
182. m an electrochemical experiment and follow the plot on the current graphic window and fit or analyze results from previous experiments on another graphic window The user has also the possibility to add graphs to existing graphic window In that case the window is divided in two graphs or more When an experiment is run the graphic window is automatically opened Default graphic pa rameters are chosen for example plot vs E for the CV technique The default graphic pa rameters can be replaced by other chosen parameters To do so right click on the graph select Graph properties and activate the box Save as default In the case of linked techniques two different graphic windows will be displayed one for all voltamperometric techniques as a function of time and one for the impedance spectroscopy Nyquist plot For synchronous multi channel protocol all the corresponding files are dis played in the same way as linked techniques The graphic window contains a right click menu different from the Parameters Settings window right click Plot Mouse Mode Autoscale 3D Analysis Show Analysis Results Comments Hide OCV Points Hide Selected Points Show All Points Load Files Alt O Add Files Remove Trace Alt R Save Data File As Ctril LOG History Edit Surface and Mass Load Settings On Channel Es d E x fe Op Add Graph Remove Graph Copy g Print Ctrl P Graph Pr
183. mat Absolute Time mm dd yyyy hh mm ss sss op tion For impedance data files an export text in ZSimpWin or Zview formats is available and allows to paste directly data into ZSimpWin or Zview software An export text in Bio Kine con ductivity Ascii file is also available For cyclic voltammetry files an export option in DigiElch format is available A use file is created in that case 174 EC Lab Software User s Manual While running experiment it is possible to export files To do so the user must check the Text export option into the Cell Characteristics window before starting the experiment Loops cycles text exportation If the selected file contains linked experiments loops or the cycle number variable processed files only then one can export specific loops or cycles Cyclesloops selection W Same selection for all files Export cycles E 8 Export all files into a single tet file Fig 239 Loops cycles text exportation Proceed in the same way as with the Selector check Same selection for all files if you want to apply the loop cycle selection to all the selected files If unchecked each selected file will have its own loop cycle selection Select loop or cycles if present with the Export box and edit the selection list with the following rules separate each single item by a lt item1 gt lt item2 gt lt item3 gt use to generate a list of consecutive items lt first item g
184. mi conductor E is the applied potential Erg is the flatoand potential The donor density can be calculated from the slope of the 1 C vs Ewe curve and the flatband potential can be determined by extrapolation to C 0 The model required for the calculation is based on two assumptions a Two capacitances have to be considered the one of the space charge region and the one of the double layer Since capacitances are in series the total capacitance is the sum of their reciprocals As the space charge capacitance is much smaller than the double layer ca pacitance the double layer capacitance contribution to the total capacitance is negligible Therefore the capacitance value calculated from this model is assumed to be the value of the Space charge capacitance b The equivalent circuit used in this model can be either aresistor and a capacitance the space charge capacitance in series The capacitance is calculated from the imaginary component of the impedance Im 2 using the relationship miz 2rr C aresistor and a capacitance the space charge capacitance in parallel The capaci tance is calculated using the following relationship Co Im Z 21f Z 2 This model is adequate if the frequency is high enough on the order of kHz The Cs variable is available for all the impedance techniques The C variable is available only for the SPEIS technique 4 3 4 2 The Mott Schottky plot The Mott Schottky plot presen
185. n 0 3 0 2 0 1 0 1 0 2 0 3 0 4 0 5 0 6 0 7 Fig 104 Comment zones on the graph To add Comment zones on the graph the user must right click and select Add comments Then an empty comment zone appears on the graph To modify this zone double click on it or right click on the zone and select Edit comments The following window appears Comment Text Comment 0 Properties Font Size B ER Alignment Align Lett z Font Color E Black Background Color _ Custom Transparency U F Show Arow Fig 105 Comment window 78 EC Lab Software User s Manual The user can paste analysis results or other comments into the text frame Several comment zone properties are available and the user can display an arrow and direct it through the de sired part of the curve by clicking on the end of the arrow To remove comments right click on the zone and select Delete comment or click on the Del keyboard button Note e The comment zone is automatically printed on the graph o If the graph window is being resized the size of the comment will remain the same Make sure the graph window is at the convenient size before adding a comment zone 3 2 4 Three Dimensional graphic A 3D representation is available by right clicking on the graph menu It is possible for files having less than 15000 points After clicking on the 3D menu the Selector menu is available and allows the user to c
186. n A0000 Beraliona Spin 5000 eat 7 weage B y 154403 e far 35553 100 200 lesioni 5000Erple Cycle Oca Rei Ghm Hamas ji z y Fig 190 Fit results with a combination Randomize Simplex and Z as weight In the case of a weight Z the x value is much smaller than without weight and tends toward zero It shows that weighing the data points with respect to the modulus of their impedance is 137 EC Lab Software User s Manual beneficial for the quality of the fit The results can be copied to the clipboard or saved in a fit file filename fit When the mpr file is displayed the fit results can be reloaded with the Show analysis results button Note that ZFit can be used with data represented with the Bode plot or the Nyquist plot Please note that it is now possible to stop the minimization before the number of iterations is Stop Pseudol Copy Save reached using the Stop button 4 3 3 4 Fit on successive cycles ZFit tool includes an option to fit successive impedance cycles For example in the case of potential steps with EIS measurements on each step we can make an automatic data fitting on each cycle successively without any action by the user The EIS spectra obtained on each step can be seen on the graph in the left hand corner on the figure below The potential was scanned from 0 to 1 V with 20 steps of 50 mV We can see the 21 EIS spectra that can be fit one by one at the user s conven
187. n of two CV graphs one compensated and one uncompensated 45 EC Lab Software User s Manual EC Lab V10 36 VMP3 192 109 209 236 channel 5 experiment Test technique Potentio Electrochemical Impedance Spectroscopy Experiment Edit View Graph Analysis Tools Config Windows Help amp bk 1f2 3 4 s e6 7 e o 10 1 12 13 14 15 16 A Felons Turn to OCV between techniques s l TE amp bal Nyquist Impedance Vv map gt Multi Sine aj_01_PEIS_C05 mpr kn Z vs Re Z Set Eweto E D0000 Y vs for tes hf m fas Experiment Record every d Advanced Settings o dt fos imiZ Ohm N Cell Characteristics Scan from fjs 00000 External Devices to ff Ng points per decade with or NT points from fi to ff lt gt vs Ewe 02 _CV_COS mor aj 04 CV_COS mer Re Z 0hm Logarithmic spacing mi o Show frequencies gt gt Linear spacing sinus amplitude Va mv Mims 7 07 mV With ohmic drop compensation wait for py period before each frequency average Nag measure s per frequency drift correction Repeat ng time s 0 Without ohmic drop compensatio E Range Ferati IAY Range width 05 Bandwidth 1mn32s scan Ewe V vs SCE qjtatus Stopped Time 0 01 15 Ewe 0 088 mi 0 000 4 Buffer 0 point 38 38 Eoc 0 088 mv freq 100mHz Range open cycle 1 VMP3 JL 192 109 209 236 Channel Readmode e 4 42e6 206 496 24 670 b s Fig 67 Linked
188. n sequences It is the user s responsability External device control and recording 6 4 1 General description EC Lab software enables the user to control external devices such as rotating electrodes and thermostatic baths and record external analog signals through the auxiliary DB9 connector The user must configure the output to control an external device and configure Analog In1 and Analog In2 inputs to record external signals Our instruments can control and record analog signals from 10 to 10 V Most of the external devices work in a 0 to 5 V range The figure below shows the external device window where the user sets parameters Many instruments are already configured in the software to be controlled by our potentiostats The list will be completed in the future versions of EC Lab software To configure external devices select External Devices in the Config menu The following window is displayed 185 EC Lab Software User s Manual Device Type Device Name Analog OUT T 0 0 0 0 0 Analog IN 1 e Convert EM to Delta Freg Hz Ww with 10 ee 200 Hz ma 10 Y 200 Hz mit Analog IN 2 Convert Ev to DeltalAVvOhm 8 with fo Y 1000 Ohm mas 10 y 1000 Ohm min Fig 253 External device configuration window The user must define several parameters to configure the external device to either be con trolled via the analog output left column or record measure data via analog input 1 and 2
189. n the inductance model L The modified inductance can be used to represent the presence of an unusual in ductance in the Nyquist diagram It has an impedance with a frequency dependency similarly to the inductance but with an additional parameter a1 as shown on the impedance equation Fig 171 The Nyquist plot of a modified inductance is a straight line in the imaginary negative part but not vertical Im Z lt 0 with phase a111 2 More info can be found in the correspond ing Application Note 42 122 EC Lab Software User s Manual 4 3 1 4 Capacitor C Description Capacitor Li Impedance 21 Cyjent Mpquist Diagram mf vs Rel Fig 172 Capacitor element description Capacitor C is a common electrical element representing an ideal capacitor lts impedance is frequency dependent The Nyquist plot of such an element corresponds to a vertical straight line in the imaginary positive part Im Z gt 0 or phase 11 2 The faradaic impedance de creases when the frequency increases 4 3 1 5 Constant Phase Element CPE Q Description Constant Phase Element CPE PE A Impedance 1 ale W Dilja Noguist Diagram Am vs Rel Fig 173 Constant Phase Element description The CPE impedance is also frequency dependent The Nyquist plot of such an element corre sponds to a straight line in the imaginary positive part Im Z gt 0 with a aTr 2 angle with the real axis The faradaic imped
190. nalysis Tools Config Windows Help Fig 5 The bar menu of EC Lab software main window The Main Menu bar has been designed in such a way that it follows a progression from the experiment definition to the curves analysis Each menu is described below 11 EC Lab Software User s Manual Experiment Edit View Graph Ana Edit View Graph Analysis Tools Cor 2 New Ctrl N New Stack da Load Settings Ctri L Load Stack Settings Import Settings From Text 4 Load Data File Ctrl 0 le Save Settings As Ctrl 5 save As Custom Application Import From Text Export as Text Ctrl T Accept Ctrl M pe Cancel Modify b Run Ctrl R Pause Next Sequence Next Technique Print Settings Print Graph Ctrl P Exit ZA test 06 _DPA_C03 mpr ZA Mtest_05_DNPV_C03 mpr ZA test 04_RNPV_C03 mpr ZA test 03_NPV_C03 mpr ZA test 02 SWV_CO3 mpr ZA Atest_01_DPW_C03 mpr Fig 6 Experiment Menu This menu allows the user to build a new experiment and load an existing setting file or an existing data file made with a Bio Logic potentiostat or another one EC Lab is able to read other manufac turer files formats Saving options are also available The second frame offers the user the possibility to Export as or Import from Text Experiment commands Ac cept Cancel Modify Run Pause Next Sequence and Next Technique are in the third frame Print and Exit commands can be found in the fourth frame The las
