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EC-Lab Software User`s Manual

1. ccooccccoccnccncnnnnncncnnos 175 55 Preconditioning methods before an electrochemical experiment ceceeeeeeees 176 5 5 1 Equilibrium state establishMenlT ooccconcconcconcconoconoconoconocononanocanonanonanonanenones 176 5 5 2 Preconditioning Meno Siri o o eta e ai 177 5 5 2 1 Mechanical Modification occccocccccncconnoconncnnnocaninonnnnnnnonannnnnnonannonanonanoss 177 5 5 2 2 Electrochemical MOJITICAIONS durar a 177 5 5 3 EC Lab facilities for the pretreatment before an electrochemical measurement 177 TrOUDIESNOO MINO ticas ra nic 178 6 1 Dale SAVING araceli acgtuntanotdahsacstuntadostdehiacstuntstestdehdacstentatentdaiiadiie 178 6 2 PG DISCOMMO CIO asepsia 178 6 3 Effect of computer save options on data recording ooccocccoccccncococcncncncancnnonanonons 178 A O 179 A mn 185 EC Lab Software User s Manual Introduction EC Lab software has been designed and built to control all of our potentiostats single SP 150 SP 300 SP 200 or multichannel MPG VMP VMP2 Z BiStat VMP3 VSP and HCP 803 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 interrupting the experiment The channels can be interconnect
2. Shift Ctrl E wf Options Shift Ctrl O Fig 22 Config Menu The config menu is dedicated to instrument and software configuration define the user name connect the instrument configure an external device software display options The virtual potentiostat option is available only when the computer is not connected to the instrument off line Cascade E Tile 1 Channel 1 no experiment w 2 Graph Fig 23 Windows Menu This menu is used to display and select windows T EC Lab software user s manual T EC Lab software techniques and applications E ir VMPS installation and configuration manual db Bio Logic Home Page Check for Updates Newsletter a About Fig 24 Help Menu The help menu contains pdf files of the software manual the instrument installation and configuration manual and several quickstarts This menu provides also a direct link to the Bio Logic website and a way to check for software updates lt is also possible to access to the Newsletter this Newsletter IS also automatically displayed when the software is installed for the first time on the computer and for each upgrade First select a channel on the channel bar There are three different options for loading a new experiment 1 Click on the Modify button then the Accept button activates A the New experiment button 2 Click on the blue New Experiment link on the parameter settings
3. 34 EC Lab Software User s Manual lt l 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 49 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 35 EC Lab Software User s Manual 2 2 Accepting and saving settings Once you have set the parameters of your experiment click on the Accept icon Y validates the parameter settings the cell characteristics and the advanced settings and sends them to the instrument If the option is activated in the Configloption Warning menu the following window will appear before to accepting the settings Accept the modifications for channel 1 7 technique CA electrode connection standard LE vs WE compliance 10W to 10 experiment Limits Ewe min 1 00 4 Ewe mas 1 00 fort gt 10 me E control resolution 50 py Fig 50 Summary window before to Accept settings This window summarizes 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 settings can be saved as an mps file in Experimentisave asi or right click on Save Experiment or click on 2 2 8
4. i Selection The software will automatically find the max current eee ap es ste value in the selected zone according to the baseline From Point 3914 Data points used in the peak analysis are selected by A 0 063 64 Y default from 35 of the beginning of a zone starting eg a at the beginning of the selected zone and ending at V 0587W the max current value to the end of the zone The T 0 092 26 m data point zone for the analysis is shown in the Total points 456 Selection frame by the extreme points Results The results of the analysis are displayed in the Position 0 2315 Results frame Several values for the peak are Height 0 224 mA displayed the position E height width 1 2 ee see E Ep2 charge pos and charge neg These values Fiera Bas AOA a are explained below Sharma Hem Oat 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 Fig 125 Peak results tab 3 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 96 EC Lab Software User s Manual CV Fe_basique_1onmpp al ve Ewe cycle 2 Marker Data point selected zone lt 1 gt mA Regression line Width 1 2 0 2 0 0 2 0 4 0 6 Ewe V Fig 126
5. El Cancel Fig 63 Option window Colors tab e Select the grid line colors for the multi line parameters settings see the GCPL protocol e Select the flow chart s backgrounds and text colors The custom buttons allow the user to define additional colors that appear at the end of each list 2 9 5 Reference electrode options e Display all the reference electrodes registered in EC Lab The default reference electrodes are in black 90 EC Lab Software User s Manual Options default Text export Colors References Tool bars menus References Electrodes Electrode Mame Voltage M Ag AgCl ECI 3 5 0 205 Ag AgCl EC sat d 0 1397 Ag AgCl Nall sat d 0 1394 Hg Hg2504 2504 sat d 0 650 NHE Normal Hydrogen Electrode 0 000 SCE Saturated Calornel Electrode O41 SSCE Sodium Saturated Calomel Electrode 0 36 User s reference 0 000 Add E dit Remove Fig 64 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 User s Reference 0 500 y Cancel 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 references Electrochemical Methods A J Bard amp L R Faulkner Wiley New York 1980 Electrochemistry for Ch
6. Selector select Selector in EC Lab Graph menu or click on the Selector button to open the selection window The following window will be displayed 99 EC Lab Software User s Manual re Selection Variables CNEC Lab DataS amples CY platinum 10 cycles mpr Representation Eve we t Pi mode osred error control changes counter Inc times s control Ewes ls fn HIE aaa aa A A A E 7 popa esa a O A El MU Same selection for all files Hide Additional Variables keep previous axes process keep previous zoom Load Remove Undo Fig 74 File selection window The user can choose to plot another visualization for example time s for X Ewe V for Y1 and lt l gt uA for Y2 The loaded file contains the recording of the following variables the time time s the working electrode controlled potential control V the working electrode measured potential Ey V the average current average 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 statuses of the experiment Most of the time the user may not be interested in showing the state byte that is more dedicated to int
7. Below in the middle The default window displayed when EC Lab is launched is the Parameter Settings window Three buttons permit the user to switch between three windows associated to the protocol the Advanced Settings the Cell Characteristics and the Parameter Settings When no technique or application is loaded in the settings window a small text is displayed indicating how to proceed No experiment loaded on current channel Turn into modify mode menu Experiment Modify to unlock the channel and define a new experiment set with Experiment New or Experiment Load setting A white column and a blue row are displayed The column will contain the techniques of a linked experiment The settings of each technique will be available by clicking on the technique s icon The Turn to OCV between techniques option offers the possibility to add an OCV period between linked techniques Turn to 00 between techniques lt lt Default Fig 13 Row in the parameter settings window showing advanced parameters 2 2 1 6 Right click on the Parameter settings window EC Lab software contains a context menu Right click on the main EC Lab window to display all the commands available on the mouse right click Commands on the mouse right click depend on the displayed window Other commands are available with the mouse right click on the graphic display 13 EC Lab Software User s Manual Adva
8. My comment on this anodic current peak Properties Font Name Font Style Font Size Alignment Font Color Background Color Transparency Show Arrow EC Lab Software User s Manual Arial Standard Align Lett Me Black e als TOU Fig 78 Edit Comment zone 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 desired part of the curve by clicking on the end of the arrow To remove comment zones right click on the zone and select Delete comment or click on the Del keyboard button Note The comment zone is automatically printed on the graph 3 2 4 Three Dimensional graphic A 3D representation is available by right clicking on the graph menu After clicking on the 3D menu the Selector menu is available and allows to the user to choose the variables to display An example of the Bode diagram obtained with the 3D representation tool is given Fig 79 64 EC Lab Software User s Manual SPEIS mpr A E h R eS NEO TUITE ARAS LLULLU IILS A LL ALINLIK E ZA Oo 344 ne N 324 KL le gt 33 a cycle number E oot 2 a d 1 000 10 000 10
9. TT CONDECON files CVF CONDECON E wen 184 PCY Cen view les THT FRA files 400 Garry files 075 GPES files 004 GPES CY E wer 18 OCW GPES CM Timetz 1486 E 0ra GPES VA Ewen A FO GPES PSA Ewen dvds Timers OPW GPES ECH Time s Eee KA ON PowerSuite TT PomwerCor 145 E we TXT Powerly Eme 18 TT PowerPulse E step Idelta amp TT Powersine Rel Ohm Imek hm TT Powerstep Timers 144 TXT Yoltamaster files CLAY Fig 70 File type selection If a file format is not listed above the user can use the import from text option in the experiment menu to manually load its data file This option is described in a following section 57 EC Lab Software User s Manual 3 1 3 EC Lab graphic display Running a Cyclic Voltammetry settings will display the following graphic window 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 and moves along the curve This option avoids not seeing the state and the evolution of the experiment especially the position in the potential sweep when several cycles are recorded and overlaid EC Lab Graph D Experiment Edit Yiew Graph Analysis Tools Config Windows Help i B e ugat eog O gt p 19 REM ass a a CV_Fe_basique_1 mpr lt l gt vs Ewe x 0 44468 V ly 0 105199 mA i Point 2295 Ewe V vs SCE V
10. the user can process the data file to create a new variable dl dt the derivative of the current versus time Click on Display to automatically display the processed variable on the graph The example below shows the Current derivative curve plotted versus the potential overlaid with the native cyclic voltammetry 144 EC Lab Software User s Manual CUEC LabiData Samples CV Fe basique 1 nd mpp al vs Ewe cycle 2 bt ve Ewe cycle 2 gt mA S UP pP Ewe V ws SCE Fig 185 Overlay Cyclic voltammetry with derivative curve All the graphic tools and fits can be applied to the derivative curve 3 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 resulting 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 important 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
11. 114 Sampling 0 986 1 2 1 014 Hz Parameters Winds freqiHz Frequency range Auto Freg Min Hz Freg Max Hz Nb Points 56 Fig 118 Fourier transform analysis 91 EC Lab Software User s Manual 3 4 1 8 Filter Data may be distorted by external perturbation for Filter instance the 50 or 60 Hz frequency signal coming from an the electrical grid The Filter tool Y available in ae L EC Lab software allows the user to remove this 90s additional signal and then yield to smoother results ye 69 93e 6 m To point 35983 l A 108 Several filtering methods can be set Y 55 Gde 6 m e Moving average method For this method the Total points 35984 window size must be defined a e Savitzky Golay method This method is based Vier on polynomial calculation in a defined window The window size and the polynomial order have Freg min 0 055 55 Hz 7 ston and kecdi thod Freg max 999 5 Hz e Low high pass or band pass reject methods ono These methods are based on Fourier Transform DUS The window Rectangle Barlett Hann frequency band Hamming Blackman Welch and the cutoff 50 000 um frequency ies have to be defined please refer 60 000 max to the Fourier transform part for more details on this point neice a OT The results can be copied in the clipboard to be pasted eee ven Theatr in the print window comment zone or in a text file They OOO can be saved in a text file A Calculate Clo
12. 42 12 V battery WE on the plus 30 EC Lab Software User s Manual 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 43 12 V battery WE on the minus Warning the compliance must be properly set before connecting the cells to avoid cell disturbance For SP 300 and SP 200 instruments the compliance is not adjustable and is equal to 12 V With the 1 A 48 V booster the compliance is 48 V For HCP 1005 HCP 803 and CLB 500 compliance value is fixed 2 2 6 2 Electrodes connections 2 2 6 2 1 CE to Ground connection mode 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 Electrodes Connection For VMP3 technology Modify on disconnected cells only Disconnect the cables from the cell select Electrodes connection CE to ground and CE reconnect the cell as follows refs CE and Ref3 leads to the working a electrode E Ref2 lead to the reference electrode refl GROUND and Ref1 leads to the counter ground electrode Fig 44 Configuration CE to ground N Stat for VMP3 technology For SP 300 technology Disconnect the cables from the cell select Electrodes Connection Electrodes connection CE to ground and debes estad