191. ng part from the others please refer to the part 6 1 page 178 for more details Usually the controlled current value cannot bypass the range If the user wants to apply 15 WA current to the cell the 100 LA current range must be chosen With all the instrument of the Bio Logic range the user can bypass the current range in the control mode in a limit of 2 4 times the range with several conditions on the potential In the galvano mode when the controlled current value is higher than the range the measured po tential range is reduced to 8 6 V instead of 10 V whatever is the chosen current range see figure below HA 15 10 5 6 5 O 5 0 6510 15 Ewet Fig 251 Current versus Potential available domain in the galvano mode 6 3 3 Particularity of the 1 A current range in the galvano mode The 1 A current range is a very special range The label 1 A of this range has been chosen according to the control in the galvano mode and the measurement in the potentio mode In the galvano or potentio mode the channel board structure limits the maximum continuous applied or measured current to 400 mA 800 mA for SP 50 SP 150 and 500 mA for SP 300 SP 200 SP 240 VSP 300 and VMP 300 In certain cases the user can bypass this value to apply or measure current pulses up to 2 4 A corresponding to 2 4 times the 1 A range see 6 1 The average current for either measurement or control must not bypass 400 mA 800 mA for SP 150 and SP 150
192. ni Nb points a Nose J Add noize Noise level 10 1 00 Lu Calculate Copy Save Close Fig 215 Corr Sim window for Linear Polarization The results provided by Corr Sim are used to present the CASP and VASP fitting tools 4 7 4 Variable Amplitude Sinusoidal microPolarization Fit VASP Fit A potential sine wave of constant frequency and increasing amplitude from Va min to Va max is applied to the system The frequency is chosen such that the impedance shown by the system Is its polarization resistance The amplitudes must be large enough such that the non linear behaviour of the system is reached The R determination is performed at each ampli tude OE see Fig 191 155 CorrSim mpr gt Rp vs sin ampl 0 1 sin ampl V EC Lab Software User s Manual 0 2 Fig 216 Output data for VASP simulation Please refer to the Application Note on VASP For a non linear system the inverse of the polarization resistance of the system can be calculated using a Taylor series 3 4 2k 1 2k 1 1 Da be per lcor Y TP PU Ro e 2k k 1 This shows that by plotting Rp as a function of SE one can obtain the corrosion parameters leor ba and De VASP Fit allows the user to fit data from VASP measure ments The output parameters can be given as f or b con stant The x is defined by the following equation K 1 N XxX N 2 X reas Xcari 3 K Darowicki Corrosion Science Vol 37 n 6
193. nnnnss 38 2 6 Accepting and saving settings and running a technique cccoccccoccccccncccnccncnccnnnnos 40 2 6 1 Accepting and Saving SettingS occccocccccnncconcconnocannnnnnocannnnanonnnnonannnnanonannnnons 40 2 6 2 Running AN experiment cccccceecceeeceeeceeeseeeceeseeseeeceeeseeseeeseeeseesseeeseeesaeees 40 2 7 LINKING TECNIQUES turas ss cda 41 2A MNJESCHPUOM and Set Si 41 Are APPICA ION as 43 2 7 2 1 Linked experiments with EIS techniques occccoccccnnccccnncnconcnnonannnoncnnonanoos 43 2 7 2 2 Application of linked experiments with ohmic drop compensation 45 EC Lab Software User s Manual 2 8 Available commands during the rUN oocccocccocccocncocncococonnnocnnonnnonnnonononnnnnnnonnnononos 46 2 o 0 IS 0 TNO UNS ar ace sce o E 46 2 8 2 Next Technique Next SequenCe ooccccocccccccnccoconononnooncnononononncnnnnnnnonncnonnnnnnnnnnnnos 46 2 8 3 Modifying an experiment IN prOQTESS ccoocccocccococncncnconnconnonnnonnnonanonaronnronaninanons 47 204 Repar CHANME luciana adi 47 2 8 5 Use of the Repair channel tOOl cooccocccccocnccocnoconnnnnnocncnnnanononnnnnnnnnanonannnnons 48 2 9 Multi channel selection Grouped Synchronized Stacked or bipotentiostat A ra ee ee 50 2 9 1 Grouped or synchronized experiMentS ccoocccnccccccnconcncncnconcncnnnonnnnconcnnnancnncnnnnos 50 232 Stack oxper mensa 52 OVO BANGIN OOS rad ee 55 21t Dala proper 57 201 Type of data Messina
194. not modified during the minimization the sign of the parameter value that can be changed by double clicking in the box If is displayed it means that the sign will be determined by the minimization the unit of the parameter adev parameter calculated using the Levenberg Marquardt algorithm This parameter can be assimilated to a standard deviation lt gives an estimate of the relevancy of the param eter if the dev is very high it means that a great variation of the parameter will not affect very much the quality of the fit Hence the considered parameter is not critical in the minimization process The Calculate button will calculate and plot the data points for the parameter values set in the table without performing any minimization 4 3 3 2 The Fit frame Select current cycles The Z Fit tool can perform successive fits with the same model on successive curves in the same data file The first thing to be defined by the user is the cycle 134 EC Lab Software User s Manual for which the minimization is performed either one single minimization performed on the cur rent cycle displayed on the graph or successive minimizations made on all the cycles of the experiment Minimization Method Default values are set for every parameter but they rarely fit the real experimental values Before fitting in order to help the algorithm to find the best values it is necessary to use initial values as close as possible to t
195. ns P1 and S1 leads to the working electrode 2 lead to the reference electrode S3 and P2 leads to the counter electrode Then click on Apply configuration button CE to ground See Fig 52 Disconnect the cables from the cell select Electrode Connections Electrode connections CE to ground and reconnect the Modify on disconnected cells only cell as follows P1 and S1 leads to the working electrode ill S2 lead to the reference electrode P1 GROUND and S3 lead to the counter electrode a Se 5a ground Fig 54 Configuration CE to ground N Stat for SP 300 technology WE to ground connection mode In addition to the CE to ground mode a WE to ground connection mode is available with the SP 200 SP 300 VSP 300 and VMP 300 Electrode Connections Modify on disconnected cells only ground Fig 55 WE to ground con netion for SP 300 technology This configuration is very useful for hydrogen permeation measurements where one working electrode is grounded and connected to two different couples of counter electrode and refer ence electrode Refer to the Installation and configuration manual of the corresponding instruments for more details on the CE to ground connection 38 EC Lab Software User s Manual Warning it is important to disconnect the electrodes from the cell before changing the elec trode connection because of the difference between the leads assignment the OCV m
196. nsions mp are created sion Automatically created file Raw data binary file which contains the current parameter settings re freshed at each modification of the detailed diagram and cell characteristic windows This file includes all the information of the mps file Files created by the user Settings file which contains all the parameters of the experiment The set tings can be saved as default for a given technique It corresponds to the header of the raw data file This file can also be generated for linked tech This file is generated when the user makes one or several fits on an mpr or a mpp The results of the fits are saved one after the other when the user clicks on the Save button This file is a text file that can be opened Each fit result can be printed alone or with other fits Temporary binary file available for particular protocols derived from the mpr file This file is used for real time display of parameters obtained by raw data processing e g the integrated charge since the start of the exper iment the average current between two recordings chronocoulometry Temporary files Temporary text file which contains the experiment conditions the instru ment IP number the channel number the username the filename and its location the parameters settings and the cell characteristics at the begin ning of the experiment The user can choose to keep this file using Con fig Options menu Hidden files H
197. nt maintenance documentation must do adjustments maintenance or repair EQUIPMENT MODIFICATION To avoid introducing safety hazards never install non standard parts in the equipment or make any unauthorised modification To maintain safety always return the equipment to Bio Logic SAS for service and repair GUARANTEE Guarantee and liability claims in the event of injury or material damage are excluded when they are the result of one of the following Improper use of the device Improper installation operation or maintenance of the device Operating the device when the safety and protective devices are defective and or inoperable Non observance of the instructions in the manual with regard to transport storage installation Unauthorized structural alterations to the device Unauthorized modifications to the system settings Inadequate monitoring of device components subject to wear Improperly executed and unauthorized repairs Unauthorized opening of the device or its components Catastrophic events due to the effect of foreign bodies IN CASE OF PROBLEM Information on your hardware and software configuration is necessary to analyze and finally solve the problem you encounter lf you have any questions or if any problem occurs that is not mentioned in this document please contact your local retailer list available following the link http Awww bio logic into po tentiostat distributors html The highly qual
198. nt measured can be 24 mA with a potential range 9 V The same thing is possible when the current is controlled For more details about that please see section 6 3 23 EC Lab Software User s Manual With booster ranges and 1 A range of VMP 300 VSP 300 SP 240 SP 300 and SP 200 this relationship is not valid Bandwidth The VMP2 Z VMP3 VSP MPG2 XXX series SP 50 SP 150 HCP 803 and HCP 1005 de vices propose a choice of 7 bandwidths damping factors and 9 for SP 300 SP 200 SP 240 VSP 300 and VMP 300 devices in the regulation loop of the potentiostat The frequency bandwidth depends on the cell impedance and the user should test filtering effect on his ex periment before choosing the damping factor The following table gives typical frequency bandwidths of the control amplifiers poles for the VMP3 VSP MPG2 SP 50 SP 150 HCP 803 and VMP2 Bandwidth 7 6 5 4 3 2 680 kHz 32 Hz Note For more details about bandwidth definition for the SP 300 SP 200 SP 240 VSP 300 VMP 300 instruments refer to the installation and configuration manual for VMP 300 based instruments When the mouse pointer stays for several seconds on a box a max 100 hint appears The hint is a visual control text that gives the user mir 0 information about the box It shows the min and the max values SA of the variable as well as the value that cancels the box i e the Fig 33 Hint value for which the box will be skipped