13. A Connection Virtual Potentiostat L External Device RDE ShiFk Ctri E W Options Shift ctr o Fig 222 Menu to choose for rotating electrode control Note this menu is available only if channels designed to drive a RDE since 11 04 are connected with the RDE electrode rotator Then the following window is displayed External Devices RDE Configuration Channel Device Type Device Name Analog OUT Analog IM 1 Sloane EN 8000 with 0 Y 0 max oo D Wee D min Manual Control Analog IH 2 with O Y D max o D y D min Fig 223 Rotating electrode control configuration Under Speed control unit one can select the standard supplied ALS RRDE 3A or PINE RRDE or RADIOMETER CTV101 electrodes rotator For these devices the calibration parameters 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 wou
14. CUENTA ANS tutti liada oe 21 Current Range vo tee ence eu tuadeens 168 Current Range 185 EC Lab Software User s Manual OIA Oct cannes toa ace tnaassate AA 169 Current Range A a e e aided clint EE 169 EVESIMUIAION oa 100 AA e o ee E eee ee ee 100 CONCERTO Nara ana alt chanted sanatiagsaneian 103 A en cn nce ahaa memnee ra ucaee meee act est anata E eases treet ncenents 102 palo Sear rie estan o E ie tla poa cutie sap aati eta AIS 104 A oe ee oe eee ee 101 OVIE Lome ee ee nee E A ec ee ee eee er 61 153 ENCIMA MAME a ee at el aed oa eae 19 Data AWOME eo AW ING a eee cena acute gee tea es esc enta eesti eacetnesee 47 Save with automatic incremented NAME occcoccnccncncccccncnncnncnnnnonncnnonnnnnnnnnonnnnnnnnnncnnnnnnnnninnns 47 Save With Channel NUMDEN as as 47 dalla LEO AS EIEE A T E E o ls 57 Data TOI Geena e a e a e e Cra Ly hl eo Le 36 45 DEAE stay acta ae oe tesi duda tardado docu bres Carito san baa Casio tatu baat puna year eam pane doi das 24 135 GERIV ALVES CUI Varia 144 Descubrir ee tert tree 18 ISP DIOCSSS COMING ooo sai 61 Bea NO OC PRE RO E EA e e A A 7 Electrochemical NoiSe ANANS Sissi 139 Electrode sunace Tal ea ds dee 24 Electrode surace AOA senei a A 68 EGN E ee ee E E A 175 EGUVAICNEWEIQAT arren oca 24 135 Experiment IMIS ds 32 EXPO AS o oo a o oo Ea o A 152 A e E E OR eesarsasaeeeauesmeas 153 Ms A o ERER 153 Export text GYCIE1OOD SEIS e o 153 EXA Gala al 57 ExtemaldeViC gt APA Sn POE
15. Density 10 000 grcma ele LE Reference electrode SCE Saturated Calomel Electrode sos Offset potential vs Normal Hydrogen Electrode 0 241 W Fig 34 Cell characteristics window for a Cyclic Voltammetry experiment You can either fill blank boxes entering comments and values or load them from a mps setting file or a mpr raw file using Load Setting on the right click menu This window allows the user to e add information about the electrochemical cell material initial state electrolyte and comments e set the electrode surface area the characteristic mass the equivalent weight and the density of the studied material When defined these parameters are automatically used to 23 24 EC Lab Software User s Manual calculate the corrosion rate after a Tafel Fit They are also used for the density plot To modify the electrode surface area or characteristic mass select Edit surface and mass in the Graph menu Then the window below appears i j _ Edit parameters A File CME C Lab D atas S amples ly platinum 10 cycles mpr Parameters Electrode surface area Characteristic mass Don Fig 35 Edit surface and mass window set the reference electrode used in the experiment either chosen in the list or added while clicking on the corresponding tab record the counter electrode potential Ese calculate Ene Ece V and store the values into the data file record the power Ewe l calc
16. leor Ba and Be will remove the corresponding value from the minimization And at any time one can restart the calculus from the linear fits by clicking on the Calculate button Reference 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 3 4 6 4 Constant Amplitude Sinusoidal microPolarization fit CASP fit The relationship describing the potential modulation vs the sinus of the frequency is given by E Ecor SEsin 27fst Then by applying a Fourier Transform to the former relationship the resulting current can be described by the following equation 3 4 I t o of sin t l cos2at dl sin 3at where the fundamental is 6 and the two first harmonics are 6 2 6 3 respectively 137 EC Lab Software User s Manual 3 3 5 5 oh bo b bc SE Da De sp oO OE CASP Fit Selection a o a E T lve H Bas hof ESBS age BEADS aea e Naa a Us 3 _ E a aie 5 b5e 6 m dl on Be E A To point 30000 24 384 Y 300 s It is assumed that the harmonics superior to 3 are not a a e m significant so they are neglected in the calculation of lcorr Ba sia and Be To validate the fit 54 d and h are given in the Input potential window His method yields to valid result if 5 is positive 5 E Ego e sine Tht is positive or equal to O and h is negative Auto detect Wa Mf T
17. 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 Protection mode A A 1 2 one channel limit No limitation t ms Fig 208 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 163 EC Lab Software User s Manual different currents l and l2 are applied for two durations t and ts respectively The average current on a period is defined by It 1 Toa 2 2 W Lert 0 ty t2 t Fig 209 Example of a current pulse protocol 3 The power supply has a limit of 10 A To avoid having the instrument enter the protection mode the user must respect the following equation Nb Y Ios lt 10 A 1 where 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
18. 10 mpp E 15650_2POT_1 mpr eS 18650_GITT_030604_1_cxR mpp E 18650_GITT_030604_1_IGx mpp eS 18650_GITT_180604_1_IGx mpp Ej CV Fe _basique_1_cnQ mpp Ej CV Fe_basique_1_n mpp Desktop fel PITT_2300604_1_cql mpp Ej 18650_cyclage_260504 GCPL_1 mpr es 18650_GITT_030604_1 mpr 3 18650_GITT_180604_1 mpr es 18650_linked_1_GCPL_1corr mpr l 18650_linked_2_ZPOT_1 mpr eS 18650_linked_3_GCPL_1corr mpr E 18650_linked_4_ZPOT_1 mpr es 18650_linked_5_GCPL_1corr mpr My Recent Documents My Documents My Computer 3 APGC_GSMdischarge_1 mpr E CA_Fe_1 mpr E CA_loop_Fe_1 mpr E CPW_RAGONE mpr CY _Fe_basique_i mpr E opy_Fe_basique_1 mpr eS PITT_2300604_1 mpr E pyr Cz mpr E prrtest mpr Ej POT_Fe basique_1 mpr Ej zpotb_i loops mpr E potBorniers_1 mpr a g My Network Places Files of type File name EC Lab data files MPRA MPP MPT Lancel C4_Fe_basique 1 mpr Fig 69 Open file window Select the data file you want to open and click on Open The user can also select and a open data file from ther 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 Files of type EC Lab raw tiles MPA EL Lab processed files MPP EC Lab text tiles MPT Chi files
19. 12 3 2 9 1 Multi raphs in A WINAOW sia aaa a aa 72 32 92 MUI WIOOWS e a o e icine tue ater teas coke 73 3 2 10 Graph Representation Menukaart a a a a a 74 3 2 10 1 AXIS PROCESS ING sia a a Maine ieee 75 3 2 10 2 How to create your own graph representation for a specific technique 17 3 2 10 3 Howto create a Graph Style oococonccconnccccnnccoccncconnnonnnnonnononnnncnnnnonononos 78 3 3 A a tein damoudedcenawatee te 80 dudo OMS SIC CU OM aa 81 3 4 Analys Menta atra 82 Sek Wath WICH tal a SO 84 3 4 1 1 Min and Max determination ooccooccoccnccccncconnoconcnonnnnnnnonanonnnnonanonnnncnncnnnaninos 84 2w e2 METIS AN F ta het eat eal rt eee ae ae al a el al sae ele aa al 85 Sia IS E 6G 2 A OMe eet AF OO OE E a A 86 3 4 1 4 Linear interpolatioN cooccconcconcconcconoconoconoconononononononocononanonanonanonanenanenanes 87 3415 SUBACT TICS ei iii iodo 88 A A O 89 Sar FOUMenttansio Massi S 90 SAO MM iia 92 3 4 1 9 Multiexponential Sim Fit occoocccccnnnccncconcnnccnccncncnnnononnnoncnonnnnonrnonaronnnnconcnnnnnonos 93 3 4 2 General Electrochemistry Menu ooccccccncccccnccccnconcnnonncnnnonnnonarononnnnnnnrnnnnnnnonannnnnnnnss 94 See CAR A O NON 94 EC Lab Software User s Manual 3 4 2 1 1 Baseline SCISCHOMN i059 siavciad cuss era siaiotad isd eum cian edad isd eam pian sad ander uated inde 95 3 4 2 1 2 Peak analysis results cccccceccseccseeeseeeneeeneeeseeeneeeseeeneeese
20. 2 E DLSI Rohm Felll Fell 3 E DLSI Rohm Cdl 4 E DLSI Rohm Cdl 5 E DSSI 10 EEE DLSI Rohm Cdl 11 EEE DLSI Fe 1M Fe D Fe Feco 12 EEEE DLSI 13 EEEEE DLSI Mechanism EE El Reaction Reduction A ze lt gt B Zz 1 E0 0 2 V k 0 1 0m s 1 af 0 5 species CAD 0 01 mol L 1 DA 10e 6 cm2 s 1 DB 5e 6 cm2 s 1 EX 14 EEE DLSI e 111 Reaction 15 EEE DLSI e 123 Reduction B ze lt gt C z 1 E0 0 3V k 0 1om s 1 af 0 5 Title Species DC 3e4 cm2 s 1 EE DLSI Rohm Cdl a Electrode Comments Geometry Linear Semiinfinite Radius 0 1 Surface 0 031 42 on2 Experimental Conditions Temperature 25 deg Rahm 30 hri Fig 136 CVsim examples window 15 examples are available in this window The corresponding parameters are displayed on the right column When clicking the Add button the corresponding curve is displayed 3 4 3 Electrochemical impedance Spectroscopy menu 3 4 3 1 Impedance data analysis Simulation Fit and Kramers Kronig criterion Impedance analysis is a powerful tool to determine the kinetic of an electrochemical reaction and values of the kinetic parameters Electrochemical impedance data analysis allows the user to propose an electrochemical reaction mechanism To be interpreted electrochemical impedance data points need a comparison with an electrical circuit simulating the electron and electroactive spe
21. 2 9 2 Warning options Options default General warning Text export Colors References Tool bars menus Display warming messages on Pause stop Modify auto Accept Next technique C Remove technique V No record Z Multiple ranges e Urbain Cycling Simulation Test Experiment Limits Cancel Fig 61 Option window Warning tab e Display or hide warning messages when the following functions are used Pause Stop Modify Accept Next technique Remove technique No data points recorded and Multiple ranges different current ranges are selected in the different sequences 48 EC Lab Software User s Manual 2 9 3 Text Export options Options default Tete per Tool bars menus Text file exportation format Time Elapsed Time in e 5 Absolute Time mmidd yyyy hh tmm s 333 Fig 62 Option window Text export tab e Select the time recording format for the exported files e Export VMP2 impedance files to ZSimpWin format 49 EC Lab Software User s Manual 2 9 4 Color options Options default Text export Colors Tool bars menus Grid lines colar Curent Values Color gt Ewe Flow chart colors Time Coord _ g Text E Colorz k Sl T a Back Display the next variables in bold we Application background Ece Color le Colors 7 Ej Test O
22. 3433 0 o A elaine eenecd ade cu deiica calcutta 121 34 34 E ieettdes anit ecisee bed ease ae 122 3 4 3 4 1 Mott Schottky relationship and properties of semi conductors 122 3 4 3 4 2 The Mott Schottky plot oocccoocccccococcocncoconnccanoconanonnncnnnnnnnonanonnnnns 123 34 343 ThE Mott Schotlky Plenos is iii 124 3 4 3 4 4 Saving Fit and analysis r Sults cccccccsseecesececeseeceeeeecueeceueeeseeeensaees 125 3 4 3 5 Kramers Kronig transformation cccccccsccceceseeeseeeseeeseeeseeeseeeneeenseeseeeneeenes 126 A A ai 128 3 4 5 Photovoltaic fuel Cell MONU cccccseccceeecceeeceueeceeeceeceueeceeeceueesueeeeeessueeseesseas 128 346 COMOSIOM Me Usina era di 129 Ao dl Linear microPolarization Paca 130 3 4 6 1 2 Constant Amplitude Sinusoidal microPolarization CASP 0008 130 3 4 6 1 3 Variable Amplitude Sinusoidal microPolarization VASP 000 131 LI og Cea a re ee ene ene ee ere ee ee ere eres 132 240 Talca ari toldo adas 134 340 301 Tafe Fil WINDOW iii ai 134 340 32 9 61016 el fc eee ee ee eg oo 136 IAG S MINIMIZ OPTION aaa caverns cubiadinnen buen baceimensieuiuee 136 3 4 6 4 Constant Amplitude Sinusoidal microPolarization fit CASP fit 137 3 4 6 5 Variable Amplitude Sinusoidal microPolarization fit VASP fit 139 3 4 6 6 Electrochemical Noise Analysis cccccccceccceeeseeeseeeseeseeeseeenee
23. 803 VSP SP 150 CLB 500 HCP 1005 SP 300 and SP 200 with the new ARM communication board delivered from 11 2005 with USB port and Ethernet port the memory size has been extended to 640000 points for a 1 channel unit and to 40000 points considering a 16 channel configuration 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 saving frequency in the Option General menu see section 2 9 1 page 47 In the same menu the user can also define an automatic creation of the data file name Changing the channel owner Click on Config User and enter your username in the following window i User Name User name Use personal options Show window at startup Cancel Fig 57 User name window In the case where the new user will replace 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 continue It is not possible to change the user name of a channel when an experiment is running Changing a channel owner is only possible when the channel is stopped Virtual potentiostat When the software is not connected to the instrument it is possible to prepare a setup of parameters in the virtual mode including boosters and options for the instrument Whe
24. Axes Units Graph and Option done user has to click on OK and the new graph style is added to the Graph Style list 19 EC Lab Software User s Manual Graph Representations Ewe vs t A Name vs t Ewe vs t Ewe vs vs Ewe delta vs Estep Graphic style association Lodlll vs Ewe Ewe vs Loglll Style lt None gt Graph properties Q vs t Predefined Graph Style Rp vs t Technique s association Bode Impedance Fr Selected techniques Bode Impedance odd Nyquist Impedance Nyquist Impedance oc Traces Name Black Impedance Axes Black Impedance odd Zl vs t Mott Schottky 3 Graph a Options Add Style Representation Advanced lt Line style Units Plat Lines Markers v Line Solid y Marker SNE y Options Hide OCW Points parameters for all graphic windows Undersample traces over points Draw only lines over points Note common Traces Name 1 al AAA IN 3 El A E y Style Fig 97 Definition of traces properties in Graph style definition 3 3 Graph Tools The EC Lab software contains powerful graphic tools It is possible to perform Linear Fit circular Fit R Fit Tafel Fit Integral calculation Min and Max determination peak analysis wave analysis in convective regime Linear Interpolation Z