199. ntations window will be displayed in this window select the Advanced tab and the four already predefined Graph Styles will be displayed 91 EC Lab Software User s Manual Fig 123 To define your own Graph Style click on the button the window Graph Properties will be displayed as shown Fig 124 Graph Representations Mame Ewe vz t Representation 4dvanced Ewe we vs Ewe Graphic style association delta vs Estep logll ve E we Ewe ve logll O vs t Techniquel Line style Line Markers style x ve t Select ety prop style Power vs t Monochromatic style Energy vs t Ap vz t Bode Impedance Nyquist Impedance Black Impedance Fig 123 Graph Style selection Graph properties NES Predefined Graph Style 22 8 Traces Y Legend Axes Position Top E Units Font Name Arial Font Style Standard 8 2 Options Background White v Transparency L 0 Title Text Title Font Name Arial Font Style Bold 12 Font Color H Black Graph Back Color _ White Graph style name Mame My Style Fig 124 Graph Properties window in the Graph Style creation 92 EC Lab Software User s Manual When clicking on the e button a Graph Style name window appears then the user can choose the name of the new Graph Style For this example a Graph style named Style ex ample is defined in such a way that the curve 1 i
200. ntrol V mA Ece CE potential versus REF Ece V Ewe Ece WE versus CE potential Ewe Ece V lt l gt average current over the potential step calculated from dQ dt lt I gt mA Mode Intentio Potentio Relax State byte bits n 1 and 2 mode Oxidation Reduction State byte bit n 3 ox red Error bit State byte bit n 4 error Control changes State byte bit n 5 control changes Changes of Ns State byte bit n 6 Ns changes Experiment counter value has changed bit n 8 counter inc Temperature control control C Temperature measure T C Rotating electrode speed control value speed rpm User defined recorded variable with its unit set User Unit as additional analog inputs QCM frequency variation Af Hz Hz Dilatometer displacement Displacement um Additional analog input 1 Analog In1 V Additional analog input 2 Analog In2 V Additional analog input 3 for VMP only Analog In3 V dQ charge on a potential step dQ mA h AQ charge on a cycle AQ mA h forward in pulsed techniques current measured at the end of the pulse I forward A reverse in pulsed techniques current measured on the reverse part reverse A delta difference between forward and reverse delta A E step potential step increment Sweep pulsed techniques E step V 98 EC Lab Software User s Manual Q Qo charge from the beginning of the experiment Q Qo mA h Q charge Q for a charge cycle reinitialized every cycle Qcharge mA h Q discharg
201. nts in parallel the sign is For example for R in parallel with C the equivalent circuit will be R1 C1 3 If several elements are in series or parallel with each other then the considered ele ments must be set between brackets For example for R2 and C2 in series together and in parallel with R1 the equivalent circuit will be R1 R2 C2 4 To write circuits it is necessary to give a number for each element to differentiate the elements If the syntax is not correct an error message will be displayed A circuit definition error empty circuit 5 Ifthe new circuit is already in the list this message will be displayed A R1l Q1 R2 C3 R3 is already included inte the circuit list 6 If the new circuit is equivalent to an existing circuit the following message will be dis played 131 EC Lab Software User s Manual Circuit R1 Q1 R2 C2 R3 is equivalent to circuit RL Q1 R2 C3 R3 Do you really want to add it 7 Circuits created by the customer will be stored in the list in blue They can be modified removed from the list or moved in the list 8 For the selected file PEIS_Fe_basique mpr find the correct circuit Randles Circuit R1 Q2 R2 W2 9 Click on Calculate to show the corresponding curve on the graphic window Z Sim Set Frequencies fom F 100 000 kHz e E en Es e a Es ma HE WE ho H 1 000 mHz Nyquist Impedance Show with 10 points
202. ode surface area or for the characteristic mass The following window will be displayed Edit pararneters File CY platinum 10 cycles n mpp Parameters Electrode surface area cre Characteristic mass 0 001 go K Cancel Fig 111 Electrode Surface Area and Characteristic Mass window The Electrode Surface Area and Characteristic Mass window is used in the unit window for charge density or current density plot The characteristic mass is also used for specific power or energy plot The user has to set the working electrode surface area characteristic mass and choose the unit Clicking OK will modify the graph according to the new surface but this area is not saved in the raw file 82 Graph properties Line style Custom Graph Style Traces Axes Units Options O Predefined Graph Style v Legend Position Font Name Font Style Background Transparency Title Text Font Name Font Style Font Color Graph Back Color Top Arial Standard C White Title Arial B old BB Black C White 0 Graph properties O Predefined Graph Style Line style Custom Graph Style Traces Axes Units Graph amp Current polarity convention Positive oxidation standard IUPAC convention pP Positive reduction inverted convention Monitor Monitor format auto Fig 113 Options win
203. of reaction can be represented by an equivalent circuit of resistors capacitors inductors and diffusion ele ments with specific values Knowing these values and the type of equivalent circuit help inter preting the impedance data The EIS section of analysis menu is especially dedicated to the analysis of EIS data It is possible to simulate various EIS diagrams with Z Sim tool or to fit with various electrical circuits an existing diagram with Z Fit tool woe Fit A Z Sim ut Mott Schottky y EK Kramers Kronig Fo cz F5 FS Fig 168 EIS menu The following section describes the electrical components Z Sim which is the EC Lab Impedance graph simulation tool Z Fit which is the EC Lab impedance fitting tool the Mott Schottky fit dedicated to semi conductor analysis and the Kramers Kronig transformation which helps determining that the impedance measure ment was performed on a linear stable time invariant system and is hence valid 4 3 1 Z Fit Electrical equivalent elements The impedance analysis tool contains currently 13 different electric components These com ponents are R resistor L self inductor La modified self inductor C capacitor Q Constant Phase Element CPE W Warburg element simulating the semi infinite diffusion Wa Warburg diffusion element simulating the convective diffusion M restricted linear diffusion Element Ma modified restr
204. oltammety CY is the most widely used technique for acquiring qualitate informations about electrochemical reactions CY prowides informations on redox processes heterogeneous electron transter reachons and adsomption processes It offers a raped location of redox potential of the electroactwe species LY consists of scanning linearly the potential of a stabonary working electrode using a triangular potential wavefonmn Durning the potential sweep lhe potentostal measures the current resulting from electrochemical reachons consecutive to the applied potential The cycle voltammogram is a current response as a function of the applied potential Fig 29 CV technique picture and description on the experiment window 2 5 1 3 Changing the parameters of a technique When a technique is selected the default open window is the Parameters Settings window The user must type the experiment parameters into the boxes of the blocks Two ways are available to display a technique either the detailed flow diagram Fig 30 and its table or the detailed column diagram Fig 31 It is possible to switch between the two modes of display using the o button Setting pa rameters can also be done using selected settings files from user s previous experiment files Click on the Load Settings icon B then select an mps setting file or a previous mpr raw file corresponding to the selected technique and click OK You can right click on the mouse and select
205. om 10 Y 10 Y More information gt gt Safety Limits Ene Max oo Ewe min 0 00 vw Il 000 m I Gol 0 00 m s h on IN 1 max 000 Analog IN 2 max F oo y for t gt Wo me J Do not start on E overload Electrode Connections Modify on disconnected cells only LE to ground ref refs Miscellaneous Text export Filter uy Edil Smooth on paints Create one data file per loop linked techniques only Default Fig 49 Advanced settings window for HCP 803 HCP 1005 CLB 500 and CLB 2000 in strument 2 5 3 3 Advanced Settings with MPG 2XX It is the same window as Fig 49 except that the electrode connections are not displayed as only one connection is available with MPG 2XX CE to ground connection 34 EC Lab Software User s Manual Safety Limite Ene Max ooo Y Ewe min 0 00 w Il o 000 ma IQ Gol m s h Analog IH 1 000 Y Analog IN 2 ooo 8 y hor t gt ES me Do not start on E overload Miscellaneous Text export m Smooth an points Create one data file per loop linked techniques only Fig 50 Advanced settings window for MPG 2XX instruments 2 5 3 4 Advanced Settings for SP 200 SP 240 SP 300 VSP 300 VMP 300 The main differences with the VMP3 technology is that Analog filters are available the com pliance cannot be adjusted and it is possible for the channel to be floating Filtering Ewe l 50kHz Safety Limits
206. on notes Orr In0 E E The corrosion analysis menu contains the classical corrosion tools such as Rp Fit and Tafel Fit but also a tool to simulate corrosion curves an analysis of electrochemical noise and two tools to determine easily and quickly current and coefficients of corrosion Moreover two dedi cated processes are available for the VASP and CASP techniques E Tafel Fit FS Rp Fit FS re Corr Sim fe VASP Fit ltt CASP Fit hh Electrochemical Noise Analysis F3 Polarization Resistance Ctri Fb La Multi Pitting Statistics Ctrl F7 Fig 207 Corrosion menu 4 7 1 Tafel Fit The Stern equation predicts that for E gt gt Ecor the anodic reaction predominates and that for E lt lt Ecor the cathodic reaction predominates This is known as the Tafel approximation Int0 E E e for E gt gt F sei InlOjE E I hor op E for E lt lt E soir This can be written 149 EC Lab Software User s Manual E Ecorr Egel 0 y for E gt gt Ecorr HE Ecorr lx 10 Po for E lt lt Esorr corr So in a log I vs E representation one should see two linear parts for E gt gt Ecorr and E lt lt Ecorr E E log log hor for E gt gt a B E E log Xy g log hor j for E lt lt Exon C 4 7 1 1 Tafel Fit window The Tafel Fit window allows the user to find the anodic and cathodic Tafel coefficients using a log I vs E represent
207. operties Alt P Fig 93 Mouse right click on the graphic window The right click window is divided into several blocks e Inthe first block four menus are available 69 EC Lab Software User s Manual Plot d e Mouse Mode Autoscale Scroll LS 3D We Cursor Analysis tt Selection Comments Aa room Hide OCW Points SL Zoom Hide Selected Points Zoom Back Shows All Points seats Load Files Alt 0 Ws ALS E Add Files vine A Beis A A Remowe Trace Alt R Ta WL Axis 4lt lel Save Data File As Ctrl S E WO Axis A LOG History F Edit Surface and Mass Load Settings On Channel ES Add Graph Remove Graph Copy Print Ctrl P Graph Properties Alt P Fig 94 Plot Mouse mode selection and mouse auto scale options The Plot tab for the selection of variables displayed on the graph More info on this are given in part 3 1 4 You can either display the predefined representations available in the Rapid Plot selection tool bar or a custom representation see 3 1 3 The Mouse Mode selection contains The scroll is used to move the curve on the graphic window The cursor allows the user to display the coordinates of all the points of the curve The selection allows the user to select zone of the curve data points either before a fit or an analysis or to hide bad data points Zoom and Zoom are used either with a zone selection smoothing or by a mouse left click on the part of t