25. 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 SP 200 and SP 300 with a resolution equal to its LSB Least Significant Bit that corresponds to the smallest potential step avallable and is defined as LSB a ee ee 305 18 uV for VMP3 family 2 1 65535 and as LSB nae 333 33 uV for SP 200 and SP 300 2 1 65535 When the user enters in EC Lab a potential value Es the value sent to the DAC is a 16 bits value corresponding to an integer number of LSB i e defined as LSB where round is the function that returns the nearest integer of the variable E Eon N LSBwith N round Z 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 the 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 at the top of 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 E A D 65535 Adding the 0 2 V value
26. EC Lab software have been separated into two different fields Electrochemical Techniques and Electrochemical Applications Electrochemical techniques include voltamperometric techniques electrochemical impedance spectroscopy pulsed techniques a tool to build complex experiments manual control and also an ohmic drop determination techniques by ElS measurements Electrochemical Applications include battery testing corrosion measurement custom applications and special applications 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 technique already loaded in the parameter settings window This option will be described in detail in the linked technique section The technique can be loaded with or without the Cell characteristics and the Advanced Settings of the default setting file The user has now the possibility to create and save his own experiment as a custom application see custom application section 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 18 EC Lab Software User s Manual Cyclic voltammetry CV is the most widely used technique for acquiring qualitative informations about electrochemical reactions CY provides informations on redox processes heterogeneous lectro
27. Oxidation peak analysis on a cyclic voltammetry experiment using a linear regression baseline The different values in the result frame of the peak analysis window are as follows Position is the potential E corresponding to the max current value determined according to the baseline Height is the current value for the potential E always according to the baseline Width 1 2 is the potential peak width determined when it is possible at half the peak height parallel to the baseline E E 2 is the semi width for the growing part of the peak Charge Pos is the charge corresponding to the integration of the peak versus time according to and above the baseline in the case of an oxidation peak The part of the peak considered for the calculation of the charge is limited to the green circle markers This zone can be adjusted by moving the markers Charge Neg is the complementary part of the charge in the case where the selected zone crosses the baseline below the baseline for an oxidation peak Note it is possible to save the results of the analysis to a text file using the copy option The results are copied to the clipboard and can be pasted in notepad or other software 97 EC Lab Software User s Manual 3 4 2 1 4 Results of the peak analysis using a polynomial baseline In fact it is often difficult to apply a linear regression to simulate the capacitive part of a curve or remove the beginning increasing part of a s
28. Running acquisition d Click on the Run button A filename selection window will appear My Recent Documents y My Ne File name ICY mpr ki Places Save as type EC Lab raw files MPA Cancel Fig 51 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 36 2 3 2 3 1 EC Lab Software User s Manual Note the filenames can be forced to end with the channel number using the Config Option command This option is always fixed for grouped channels Clicking Save or pressing lt ENTER gt will start the experiment and the Run button switches to the Stop button Two files are created when running the experiment a binary raw data file with an mpr extension automatically added and a text file which contains all the information for the experiment the selected protocol initial settings instrument IP and channel N files directory etc This last file is called the Log of the experiment lt has the same name as the raw file but with an mpl extension Available commands during the run During the experiment several commands remain actives Most of the parameters of the flow diagram can be changed while the experiment is running Changes are saved in the log file Stop and Pause Clicking on the Stop button n will display a message asking for confirmation Clicking OK stops t
29. Units frame Graph The available trace Options properties are the plot style Line Plot Lins O Undersarplirug perk coji reia T the line properties solid mi dash ae and size da En a E Buc 2 Sl the marker properties rectangle circle color Options i C Hide OCW Points nee i Draw only lines ower points Mote common A gt INQ option parameters for all is available when lines Undersample traces over points graphic windows are plotted not with markers Fig 81 Traces window In the Options window it is possible to choose to hide OCV point 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 when the mouse becomes a hand with a pointed finger C It is also possible to select between four styles already defined 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 scientific articles Nevertheless the user can define his own style defined with all the functions of the Graph Properties windo
30. Warburg Wy n Impedance ZIf Na 4 Za Nyquist Diagram mf vs Rel Fig 141 Warburg diffusion element description 107 EC Lab Software User s Manual The Warburg impedance is an example of a constant phase element for which the phase angle is constant 7 4and independent of frequency The Warburg is unique because absolute values of the real and imaginary components are equal at all frequencies 3 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 homogeneous outside this layer The impedance when the material diffuses through the Nernst Diffusion Layer is described by W Description Diffusion convection Impedance lr iz Talent Zj Fay Hyquist Diagram lm vs Reli Fig 142 Warburg element for convective diffusion The Warburg element for convective diffusion is equivalent to the Warburg element in the 2 34 2AT 4 high frequency range f Y 3 4 3 1 8 Linear diffusion element M This diffusion element is used for finite length linear diffusion for example in the case of insertion reactions 108 EC Lab Software User s Manual Description Linear diffusion May Impedance 2111 Pas