208. opy Pun on channel 5 SN 5702 Grouped channel s 5 User CE vs WE compliance from 10 to 10 Y Electrode connection standard Ewe ctrl range min 2 50 Y max 2 50 Y Acquisition started on US 20 2011 17 02 25 saved an File peis3_ 05 mpr Directory Echeu wi b4bites manipwib4b Nicolas Mtests_ Host 192 109 209 103 Device VMP3S SN 0230 Address 192 109 209 255 EC Lab for windows vl0 le software Internet server v10 12 firmware Command interpretor v10 12 firmware Electrode material Initial state Electrolyte Comments Electrode surface area 0 001 cm Characteristic mass 0 001 q Equivalent Weight 0 000 greg Density 0 000 g cm 4 WW j or can Fig 114 Experiment history window The parameter modifications while the experiment is running are added to the end of the file The number of points and the file size are displayed on the top of the window near the file name This file is contained in the mpr file but can be separately saved if needed using Con fig Options General For bipotentiostat technique the log file includes the parameters of setting and probable mod ifications for both disc technique and ring technique The user can display and shift from the experiments detail of the technique performed on the channel disc channel to the experiment details of the technique performed on the ring disc by checking the appropriate box CV CA bipot mpr LOG RING CHANNEL SETTING
209. opy Graph Alt G f Copy Data Alt D Copy Graph Advanced a Copy EIT Data Condecon Fig 95 Mouse copy mode The copy mode contains the graph copy the data copy and the Z data copy Copy graph is a copy of the graph to the clipboard in a bitmap format Copy data makes a copy of the active data plot X Y1 Y2 displayed variables Copy Z data copy data in ZsimpWin compatible format in order to paste data directly in this software e The ninth block Graph properties can be used to change all the graphic parameters of the trace All these options are explained in more details in the following paragraphs 3 1 1 Loading a data file The EC Lab software is provided with sample data files The user can load data file in Exper imentiLoad Data File or in the graphic window with the mouse right click select Load Files The following window is displayed 71 EC Lab Software User s Manual a Open G di t Computer 05 C Data F4 Organize New folder Y E Mame Date modified RI Desktop CA ULC COL 18 07 2014 14 38 MPR File de Downloads OCV_CD2 17 07 2014 14 35 MPR File El Recent Places ZRA_CO1 21 07 2014 09 20 MPR File all Libraries Documents al Music Pictures EE Videos Computer E Os C G bio logic bio loaic loc ZA File name Fig 96 Open file window Select the data file you want to open and click on Open The user can also select and open data file from othe
210. orm an autocalibra tion usually after connecting the instrument to EC Lab the user name the mouse coordinates on the graphic display the data transfer rate in bit s 2 3 5 Current Values Tool Bar On the left side or at the bottom the Tool Bar with the Current Values can be seen o se Pa E it A eed al eel Fig 22 Current Values Tool Bar e Status gives the nature of the running sequence oxidation reduction relax open cir cuit measuring the potential paused or stopped Buffer full will be displayed in the case where the instrument s intermediate buffer is full saturated network e Time Ewe and Current are the time the working electrode potential and the current from the beginning of the experiment Buffer indicates the buffer filling level Eoc is the potential value reached at the end of the previous open circuit period Q Qo is the total charge since the beginning of the experiment range The current range 2 4 EC Lab Software User s Manual e Io or Eo lo is the initial current value obtained just after a potential step in potentiodynamic mode e N is the number of the current sequence e Neis the number of the current cycle or loop Note Two protocols Batteries GCPL and PCGA propose the additional variable X Xo which is the insertion rate This Tool Bar can be unlocked with the mouse and set as a linear bar locked to the status bar at bottom of EC Lab window or to the gra
211. ormation is displayed on the global View window e user the channel is available no username or is was used by another user Several users can be connected to the instrument each of the users having one or several chan nels e status the running sequence if an experiment is in progress Oxidation Reduction or either oxidation or reduction in technique Relax for open circuit potential for a paused experiment and for channel where an error happened e tech the experiment type once loaded e g CV for Cyclic Voltammetry GCPL for Gal vanostatic Cycling with Potential Limitation PEIS for potentio impedance etc e cable only for SP 300 SP 200 SP 240 VSP 300 and VMP 300 the type of cable con nected to the board standard if a standard cable is connected to the board low current if the Ultra Low Current option is connected or straight if no cable is connected e amplifier the booster type if connected 1 A 2 A 4 A 5 A 8 A 10 A 20 A 80 A 100 A a 500 W a 2 KW load or none VMP2 VMP3 technology 1 A 48 V 2A 30V 4A 14V and 10A 5V for SP 300 technology For VMP 3 technology a Low current is displayed as amplifier tyoe when the low current board is connected to a channel board The user has the ability to add several current variables on the global view such as time Ewe buffer Temperature control Ese Ewe Ece These variables can be chosen by right clicking anywhere on the Global View Note that t
212. ot converge if the initial values are too much different from the minimum ones it may fall into a local minimum of yx Ecorr lcorr Ba Bc or if the I Ewe curve is linear around Ecor In that case the following message will be displayed The trace KE appears to be linear within the selected zone The minimization may fall Do you want to proceed anyway ee a Fig 212 Tafel Fit minimization message For this reason it is possible to enter directly Ecorr corr Ba and Be values and then start the minimization Unchecking the boxes around Ecorr corr Ba and Be will remove the corresponding parameter from the minimization At any time one can restart the calculation from the linear fits by clicking on the Calculate button Reference 1 Stern M and Geary A L J Electrochem Soc 104 56 1957 2 Press W H Teukolsky S A Vetterling W T Flannery B P Numerical Recipes in C second edition Cambridge University Press section 10 4 408 412 1999 4 7 2 Rp Fit For E sufficiently close to Ecorr it is possible to simplify the Stern equation so that f E E Ba Pe into ar cC This equation is commonly presented with E as function of I l E o abe Ey lanbi B In10 When expressed this way it is easy to see that E Ecor for 0 The slope of this equation dE dl is named the polarization resistance because it has the unit of a resistance if the current is used and is commonly abbreviated R
213. other two tools gt Simplex also called Downhill Simplex is a minimization method per se mostly used to minimize linear functions gt Levenberg Marquarat it is also a minimization method mostly used to minimize non linear functions Using the parameters entered in the table as initial values these two iterative methods that will provide the parameters yielding the lowest x If the initial values are too far off these two algorithms will not converge It is the reason why two other minimization processes are offered gt Randomize Simplex Randomize is first used to provide optimal initial values for the subsequent Simplex minimization gt Randomize Levenberg Marquarat Randomize is first used to provide optimal initial values for the subsequent Levenberg Marquarat minimization Randomize if the experiment contains several cycles and all cycles are selected for the fit the user has the possibility of selecting the Randomization on the first cycle only or on every cycle The number of iterations for which the Randomization is stopped can be chosen 135 EC Lab Software User s Manual The more iterations the more likely it is that the optimal initial values will be found The more parameters are used the more iterations are needed Stop Fit it is possible to set a stop condition for the minimization iteration either on the number of iterations or on the relative error The relative error is the difference between the va
214. parameters is sent to the instrument when clicking on the Accept button l It is taken into account within 200 us for instruments of the VMP3 family and VMP 300 family All information on the change the time it was done the new settings etc is appended to the Log file see section 3 2 6 page 83 Note that a warning message could appear before ac cepting the modification if this option is selected in Config Option Warning Among all the parameters some of them cannot be modified on the fly such as range E range and Band width 2 8 4 Repair channel This tool allows a user to repair a channel board To have repair channel window click on Tools menu and then repair channel windows The window below will be open The window contains four blocks 1 Channel 2 Data buffer 3 Change saved file name 4 Reset Repair Channel single channel with no technique Channel Data butter Lock input channel data butter Change Saved File Name File z lt Mone gt Reset Data buffer will be emptied and esperments settings will be deleted Fig 68 Repair channel window First block Selection of the channel the user wants to repair The user should not modify the connection mode Ethernet or USB In case of a multichannel instrument it is recommended to select the channel to repair and then select the same channel number in the repair channel window 47 EC Lab Software User s Manual Second block This block allows use
215. phic bar at the top of the window Channel 4 values ES PA AE Fig 23 Current Values Tool Bar in a linear format Note In the default configuration all the tool bars are locked in their position At the user s convenience tool bars can be dragged to other places in the window To do so click on Con fig Option Tool bars menus and deactivate the Lock Tool bars box This will be effective after restarting the software Once the user has defined a new configuration of the tool bars the tool bar can be relocked the same way it was unlocked Note also that some of the current values can be displayed in bold using the Config Op tion Colors tab Devices box As mentioned earlier it is now possible with only one EC Lab open session to be connected to and control several instruments In earlier versions of EC Lab it was necessary to open as many EC Lab sessions as the number of instruments The Multi Connection is performed using the Devices box on the main window See Fig 4 and 23 The and buttons allow the user to add or remove instruments linked to the computer either through USB or Ethernet The and ve buttons are used to connect and disconnect respectively an instrument to the computer The button is used to show the global view PEETI 5 as described in the beginning of part 2 1 Finally the in potentiostat See part 2 13 button is used to connect to a virtual Devices elt MMPS 23
216. pression SEE AO xIlOIOII IIII logh logarithm for a specified base LogN Base X Variabla sing sine of an angle in rad ys 1 cosi cosine of an angle im rad tan tangent of an angle in rad fly Infos arcsing Inverse sine in rad arccos inverse cosine in rad arctan inverse tangent in rad sinhQ hyperbolic sine of an angle in rad cosh hyperbolic sine of an angle in rad tanh hyperbolic tangent of an angle in rad arcsinh inverse hyperbolic sine in rad arccosh inverse hyperbolic cosine in rad arctanhd inverse hyperbolic tangent in rad PI 3 1415926535897932385 degtorad conversion of degrees to radians radtodeg conversion of rad to degrees Fig 121 Axis processing window and available mathematical functions 3 2 10 2 How to create your own graph representation for a specific technique To facilitate data treatment it is possible to create a specific representation for each technique For this the user has to click on Add in the bottom of the Graph Representations window then a User x variable is automatically created The user can change the name of the dis 90 EC Lab Software User s Manual play and select variables to be displayed on X axis and on Y1 and Y2 axes in the Represen tation window A processed display for each axis in the Advanced window can also be de fined Once definition of each axis done it is possible for the user to define the Graph style but also the techniques to whi