31. a reduction lcorr Bo m process This model is based on the Tafel equation that predicts that the logarithm of the current observed QUse and 8 in an electrochemical process is directly related to the Use b and 6 difference between the applied potential and the open circuit potential bi 10 000 ve bi E 30 000 Ye Output E E or EE cor Technique Be KE bor 10 10 The Stern equation can be expressed as follow la e meet Ss where I E is the total current at a specific applied Ecom fjoo 000 m potential E Ecor is the open circuit potential of the Nb points T000 system Ba and Be are the Tafel constant for the anodic oxidation and cathodic reduction reactions and are Noise defined as positive numbers lcorr IS the Corrosion current corresponding to the anodic and cathodic current at E Eco The total current Noise level 1 000 p I Ecor resulting into the difference of the anodic and cathodic current being null as expected Fig 165 Corr Sim window Add noise The three proposed methods are presented hereafter The appropriate method has to be selected in the combo box of the output frame Noise in current in potential or in resistance depending on the technique can be Superimposed to the resulting simulated data 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
32. cell 1 35 A h 3 5 1 8 Polarization resistance Polarization Resistance determines the Rp and Ico 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 electrode surface area value for R in Q cm calculus here 149 EC Lab Software User s Manual Polarization Resistance Process ES File CAMPS Files PR mpr Load Settings n 2 AE 20 0 mm 10 pe Apply a second set of potential stepele with reverse sign on AE electrode surface area 10 001 cre Options f S3ponte AE 2AE SAE Method le 4dports AE 2AE AE 2AE point I to point 10 Calculate lt I gt for f all the points CL cre Calculate R_ in p eo Outputs Linear Polarization resistance Ap anodic 3359 58 Compute Ap cathodic 9 963 1 Copy Rp averaged 3361 45 Number of digits E leor 00135777 Fig 191 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 192 4 points method Fig 193 3 points method n 2 reverse steps n 3 do not reverse steps The 4 points method gives more accuracy so it is proposed b
33. circle The depression is the angle between X axis and the diameter defined from low x intercept R is the difference between high x intercept and the low x intercept C is the capacitance determined for the experimental point in the selected zone where Im Z is max Rco 1 The parameters and results can be copied to the clipboard to be pasted in a comment zone the print window or a text file They can be saved in a text file 86 EC Lab Software User s Manual Circle Fit Selection Trace From point a ae To paint E As Total pointa m we Rele O 46 15 Ohm 0 963 5 Ohm 23 120 6 Ohm 15 33 Ohm ed Parameters lterative algorithm Results Center 4 Center Y Diameter Std Deviation Depression 87 35 Ohm 11 2 Ohm 83 71 0 305 2 16 Low x intercept 47 02 Ohm High x intercept 127 7 Ohm A ES 90 66 Ohm b 204de b F Close Fig 110 Circular Fit window PEIS_Fe_basique_1 mpr Im Z vs Re Z 100 90 80 7O 60 50 40 30 Im Z Ohm 20 20 30 40 50 100 Re Z Ohm EC Lab Software User s Manual 150 200 Fig 111 Circular Fit on the graph 3 4 1 4 Linear interpolation An interpolation tool A is available with EC Lab The raw data file is not changed after this analysis When a data point zone is selected click on Calculate The linear interpolation allows the user to space out regularly in time eac
34. cothl Y74 2aF WT lem Nyquist Diagram lml we Rel Fig 143 Linear Diffusion element The linear diffusion element is equivalent to the Warburg element in the high frequency 3 88 27TT 4 range f and to an R and C in series circuit in the low frequency range 3 4 3 1 9 Gerischer element G The Gerischer circuit element arises when an electroactive species undergoes a chemical reaction in the bulk Description Genscher lay H 3 Impedance Zi o a W14j2atq Noguist Diagram mf vs Rel IN Fay Fig 144 Gerischer Diffusion element 109 EC Lab Software User s Manual Note This list can be continued by new electric elements whenever our customers define a significant one 3 4 3 2 Simulation ZSim 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 lets consider the ZPOT Fe basique mpr data file that the user can find in the sample folder c ECLab data sample The aim of this section 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 ZPOT_Fe_basique mpr data file
35. described below 42 New Ctrl N Load Settings Ctrl L Import Settings From Text Q Load Data File Ctri 0 Save Settings As save As Custom Application Import From Text Export as Text Ctrl T gt Modify Ctrl M Cancel Modify Run Pause Next Technique Print Exit CA ACASP VASPAHPEIS mpr CALA CASP VASPAVWAPEIS mpr CA Data CVsim mpr CA 1631 GUCST aj mpr C urbain_Sminutes_moditi _coup force_last mpr CAVMP Filesi Travail aj mpr Fig 16 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 our potentiostat or another one Our software is able to read other manufacturer formats Saving options are also available The second frame offers the user the possibility to import a text data file from another manufacturer when it is not possible to open it directly Experiment commands Modify run Pause and next technique are in the third frame Print and Exit commands can be found in the fourth frame In the last frame the last opened files are listed Insert New Technique Ctrl I E Insert Technique Frorn File Ctrl F Move Technique Before Move Technique After FE Remove Technique Se Remove All The Techniques E Reset Settings To Default Ee Set Settings As Default i Group Synchronize Channel 1 Add Sequence Duplicate Sequence Remove Sequence Reset Sequence Copy Sequence Paste Sequenc
36. drop during an experiment the ZIR technique has to be set before the technique in which the compensation has to be done To illustrate this the Fig 206 is given as an example In the left side of the figure the series PEIS CV ZIR CV of 161 EC Lab Software User s Manual experiment is defined On the right side of the figure the second graph shows the superimposition of two CV graphs one compensated and one uncompensated EC Lab 10 00 Channel 9 experiment ohmic drop compensation technique 4 4 Cyclic Voltammetry Y Experiment Edit View Graph Analysis Tools Config Windows Help 2 88 E EM F HKTYQARR K xm YX A II Y dd Led dd pd pd pd sd ee gt MI Aa 9 E range min Y max Y res 200 pY Turn to OCY between techniques lt lt Default sl Advanced i ati Caltinos SetEwe to Ej ooo Vo o vs ohmic drop compensation_01_PEIS mpr Im Z vs Re Z Cell Characteristics Scan Ewe with dE dt P0000 mb s to vertex potential Eq 0o00 Y vs Reverse scan to vertex E2 0500 Y ws Repeat ne times Im Z Ohm Measure lt I gt over the last of the step duration Record lt l gt averaged over N voltage steps E Range 2 000 Fresotatine AR Range Re Z Ohm Bandwidth lt gt vs Ewe ohmic drop compensation_02_ CV mpr ohmic drop compensation_04_ CY mpr Endscanto Ef Y ys 02 dE dt 200 p 10 0 ms ForceE1 E2 dEN 20mV 01 1500 points p