217. r select Custom File Selection Files z z z Vanables C Users 5amplessEIS4PEIS Fe Bbasique_1_2htmpp Representation Custom freq Hz Rele hm Imie hm 10 hmm Phazel deg Delta Rel 2 Delta Im lt N Deltalel T DeltalPhaze lt deg Ref Ohm 1 7 Imie O Arni 1 fMi Ohm 1 Fhasefr ideg Same selection for all files Frequencies Hide Additional ariables W keep previous ares process L keep previous zoom boad Add Bemove Lindo Clear Cancel Fig 195 Selector for the Zfit mpp file offering the possibility to display the relative er rors These additional plots may be very useful in evaluating the acceptability of the equivalent cir cuit selected and the relevance of the measured data points 141 EC Lab Software User s Manual 4 3 4 Mott Schottky Fit Only the instruments equipped with the EIS measurement option have the capability of Mott Schoitky fitting 4 3 4 1 Mott Schottky relationship and properties of semi conductors The Mott Schottky relationship involves the apparent capacitance measurement as a function of potential under depletion condition A C ese N e e where Csc IS the capacitance of the space charge region e is the dielectric constant of the semiconductor o IS the permittivity of free space N is the donor density electron donor concentration for an n type semi conductor or hole acceptor concentration for a p type se
218. r cycle and sequence Summary per protocol and cycle Constant power protocol summary CED Fit Polarization Resistance Multi pitting Statistics All these functions are available off line after the experiment They create new binary files mpp based on mpr files with additional or removed variables These files can be created during the experiment at a given time or after The structure of the raw files mpr is defined to store all variables of interest and also be as compact as possible with no variable redundancy Nevertheless other variables obtained from the raw file may be of interest For example in potentiostatic mode the instrument acts as a coulometer that performs charge recordings at periodic interval in charge or time In prac tice it is more usual to display the current Thus in such a case data processing proposes calculating a charge increments between two recordings From battery experiments several variables are of interest such as resistance They can be extracted from raw data files in a compacted file Data processing 5 1 1 Process window Select Analysis Batteries Process Data to load the processing window 160 EC Lab Software User s Manual Process Data Input Files C UserselectrochimesDesktoo4PiITT A pa Technique Potentiodyranic Cycling with Galvanostatic Acceleration Processed File Co Users electrochimieDesktop PITT 1 IQsnE mpp Load Add Remove Clear Y anables
219. r ee eer eer eh ep ei ar A 74 Trans o cstic aes chet A cas etd ce seed cea See ae 63 OTN S 10 tests doce EOI E OU O A a Guanine anaeat 151 Electrode SUMACS Al Ca tii il 27 83 El ctrodes COMMCCIO NM veedor diia 33 He AS WIG OMULOMI MOG aasaiicc nat hacidaes Sicteca nad bad dan sie a a hea dae 40 DELICIA o a ce eee 39 Na 33 o es A A O ON 33 39 WE TO CV OUING usd ici 39 EQ Mint a dd dt E 193 EQUIVALE NEW etarra 27 151 153 Experiment MOI SAA o e e a aa 48 NextSequentce cats cb dis 47 Next Technique vensausnsgecsprnaudsaurantenstinaudnaunasuenabinaudaauvaauenabiaaudnaunnsudnaliaeddnaNnaaudeatiaeddaaunaeunnabil 47 A dl ao 47 O T 41 SAV rage asada eae ea eee ah ceed cant cece teehee areola 41 LO grr egr ee a eee PRTC Pe A ETT Sen OE CE EM CNET A Tene rent emer PCr 47 EXDOMDAS TO taa a ias 33 175 AS msn in God 175 Cycles LOODS Selec scsi aint atico cidcid laicidad 176 A EER 65 a Oise sap inseam apenas nn O ER a PIER 176 UNE EIE HOM costa teeta A O O A cot eee T 176 m df 1M dera net 186 SEIKO EGS Bh G8 VI pee ee O 193 FC Lab IMPOR is 178 File Extensions E E AE E E REE E AS E AN 58 PA OO EERE 58 AO e OOPS Set ae ee er Sete 58 pao A EAE EE A ante A mee eanrian cage T T E EET 58 LA E EEE ETN EE EEN E A E A E E NA EEE NN ee eee Oe EAA NN ee 58 PRIMM e EEATT A e ETEA EP E OO E OO AEAT ETE TTET 58 OPS aa da es 58 A O dee Oh win hcoe dee Oh wen bache at 58 MSc icono ooo toas 46 Al AAA A 195 Filter 202 EC Lab So
220. r manufacturers In the file type box many file formats have been defined to help the user load data files for analysis Most of them are text files that can be exported from software controlling other systems The different available formats are displayed on the figure below EC Lab data files IMPAR MPP MPT EL Lab raw files MPR EC Lab processed files MIPP EC Lab text files MPT Chi files TXT CONDECOR files CF CORNDECON Ewes DAI 0 CA Cien View files TT FRA files 200 Gamry files DT A GPES files CANA GRES CW Ewei AI A ICAA GRES Eh Time s VAJ AA GPES WA Ewe 1144 EMI GPES PSA Eve dt dE A Times OOP YY GPES ECM Tires Eve DAI C ONW PowerSuite TAT Powerlorr rA Ence OTT Powerit Ewet DA ATADO PowerPulse Estep Idelta 34 TXT Powersine RecA Ohm Im Ohrid TT Powerstep Timers IAI CTT Woltarnaster files CRY All files 2 Fig 97 File type selection 72 EC Lab Software User s Manual If a file format is not listed above the user can use the Import From Text option in the Exper iment menu to manually load its data file This option is described in section 5 2 3 3 1 2 EC Lab graphic display Running a Cyclic Voltammetry setting will display the graphic window shown in Fig 98 The default plot mode for the Cyclic voltammetry technique is lt l gt vs Ewe During the run the current recorded data point is displayed in another color a red circle and moves along the curve EC Lab V
221. r to lock the data transfer of the selected channel In the case of a multichannel because of a wrong recording parameter most of time dE or dl on one channel many data points may be recorded and fill the buffer of the com board The data transfer procedure is stuck to this specific channel and is much slower for the other chan nel of the instrument This tool allows user to block the data transfer of this channel the data point of the other channel will be retrieved Third block Allows the user to create a new file to store the coming data point lt is useful for example when the user moves an experiment file during the experiment In that case the user will have one file for the first part of the experiment and another one for data point which are not yet transferred to the PC after the creation of the new file Fourth block This will reset all the data point stored in the buffer of the communication board related to the selected channel This tool has to be used if the tool of the second and the third block doesn t work 2 8 5 Use of the Repair channel tool As explained in the previous paragraph the repair channel allows the user to unlock a channel to retrieve the blocked data on communication board buffer of the potentiostat in a new location or to reset the channel board When an unexpected event happen on a channel board for example file deleted or moved an error message appears hu Messages 1 eT ATS 10 20 10 VMPS 23
222. ral Density PSD indeed according None gt me trend removal to the Parseval theorem it is possible to link variance o and aes Lo Method Power Spectral Density of the x variable P f 0 P_ f df PSD withDFT l 00 Window i MEM order MO Note that P f x2 f where X f is the Fourier transform of x t foe er ae 0473585 A PSD with MEM The Maximum Entropy Method MEM is an Boe Mees estimation of the PSD suggested by information theory Calcula An 5 065 Ohm tion of the PSD can be done with the following relationship Ato Fig 220 Electrochemical Fall HA Noise Analysis window 1 gt a exp 2ir f At k 1 In the Parameters part of the window two choices are available doing the analysis on the cycle displayed on the graph selecting Current cycle s doing the analysis on all the cycles selecting All cycle s In this case the analysis will be performed in all the cycles in a sequential way the result of each cycle will be saved automatically Before to perform the analysis it is possible to remove the trend of the signal potential and current by using a linear fit or second order polynomial fit 158 EC Lab Software User s Manual A description of the analysis windows that can be used is detailed in the section Fourier trans form 4 1 8 page 101 Example of electrochemical Noise Analysis is given in Fig 221 CA R 100mHz_01 mpr Noise Analysis Ewe vs tim
223. rameters the user want to determine by CV Fit should be checked The box placed near each parameter allows the user to choose if the parameter is taken into account in the minimization If this box is not ticked the parameter value set in the cell is considered as the correct value and is not modified during the minimization 4 2 4 5 CV Fit bottom buttons Six buttons are displayed in the bottom of the CV Fit window Calculate Copy Save Init Guess Minimize and Stop button Calculate this button plots the voltammogram corresponding to the parameter values set in the mechanism and the setup tabs without performing any minimization 118 EC Lab Software User s Manual Copy button allows the user to copy the obtained results the setup parameters and the Fit conditions These data can be pasted in a txt document Save button saves the parameters and the results obtained by CV Fit It generates a text file filename fit summarizing the setting and the results values init guess button estimates the initial guess or initial values of the fitted parameters Minimize starts the Fit by minimizing the X parameter reported above Stop button stops a Fit under progress 4 2 4 6 CV Fit results Once all the parameters have been set the user should click on initial guess button init Guess in order to estimate the initial guess or initial values of the fitted parameters using CV Fit algorithm and then click on Minimize button
224. re are three different ways to load a new exper iment 1 Click on the New Experiment button B 2 Click on the blue New link on the parameter settings window 3 The user can also click on the right button of the mouse and select New Experiment in the menu Note It is not always necessary to click on the Modify button before selecting a command The software is able to switch to the Modify mode when the user wants to change the settings parameters In that case the following message is displayed 19 EC Lab Software User s Manual EC Lab You must be in Modify mode to insert a new technique Switch to Modify mode Do not show this message again Fig 27 Message displayed before switching to Modify mode Click on Yes and the Insert Techniques window will appear with the different techniques available with EC Lab software Insert Techniques 4 Electrochemical Techniques f de Woltamperometrio Techniques cb Impedance Spectrascapy gt fee Pulsed Techniques gt Aa Technique Builder A Manual Control gt Ohmic Drop Determination o Bipotentiostat a Electrochemical Applications 413 Batteries Testing gt e Supercapacitor gt y Photovoltaic Fuel Cells gt Lig Corrosion gt fe Custom Applications Insert Technique Load from default Custom Applications Before F Advanced setting External devices a After Fl Cell characteristics TERENE a Asus
225. re within a zone starting at 35 of an area 5 243 2 defined by the first cursor and the max value and ending at oe i the location of a second cursor The data point zone for the x 0 076 89 Y analysis is shown in the Selection frame by the extrema The a oe results of the analysis are displayed in the Results frame Sev eral values for the peak are displayed the position Ep the Results height the width 1 2 Ep Ep2 charge pos and charge neg dera o These values are explained below width 1 2 0 194 3 The results can be copied in the clipboard and pasted any pena SRA Charge pos 9225e 3 mC where as text They can also be saved in a text file Charge neg 0 609 5e 6 mC Calculate Copy Save Close Fig 149 Peak results tab 4 2 1 3 Results of the peak analysis using a linear regression baseline The following figure shows the result of the peak analysis performed on a cyclic voltammetry data file The baseline used for the analysis is a linear regression baseline CV_Fe_basique_1_n mpp al vs Ewe cycle 2 l Marker Data point selected zone lt l gt mA Regression line Ewe V Fig 150 Oxidation peak analysis on a cyclic voltammetry experiment using a linear regression baseline 106 EC Lab Software User s Manual The different values in the Results frame of the peak analysis window are as follows Position is the potential Ep corresponding to
226. reatment of the electrode surface Process function in EC Lab software made to calculate or extract values of the raw files mpr The new values in the mpp file can be displayed on the graph The possibilities of processing depend on the protocol used Please see the description of each protocol in the application part of the user s manual to know the processed values Protocol linker tool of EC Lab software used to link protocols in order to build a complete experiment with or without open circuit period between protocols 198 EC Lab Software User s Manual Record in each protocol the command to define the number of points in the data file The user can define several recording conditions with potential or charge variation depending on the galvano or potentio mode and with time frequency These data recording option reduces the number of points without losing any interesting changes in the curve Reference electrode in EC Lab software the user can choose a reference electrode in the list or add his own reference electrode Report file that can be associated with the data file to add additional information Rp Fit tool available with the graphic display used to calculate a polarization resistance Run button that starts the experiment Save data button in the experiment frame that forces the data transfer of the selected channel buffer Scan rate speed of the potential sweep defined with the smallest possible step
227. recording ocococcccccccccnccncncconococnconnncnonncncncnanocanonos 185 EC Lab Software User s Manual 6451 Generali CSCHOUON sanas 185 6 4 2 Rotating electrodes CONTFOl ccooccccocncccnccoonccncnononononnocarnonanonnnnonannnnanenanoss 187 64 21 Control DANS isis A 189 6 4 3 Temperature contro laisnisincaain aaa 191 6 4 4 Electrochemical Quartz Crystal Microbalance coupling cccooccccocccconcncnn 192 Tes TFOUDIESNOO UNO ia ida 194 7 1 Dala SAVING ti ai 194 7 2 PCD ISCOMMC CUO Narra 194 7 3 Effect of computer save options on data recording oocccconccconcccconcnconcccnnncncnnanons 194 95 COSSA ia 195 9e alo y E E 201 EC Lab Software User s Manual Introduction EC Lab software has been designed and built to control all our potentiostats single channel SP 50 SP 150 HCP 803 HCP 1005 CLB 2000 SP 300 SP 200 SP 240 or multichannels VMP2 Z VMP3 MPG 2XX series VSP VSP 300 and VMP 300 Each channel board of our multichannel instruments is an independent potentiostat galvanostat that can be controlled by EC Lab software Each channel can be set run paused or stopped independently of each other using identical or different protocols Any settings of any channel can be modified during a run without inter rupting the experiment The channels can be interconnected and run synchronously for ex ample to perform multi pitting experiments using a common counter electrode in a singl
228. riment using a polynomial baseline 107 EC Lab Software User s Manual 4 2 2 Wave analysis The wave analysis ig the most useful tool for the analysis of experiments performed in a controlled hydrodynamic regime for instance with a rotating disk electrode When a data point zone is selected clicking on Calculate will perform the anal ysis The wave analysis is made according to two straight lines defined using a linear regression fit The software will automat ically find the two parts of the curve with the shallowest slope for the fit For the first regression the first 20 of the selected data points are taken into account The last 20 of the se lected data points are taken into account for the second regres sion The data point zone for the analysis is shown in the Se lection frame by the extrema The Results of the analysis are displayed in the Results frame Several values for the wave are displayed E1 2 and the limit anodic and cathodic currents The results can be copied to the clipboard to be pasted in the print wndow comment zone or a text file They can also be saved in a text file I ma Ewe V Wave Analysis Selection Results Results El 2 0 020 62 ha i 3 651e 3 m Ne Calculate Copy Save Close Fig 152 Wave Analysis Re sults tab Fig 153 Wave analysis on a curve resulting from a RDE experiment E 2 is the half wave potential obtained by the inters
229. rode Geometry of the electrode can be linear semi infi nite or hemispherical semi infinite The surface area of the electrode is calculated from the value of the radius of the electrode e Experimental conditions Temperature in degree Celsius Ra the electrolyte resistance Ohmic drop in Ohm Double layer capacity in UF e Potential scan Scan type linear or sinusoidal scan respectively for CV or LASV simulation Scan rate in V per second The initial and the two vertex potential in V Number of scans performed for the CV or LASV simulation e Sampling The user defines the number of points needed per scan to perform the simulation The total number of points the resolution in time and in voltage is indi cated e Noise Some noise in current or in voltage can be superim posed to the simulated curve EC Lab Software User s Manual When all the parameters are set the user has to click on the calculate button to display by default the simulated CV curve CV Sim CVsim mpr Example 6 EE DLSI e Ivs Ewe Reduction x A zet gt B 1 0 2 Y 0 04 0 001 cm s Calculate Copy Save l Close J Ewe V Fig 157 CV simulation with two electron transfer It is also possible to display the interfacial concentration of the electroactive species involved in the mechanism The resulting curve can be saved as mpr file File Selection Vanables Representation Custom P
230. rom two different instruments if the instruments are from the VMP3 family SP 50 SP 150 VMP3 VSP MPG 2XX se ries the channels share the same current ranges It is possible to group one channel with impedance and the other without but then impedance measurements will not be available on any of the two channels It is also possible to choose to begin the experiment with the average potentials value of all the selected channels by tick ing the box Start grouped channels at averaged potential or to begin the experiment on each channel with its own potential Synchronizing lt is also possible to run different techniques on several channels and make them start together at the same time This is what is called to synchronize channels Any chan nels from any instruments can be synchronized The user can choose whether or not to stop the channels at the same time ars To enter the Group Synchronize Stack window click on the Modify button then in the Edit menu select Group Synchronize channel X where X is the number of the selected channel or the button can be available in the Main Tool Bar or by right clicking on the main window Settings Pop Up Menu if it has been previously configured using Config Options The following window appears 90 EC Lab Software User s Manual Group Synchronize Stack mode with synchronize 11 12 15 14 15 16 se AL J stack OOOoOOod bipotentiostat VSP virtual Select
231. rs of the elements with the experimental data points Z Fit works the same way as Z Sim If the user already knows what equivalent circuit to use it is not necessary to use Z Sim There are two tabs in the Z Fit window Selection which shows the selected points and Results The Results window contains two frames Equivalent Circuit and Fit 133 EC Lab Software User s Manual Fig li Seleion Res Equivalent circuit A RACE AS param zel eiqn value 11 792 Ohm 0 368 E 0 463 5e 6 F 11 44e 3 101 8 Ohm 0 591 5 5 14 e 6E F 3 530e 3 4290 Ohm 0 307 2 K 4 QOO0DOk kE Calculate Fit Select current cyclels Method Randomize Simplex Randomize first cycle only Stop randomize on i 0000 Iterations stop fton 5000 iterations weight Z Fi 0 029 97 TE Iterations SOOO Simple Cycle Minimize Pseudol Copy Save Fig 187 Z Fit Circuit selection window 4 3 3 1 Equivalent circuit frame As for the Z Sim selection window the Z Fit selection window enables the user to edit and create a circuit For more details about the circuit editing window please refer to the previous section In the equivalent circuit frame the table shows the name of each parameter the sel box that allows the user to choose if the parameter is taken into account in the minimization If this box is not ticked the parameter value set in the cell is considered as the correct value and is
232. rument for more details on the 30 V control connection mode 3V 14V control mode The 14V 3V is two electrodes connexion mode available with the SP 240 and with SP 300 VSP 300 VMP 300 when a 4A 14 V booster connected to the standard channel board 39 EC Lab Software User s Manual Electrode Connections Disconnect the cables from the cell select Electrode Modify on disconnected cells only connections 3V 14 V control and reconnect the cell as follows P1 S1 and S2 leads to the working electrode P1 ni S3 and P2 leads to the counter electrode sE a MIE P S The impedance techniques are not available with 3V 14V control mode CE Fig 58 3V 14V control mode for SP 300 technology 2 6 Accepting and saving settings and running a technique 2 6 1 Accepting and saving settings Once you have set the parameters of your experiment click on the Accept icon gt It vali dates the Parameters Settings the Cell Characteristics and the Advanced Settings and sends them to the instrument If the option is activated in the Config option Warning menu the following window will appear before accepting the settings EC Lab Accept the modifications for channel 1 Technique MG Electrode connection standard CE vs WE compliance 10 V to 10 V Experiment Limits none Ves Do not show this message again Fig 59 Summary window before accepting settings VMP3 technology This window summ
233. s defined as red solid lines and red triangles markers Fig 125 The Graph Style definition includes all the graph properties these properties were previously defined in the section 3 2 5 Once the definition of the Traces Axes Units Graph and Option done user has to click on OK and the new graph style is added to the Graph Style list Graph properties Predefined Graph Style hy Style Traces Ames Units Graph Options Style Plot Lines Markers Line Solid y Y 1 Marker amp Triangle Red 2 Options Draw only lines over 10000 points Note common parameters for all Undersample traces over 25000 points graphic windows Scroll graph over paints Hide OCY Points ok Cancel Fig 125 Definition of traces properties in Graph style definition 93 EC Lab Software User s Manual 4 Analysis The analysis menu is devided into seven analysis sections depending on the application Math General Electrochemistry EIS Batteries Photovoltaic Fuel Cells Supercapacitor and Corrosion These sections contain both the analysis and the processes tools The results of the analysis tools can be saved in a txt file whereas the results of the processes tools are saved in an mpp file that was described in 2 11 2 To use the analysis tools the user needs to know how to select points This is described in part 3 1 2 See Tools Config Windows Help Yo Math dl General Electrochemistry