37. 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 protocols 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 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 _ short name _ channel number mpr experiment 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 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
38. ee 33 2 2 6 4 3 Smooth with sliding average ooccccocccconcnccocnnconcnonnnnnnnnnnonnnnnnnnnnonnnnnnnnnnos 33 2 2 6 4 4 Create one data file per lOOp ooccococccocnccocnoconoconnncannononocaronnanonos 33 2 20 90 A AN 33 2 2 0 0 GMail 33 2207 Da low CURENIL OPIO asistidos dudo asado assdanido secas 34 223 ACCOPUNO ANG SAVING SENS est nds 36 2 20 RUANINO ACQUISITION aa 36 2 3 Available commands during the rUN cccoccccccnccccnnnccnconcncnanononnconcnnnnnnnnnnonncnnnnnonnronnanonos 37 23 17 Slop and PAU Sis o o 37 2 3 2 Modifying an experiment IN PrOQreSs cccscccscccseecseeceeececesececeeeceeecseeseeesseeseeenes 37 2 4 Multi channel selection Grouped Synchronized or stack experiments oocccoco 37 2 4 1 Grouped or synchronized experiments ooonccccocnccnccnconcnccnncnnoncnnonanononcnnnnncnnnncnnonanoss 38 24 2 Stack experiments sit A dee eee 39 2 5 As A A A 41 2 6 Datapro pele Sind tilda a baii 42 o ate yeaa enna gaa ee 42 2 02 MAatlables description til tte 42 EC Lab Software User s Manual 26 A ale E 1 510 6 q 9 PROPER OPEN ders PO O dons uated inate dens Lene A OR 44 2 0 4 Dala SAVING str irs 45 eS Changing the channel OWNET cascada 45 2 8 Virtual pote Osdia 45 2 9 So aidle UL ile ale e q 1 PROPER ONPE Meriter a TS PET int einer Tae Nr in eitpera 47 29 7 General ODIN iio 47 292 O 48 29 3 TEXLEXPO OPIO Sc dica nicole 49 2 9 4 GOO OPINAS a ado 50 2
39. end of the previous open circuit period e Status gives the nature of the running sequence oxidation reduction relax open circuit measuring the potential paused or stopped Buffer full will be displayed in the case where the instrument s intermediate buffer is full saturated network Buffer indicates the buffer filling level Q Qo is the total charge since the beginning of the experiment The current range N is the number of the current sequence Ne is the number of the current cycle or loop Note Two protocols Batteries GCPL and PCGA propose an additional display variable X Xo This toolbar 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 graphic bar at the top of the window Channel 2 values Fig 12 Current values tool bar in a linear format Note In the default configuration all the tool bars are locked in their position But at the user s convenience tool bars can be moved to other places in the window To do so click on Config Option Tool bars and deactivate the Lock tool bar box This will be effective after restarting the software Once the user has defined a new configuration of the tool bars he can relock the tool bar the same way he unlocked Note also that some of the current values can be highlighted in bold In the config option colors menu EC Lab Software User s Manual 2 2 1 5 The parameter settings frame
40. flow diagram or the column diagram is display 19 EC Lab Software User s Manual EC Lab V10 00 a Experiment Edit View Graph Analysis Tools Config Windows Help adesar 41 ale 4Axm YY a FU FU FU FU FU FU FU FU FU FU FU p FU 3 AS AI A A Ll Show bd 4 d Advanced fo o00 V vs Eoc y fr 000 W vs Ret y o fo 25v 25v vi 4000 points per cycle Repeat n lo time s 0 000 Eo v Force El E2 End vMP3 MC o SEENA e 923 540 4 05 402 D b s Fig 28 Cyclic Voltammetry detailed flow diagram EC Lab V10 00 Experiment Edit View Graph Analysis Tools Config Windows Help BORA E bt KTR S AK YN IN Y SS Se So Br Be AD dt E A LN A Eoc y dE dt 100 p 5 0 ms Force El E2 dEN 1 0 mv 4000 points per cycle vMP3 MERT channel CS e 923 540 4 05 402 Obrs Fig 29 Cyclic Voltammetry detailed column diagram 20 EC Lab Software User s Manual When a technique is loaded on a channel the detailed flow diagram is displayed In the blue column the icon shows the loaded technique and in the blue row the user can adjust the potential control resolution here to 100 uV for more details about the potential cegrol resolution refer to section 5 2 1 page 166 Moreover on the right of this row a button is available to show the graphic describing the technique and its variables Ewe chide Fig 30 CV graphic description The E
41. 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 corroded 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 relevant
42. in red on the trace 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 CV_Fe_basique_1 mpr Minia Ed dl ys Ewe Selection Trace lt l gt vs Ewe From point x ot F v N f To point ae Total points Results Minimum point 5157 A 0 092 62 Y ire 224 7 pA Maximum point 2083 X 0 232 6 Y ue 209 2 p lt I gt pHA EwelV vs SCE EC Lab Software User s Manual Min Max Selection Trace l gt vz Ewe From Point 3551 mt T To Paint me Te 0 299 4 0 088 32 m 3950 0 300 5 Y 0 089 07 m Total points 2000 Results Minin 5157 0 092 62 W 0 224 2 m 4087 0 236 8 W 0 207 E m Close Fig 106 Min Max fit window Fig 107 Min Max determination on the graph 84 EC Lab Software User s Manual 3 4 1 2 Linear Fit Linear Fit When the zone to fit is selected click on Calculate in Selection the linear fit window Fig 108 A straight line is Tecan Imz vs Rez displayed as a result of the linear regression between From Point 27 two green circles with the Least square method fit Fig Hi 130 5 Ohm 109 o 15 76 Ohm ToPomt 38 Move the circles with the mouse by holding the mouse g 234 8 Ohm left button to modify the range of data points selected for ye 108 8 Ohm the fit The new linear regression is automatically
43. instantaneous current variation dl and or charge variation 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 potential variation dE and or charge variation dQ Recording conditions are described in the application section for each technique 44 EC Lab Software User s Manual If the user wants to force a periodic recording in time he must set a large value in the recording resolution of the variable or more simply set the recording resolution to 0 So the box for which the resolution is O stays colored This color code means that this box is not activated and also not taken into account for recording 2 6 4 Data Saving 2 2 8 Each channel has its own memory buffer small to store data points The recorded points of all the channels are stored in the motherboard buffer The instrument buffer can store a number of points depending on the protocol and the number of channels working in the instrument The buffer size increases when the number of channels in the instrument decreases The minimum number of points considering 1 channel is 48000 points for the VM42 module and 480000 points for the VM62 module and considering 16 channels VMP2 VMP MPG is 3000 points for the VM42 module and 30000 points for the VM62 module For the new instruments VSP VMP3 HCP