234. s the control and measurement 30 EC Lab Software User s Manual of the variables are available Note that for SP 50 the adjustable compliance is not availa ble The default compliance of CE vs WE is 10 V For example while working with a gt 12 V battery with the CE electrode con nected to the minus and the WE connected to the plus the potential of CE vs WE will be 12 V That is not in the default compliance In order to have the CE potential in the right compliance set the CE vs WE compliance from 15 V to 5 V Fig 44 12 V battery WE on When the working electrode is connected to WE CE REF the minus and the counter electrode to the plus the potential of CE versus WE will be 12 Y 12 V Then the compliance must be shifted between 5 and 15 V Z Fig 45 12 V battery WE on Warning the compliance must be properly set before connecting the cells to avoid cell disturb ance 2 5 3 1 2 Safety Limits Most of protocols already have potential current or charge limits for example Galvanostatic Cycling with Potential Limitation GCPL limit Ewe to Em and AQ to AQu that are used to make decision in general the next step during the experiment run The experiment limits have been designed to enter higher limits than the limits set into the protocols to prevent cells from being damaged Once an experiment limit is reached the ex periment is paused Then the user can
235. ssible when the box associated to the value to minimize is Fig 144 Multiexponen ticked tial Sim window 103 EC Lab Software User s Manual The Multi Exponential Fit is able to perform a fit on any data Multi Exponential Fit displayed in EC Lab software The combo box in the Fit block Selection offers two possibilities to initialize the fit from the Auto estimate Fano smn values or from Current parameters Note that the xO value can e HR not be fit and must be set manually by the user The results can ee T be copied in the clipboard and pasted anywhere as text They M2 RR vie HHRH Total points sxx can also be saved in a text file Parameters Conductivity vs time nv MExpSim_mexpfit mpp MExpSim mpr y a Gona ae ES Es x Xa 5 4 5 param el value E 9 4 YN 3 35 o qPzuER 3 Calculate ec Oo Fit O AAA 25 Init Start from curent parameters 2 MD o y i NENA HHHH 5 10 lherations HEME time s Minimize Stop Copy Save Close Fig 145 MultiExponential fit result Fig 146 Multiexponen tial Fit window 4 2 General Electrochemistry Menu In this menu the Peak and the Wave analysis are available but also two processes menu and CV Sim a very powerful tool for the simulation of I E curves obtained by voltammetry Pe Peak Analysis Fl f Wave Ana lysis F2 CV Sim a CV Fit He Process Data Cycles R QCM mass Ctri Fl s
236. sult Red curve is the raw data file and blue curve is the filtered curve 4 1 10 Multi Exponential Sim Fit Multi Exponential Sim lt is possible to model data with multiexponential behavior up Parameters to order 6 with EC Lab software This tool is particularly inter esting for conductivity measurements A simulation tool Multi Exponential Sim and a fitting tool Multi Exponential Fit are available in the Math menu param value N F af z t ge k Multi Exponential Sim This tool allows user to plot a curve from a multi exponential equation First of all the order of the multi Exponential equation is selected up to 6 Several units for X axis or Y axis can be chosen for the output graph The window of the simulation is defined between X min and X max In the third block of the win dow it is possible to add noise if the box Add noise is ticked P AHIS timers Y aris Ewe Click on the Calculate button to obtain simulated curve ooi m 2 max hooo o Multi Exponential Fit tois m The order of the exponential up to 6 is selected In the table Noise a line is created for each parameter By clicking on Calculate Y Add noise the calculation without randomization or fitting of the parameters noiselevel pio will be done If the result is not acceptable it is possible to reach a better fit by clicking on Minimize This minimization is only _ Calculate Copy Save Close po
237. t lt last item gt The example above 1 3 will select the cycles number 1 and 3 Once the loops or cycles have been selected the text exportation will create one file per loop or cycle selected with the loop or cycle number added to the text file Note the user can copy data in text format Right click with the mouse and select copy data The displayed variables will be copied to the clipboard Unit selection On the graphic window EC Lab software is capable of plotting variable density for example normalized current with mass or surface These new variables are not stored in the data file and cannot be exported as text To allow exportation of densities the user can select the unit The default one will not include the density and the user s units will include densities Note A text data file can be generated automatically during the experiment if the box Text export is checked in the Advanced Settings window 5 2 2 ZSimpWin exportation It is possible to export data directly into ZSimpWin through the Clipboard To proceed open an impedance data file right click with the mouse and select Copy Z Data ZSimpWin or click directly on the Copy Z Data ZSimpWin button in the Edit menu Then the data points will be copied into the clipboard and can be pasted directly into ZSimpWin Warning For good compatibility the text file exported into ZSimpWin must contain between 16 and 199 points 5 2 3 ASCII text file
238. t opened files are listed in the fourth frame 12 t Insert New Technique Ctrl I ae Insert Technique From File Ctrl F Move Technique Before Move Technique After Remove Technique Remove ll The Techniques Reset Settings To Default Set Settings As Default Group Synch Stack Bipot eis A Add Sequence Remove Sequence Reset Sequence Copy Sequence Paste Sequence Copy Graph Copy Data Copy Graph Advanced Copy Z Data 4SimpWin Copy EIT Data Condecon Fig 7 Edit Menu The Edit menu can be used to build an experiment insert Move up or Move down or Remove a Technique from an experiment The Group Synchro nize Stack Bipot window is also avallable in this menu The second frame is for se quence addition or removal from a technique when this is possible and the two last ones offer Copy options Graph Data ZSimpWin for mat on the graphic window Hiei Graph Analysis Tools Config Wi Global view Ctrl r Current Settings Graph Description Settings With Plowcharts Channel al Tool Bars d Fi Status Bar iy Messages Fig 8 View Menu This menu is very useful as it al lows the user to show the Global View a Graph Description of the technique to switch between the Column Flowchart view of the settings The second frame shows the ac tive channel and its status The third frame allows the user to choose which Tool Bars to have displayed or to show the St
239. t type and size is also available from this option menu Note On the graph the user can move one of the Y axes with the mouse left click in order to adjust the origin of both Y axes Put the mouse on the axis to see the je and move the axis 81 EC Lab Software User s Manual Graph properties Predefined Graph Style Line style Custom Graph Style Traces Graph Units Axes Time z Graph Current m Mones Options Charge m h None gt Graph Units window is used to choose the cor rect graph units for the different variables The default units are in gray boxes If the user chooses another unit the box corresponding to the represented vari able must be ticked for the choice to be acti Frequency Hz vated Specific units are available for current and charge on one Energy Wh ge lt None gt hand and for power and Capacity uF t None gt energy on the other Potential vs Reference Electrode hand For current and charge the user can choose to display the current or the charge di Resistor Ohm None Power Vai lt Hone gt unspecified Offset potential vs Normal Hydrogen Electrode 0 000 Reset Units Edit Surface And Mass vided by the electrode area or by the electrode ok Cancel Characteristic mass Fig 110 Units window Power and energy can be plotted according to the electrode characteristic mass In sucha case the software will ask for the electr
240. tch Ouput File s _5 18650_cyclage_ GCPL_1_C05 mpr Techriquels GCPL eSBeSt xtl p Fig 80 Batch selection window When the batch window is open it is empty To add settings mps or data files mpr which also include the experiment settings click on the button then select the correct folder to find the files Files from different folders can be loaded in the same batch The user must a define an output folder where the created batch experiment files will be stored b give a file name for the batch With the batch name the software will automatically generate a data file with the name for each source file y 3 7 3 7 3 63 number in the batch list source file name channel number Batch name mpr For the user s convenience the technique used in the selected file is displayed Several func tions are available with buttons at the bottom of the window to open save or print a batch to add remove move up and down and insert setting files into the batch During the Run the user can pause the experiment and go to the next settings file Notes e if the number of techniques is lower than 20 it is often more convenient to use linked techniques e it is not possible to loop a batch i e to set the repetition of a batch a certain number of times 96 EC Lab Software User s Manual 2 11 Data properties 2 11 1 Type of data files Several files using your filename with different exte
241. th a SMTP server directly The E mail tab is dedicated to the set up of the mail server parameters The SMTP server parameters can be obtained from your network administrator SMPT configuration e SMPT Host your company s outgoing mail server name e g mail domain com or your outgoing mail server IP address example 192 109 201 211 e User name SMTP user name e Password your password used to access your email name domain com e The user name and the Password are optional They are not necessary needed for the setting of the SMPT server e From E mail your email address from which the message and the data can be sent e g name domain com e SMTP port outgoing SMTP server port e g 25 Click OK to validate the setting The user should now be able to send email and data to any other email address using the E mail tool available in technique builder section of EC Lab Fig 93 67 EC Lab Software User s Manual auebfies E Fig 92 E mail window The user can access the Email tab Fig 92 by clicking on the smpt option link More details on Email tool are available in the techniques and applications manual 68 EC Lab Software User s Manual EC Lab software Graphic Display Graphic window The EC Lab application includes a graphic facility to display experiments on line or and off line Several independent graphic windows can be opened while an experiment is running The user can perfor
242. the oxi dized metal divided by the number of electrons involved in the dissolution reaction For in stance for the corrosion of iron Fe Fe 2 EW 55 85 2 27 925 g equivalent the equivalent weight can be set up in the Cell Characteristics tab see 2 5 2 d density in g cm A sample area in cm K CR units 3272 mm A cm year mm year mmpy _1 288x10 milliinches A cm year millinches year mpy __ 4 7 1 3 Minimize option In some cases the calculation of the Tafel parameters and corrosion parameters may not yield a satisfying fit because for instance within the default potential ranges chosen the material does not exhibit a Stern behaviour but more a mass transport limited behaviour or a pas sivation In these cases it is possible to numerically find satisfying parameters and reduce the error between the model Icaic and the measured data Imeas i by minimizing the following value N gt Creasi o I ales IS 1 I meas This is obtained by clicking on the Minimize button The Nelder and Mead Simplex method ref 2 is used to minimize the y value Keep the button pressed lt Enter gt or lt Alt M gt keys 152 EC Lab Software User s Manual until the Stern and Geary parameters Ecorr Icorr Ba and Bc have stabilized Then a simulated Tafel graph is displayed this graph is displayed in agreement with the parameters obtained with the Minimize button Note that the Simplex method may n
243. the run the active row of the table running sequence is highlighted The default num ber of rows is 30 The user can insert delete append copy and paste up to 99 rows by clicking the right button of the mouse It can be a very interesting tool when the user wants to repeat an experiment with one different parameter in a sequence lt is also possible to cut copy and paste only one cell of the table Note The user can define different current ranges for each sequence if an OCV period sep arates the sequences at the beginning of each sequence for example Itis possible to repeat a block in a sequence go to sequence Ns 2 5 2 Cell Characteristics Tab Clicking on the Cell Characteristics tab will display the cell characteristics window This window is composed of three blocks Cell Description Reference Electrode and Record Please see below Leal Descoapron Devices gt ae Electrode material ERA mii Initial state eta IA B YMPI3 236 Comments Electrode surface area 0 001 Experiment Characteristic mass 0 001 Advanced Settings Battery gt gt Equivalent Weight 10 000 gen Density 10 000 acm Reference electrode External Devices Parameters Settings de SCE Saturated Calornel Electrode ka lead Offset potential vs Normal Hydrogen Electrode 0 241 VY 1 Cv Record Ece WE CA2 C Paw ref E 1 C Analog IN 1 4 a E C Analog IN 2A Ese Record external dev
244. them select the vari able The user can add his own labels and units to be displayed in the data file and the graphic window Then click on the Import button to import the file into the EC Lab mpr format The mpr file is created in the same folder as the text file Several details are displayed when the file is created such as the name the number of points and the size Finally the user can display the mpr file quickly and easily with the Display button Every analysis of EC Lab is available with the new generated files 5 2 4 FC Lab data files importation FC Lab data files can also be imported and analyzed in EC Lab using the Text file format function The FC Lab data file format is particular as all the data files for each technique are in the same file So EC Lab software will separate every file of every technique used in the experiment 177 EC Lab Software User s Manual 6 Advanced features 6 1 Maximum current range limitation 2 4 A on the standard channel board 6 1 1 Different limitations VMP2 VMP3 VSP are designed to accept a maximum continuous current of 400 mA on the 1 A current range for each channel and for a room temperature of 25 C Note that the maximum current that can be reached in continuous by the SP 50 and SP 150 is 800 mA and 500 mA the SP 200 SP 240 SP 300 VSP 300 and VMP 300 In particular conditions of current and time this limit can be passed Then the following
245. tion below A Count half cycle process is available to separate half cycles especially for charge dis charge measurements in battery testing Additionally a process is also available for QCM experiment and especially for the determina tion of Mass variations Using the auxiliary inputs of our instruments and a good setting to record the frequency changes the software is able to process the mass variations This feature is described in details in the application note 13 162 EC Lab Software User s Manual 5 1 3 The derivative process Process Data Input Files C UsersselectrochimesDesktop Cy platinum 10 cycles mpr Technique Cyclic oltammetry Processed File EA LserselectrochimieDesktop C platinum 10 cycles_nld mpp bead add Remove cear Variables To select from the input file To be added mode F cucle number ox red 4 0 0 0 fm h error G chargesm h control changes Z O discharge m s h counter Inc ddt m s times Z cycle timers control Z step time s Ewe V charge time s 1 md discharge times All All Process Average E steps 4 Allow Reprocessing Cycles definition auto Export As Text Count half cycles Process Display Close Fig 223 Cyclic voltammetry processing window For techniques resulting in a current measurement when the potential is controlled the user can process the data file to create a new variable dl dt the derivative o
246. ts the capacitance Cs or Cp or the inverse of the square of the capacitance 1 C or 1 Cp as a function of the potential Ewe see Fig 181 142 EC Lab Software User s Manual SPEIS _7MHz to 1Hz_C V_Charact mpr mpr gt Cs 2 vs lt Ewe gt Cp vs lt Ewe gt 160 0 002 mA 120 A 0 0015 A io 2 N 5 a 0 001 TI 80 60 0 0005 lt Ewe gt V Fig 196 Mott Schottky plot 4 3 4 3 The Mott Schottky Fit Once the Mott Schottky plot is chosen the frequencies must be selected If they are not the warning message will be seen A window will allow the user to select the frequencies The user can select several or all frequencies see Fig 182 Click on Ok to display the Mott Schottky curves The selection is the same for the time evolution of the impedance or of the phase Then the graphic window shows one trace per frequency see Fig 183 Use the shift key to display the frequency Frequencies 000 MHz 4 766 MHz 3 245 MHz 2 209 MHz 1 504 MHz 1 024 MHz 637 234 kHz 474 705 kHz 323 203 kHz 220 047 kHz 143 012 kHz 102 000 kHz 63 453 kHz 47 281 kHz 32 187 kHz 21 922 kHz 14 555 kHz 10 162 kHz 6 934 kHz 4 710 kHz 3 205 kHz 2 183 kHz 1 487 kHz 1 012 kHz 689 338 Hz 469 549 Hz 319 693 Hz 217 576 Hz 147 964 Hz 100 677 Hz 68 703 Hz 46 750 Hz 31 844 Hz 21 641 Hz 14 759 Hz 10 042 Hz 6 823 Hz 4 550 Hz 3 168 Hz 2 163 Hz 1 465 Hz 1 000 Hz All frequencies Cancel Fig
247. ummary Per Protocol And Cycle Cirl F3 Fig 147 General electrochemistry menu 4 2 1 Peak Analysis A peak analysis iy dedicated to Cyclic Voltammetry is available with the EC Lab software Like other analyses with the EC Lab software the user has to select the analysis and then select the data points to fit or select the data points before choosing the fit To select the peak analysis click on the button in the graphic tool bar or select peak analysis in the right click 104 EC Lab Software User s Manual analysis menu When this first part is done the peak analysis consists of two steps The user must choose the baseline and then click on calculate to have the results 4 2 1 1 Baseline selection Peak Analysis When selected the peak analysis window is displayed with two tabs Baseline and Peak In the Baseline tab the user must select the baseline type Three selections are available No Baseline Linear Baseline and Pol ynomial Baseline e If the user selects No the analysis will be per formed according to the abscissa axis e lf the user select Linear three different base lines can be set Manual mode with markers locked on the curve Regression mode with a linear regression made on the capacitive part of the curve before the peak or in a Free mode two cursors unlocked to the curve defining a straight line In the Manual mode the baseline is defined by two points represented by circles and set on the
248. utton A print preview is available to see the different parts of the page 85 EC Lab Software User s Manual Print Printer TO ET PDFCreator n Microsoft XPS Document Writer Preview Fax Brother MFC 6490CW Printer Print Graph Graph size L Z Print Comments Z Print LOG Fig 117 Print window Note the date is displayed and printed automatically in the top right corner 86 EC Lab Software User s Manual 3 2 9 Multi graphs in a window The EC Lab software graphic window is capable of displaying several different and independ ent graphs The number of graphs is not limited x Graph bo e lees Selector Shom 18650_cyclage_GCPL_1 mpr 18650_cyclage_GCPL_4 mpr 18650_cyclage_GCPL_4 mpr Ewe vs time l ve time x wz time time s time s time s 18650_cyclage_GCPL_14 mpr 18650_cyclage_GCPL_4 mpr 18650_GITT2_1 mpr 2 20 vs time dq ws time Y Hs changes vs time Ewe vs tine l vz time error vs time 0 2 a y yu bp I ba lt E y 2 Ns changes a in 4 s00 000 500 000 300 000 times time s time s 48650_GITT2_4 mpr 48650_GITT2_4 mpr 18650_GITT2_4 mpr Ewe vs time F vs time Eve vs time 2 0 vs time Ewe vs time Go vs time control vs time i Weal L o o a O y yu o 0 A 1911103 300 000 300 000 300 000 time s time s time s Fig 118 Multigraph
249. y in the galvano mode the current is controlled and the potential is measured In both cases one variable is controlled and the other one is measured The current and the potential dimensions always have to be adjusted while choos ing the range in which the experiment is performed In fact the result accuracy will be better if the range is chosen closer to the experiment s limits 6 3 1 The potentio mode The potential control range can be adjusted for the experiment with the experiment limits Emax and Emin See the installation and configuration manual for more details The result of this adjustment is the potential resolution increase from 300 uV to 5 uV In this control mode the user must define the measurement current range The closer to the experiment the current range is the better the measurement accuracy The maximum current value that can be meas ured corresponds to 2 4 times the chosen current range In other words for the 10 uA range on the figure below the user can apply potentials from 10 to 10 V and currents going from 24 to 24 yA can be measured with no restrictions 30 24 20 HAJ Fig 250 Current versus Potential available domain in the potentio mode 183 EC Lab Software User s Manual 6 3 2 The galvano mode In this mode the current range must be adjusted to the controlled current In that case the user must distinguish the 1 A current range which will be discussed in the followi
250. your inputs e BioLogic Time 0 0000 s Status Stopped Ewe 5 387 Y 0 000 4 Buffer O Eoc 5 387 Y O Qo O00Ah Range open vMP3 Channel B Read mode 0 0 0 b s Fig 1 Starting main EC Lab window If the computer is connected to the Internet a Newsletter appears Furthermore on the left column two boxes can be seen Devices box that lists the instruments to which the computer can be connected For more information on this box please see the Instruments Manual Experiment that lists the series of techniques that are used to perform the desired ex periment on the selected channel of the selected instrument EC Lab Software User s Manual When EC Lab is connected to an instrument the following Username window can be seen User Mame User name a My Name Use personal options Show window at startup Cancel Fig 2 User name window Type your username example My Name and click OK or press lt ENTER gt This User Name is used as a safety password when the instrument is shared between several users When you run an experiment on a channel this code will be automatically transferred to the section user on the bottom of EC Lab software window This allows the user to be come the owner of the channel for the duration of the experiment All users are authorized to view the channels owned by the other users However change of parameters on a channel is
251. z CV_1nA_10Vs_solution z_CV_1nA_10Vs_background mpp lt I gt nA 0 0 2 0 4 Ewe V vs SCE Fig 137 Use of the Subtract Files tool on the blue and red curves The obtained curve is shown in green 99 EC Lab Software User s Manual 4 1 7 Integral One can calculate the integral value of a selected trace between two cursors On the graphic display select the Integral by clicking on Integral button 2 in the analysis menu or the mouse right click and the data points where the fit will be performed The Integral analysis window is dis played Click on Calculate Two cursors bound the in tegrated trace The cursors can be moved to adjust the zone to be fitted The fit is updated automatically The integral is calculated according to X axis The integral is shown as a grey area The units of the integral fit re sult depend on the plotted data points For a cyclic volt ammetry displayed as vs E the units will be A V If a current time trace is selected the unit of the integral is A S The results can be copied in the clipboard and pasted anywhere as text They can also be saved in a text file CY platinum 10 cycles _n mpp lt l gt ys Ewe cycle 4 0 02 0 015 0 07 0 005 0 005 lt mA 0 01 0 015 0 02 0 025 0 03 0 05 Ewe V us SCE Integral Selection Trace lo we Ewe From point 0 6 a L243 2 T 4 2496 3 m To point 2313 e 1 192 ne 0 015 56 m

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