44. 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 166 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 5 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 modification is necessary 5 2 2 Setting of the Working Potential window lf no experiment limits are defined the potential resolution is 305 18 uV or 333 33 uV corresponding to the 10V 10 9 V range E Range is located in the setting of each technique since EC Lab version 10 00 ES 10 10 510 Ov 10 AYO AY OV oy AA a Fig 213 E Range selection Using the Edit button opens a window to define the potential range manually Entering the required Eye min and Ewe max the corresponding value of the potential control resolution appears For example entering O V and 1 V leads to 20 uV resolution Edit Potential Range E range min BR Y max i 0 000 Y resolution 305 18 pi oa
45. la ret Fig 214 Edit potential range window Application Optimization of the potential resolution is particularly interesting when trying to perform protocols based on potential scan such as CV in order to approach linear scans as much as possible 167 EC Lab Software User s Manual 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 215 below Fig 215 CV experiment potential scan with 20 uV steps 5 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 contrary 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 choosing the range in which the experiment is performed In fact the result accuracy will be better if the range is chosen closer to the experiments limits 5 3 1 The potentio mode The potential control range can be adjusted for the experiment with the experiment limits Emax and Emin see the install
46. limits are used in two ways first to protect the electrochemical cell from damages during the experiment and second for the potential 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 linker 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 settings of the experiment but no data points 181 EC Lab Software User s Manual Loop protocol available in the linked experiments and used to repeat one or more experiments It is different from the cycle in an experiment Low current option providing a sub pA resolution that can be added to each channel 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
47. 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 setting window 3 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 3 5 2 3 ASCII text file 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 Experiment menu If the software recognizes the data file EC Lab will be able to open it 153 EC Lab Software User s Manual 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
48. other users However change of parameters on a channel is authorized only if the present username 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 username at any time You can also double click on the User section in the bottom of the EC Lab software window to change the username The user can specify a personal configuration color display tool bar buttons and position default settings which is linked to the username 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 software is starting When the username is set the Global View window is displayed Global View channel 1 BZ th 2 BZ 3 42 LIZET tech status Oxidation Oxidation amplifier contral E we Ece Ewe E ce time channel UZET tech status amplifier contral Ewe Ece Ewe E ce time W Show window at startup Fig 3 Global view window When the computer is connected the global view of the channels shows the following information in standard according to the configuration of the instrument e channel number with a LE
49. ouptut parameters can be given as Fit or b constant The x7 is defined by the following equation 1 IG e 1 W Ry kk xu N Do X si a X satci i l Use E and 8 s OUse b andb 5 K Darowicki Corrosion Science Vol 37 n 6 913 925 param sel value 1995 6 J P Diard B Le Gorrec C Montella Comments Corrosion Science 40 495 1998 T 3 017e6 Iterations 190 I Fig 180 VASP Fit window 3 4 6 6 Electrochemical Noise Analysis The study of corrosion phenomena by electrochemical noise involves the analysis of random current or potential fluctuations To study these fluctuations the tool Electrochemical Noise Analysis tt was introduced into EC Lab in the version 10 00 Electrochemical noise method requires three electrodes to establish a parameter known as the noise resistance R Two of these are working electrodes and current is measured between them at regular intervals Fluctuations in current and potential are called current and potential noise Three methods are available to calculate the electrochemical noise 139 EC Lab Software User s Manual Standard deviation With the two standard deviation values EMES TE eT current and potential it is possible to apply the Ohm s law Selection relationship and to obtain the parameter Rn R Ewe with Trace ls time O Cycle 7 From point 3 CEwe and co obtained with the formula ox gt AR se T 120 ie 58 79e 6 m whe
50. properties e Predefined Graph Style Custom Graph Style EC Lab Software User s Manual Graph Units window is used to choose the correct graph units for the different variables The default units are in Traces Graph Units gray boxes If the user Axes C Time chooses another unit he F Potential must activate his choice Graph C Current by ticking the box Options F Charge corresponding to the represented variable Frequency a Specific units are C Resistor available for current and L Power i charge on one hand and L Energy i for power and energy on Capacity the other hand For current and charge the user can select a current density or a charge density according to the electrode area or to the electrode characteristic mass Potential vs Reference Electrode Offset potential ws Normal Hydrogen Electrode 0 000 Edit Surface And Mass Fig 83 Units window Power and energy can be plotted according to the electrode characteristic mass In such a case the software will ask for the electrode surface area or for the characteristic mass The following windows will be displayed Edit parameters File CY Fe basique 1 mpr Parameters Electrode surface area LATIH Characteristic mazs 0 001 Fig 84 Electrode Surface Area and Characteristic Mass window The Electrode Surface area and Characteristic Mass window is used in the unit window for area charge or cu
51. 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 Reference 129 EC Lab Software User s Manual 1 Stern M and Geary A L J Electrochem Soc 104 56 1957 3 4 6 1 1 Linear microPolarization LP Among all the techniques offered the linear micropolarization is the most standard one Resulting plot is given in vs E For this modeling the range of potential scan around the corrosion potential and the number of points are set Corr Sim Parameters Ecom 200 000 rity ane leon 3 000 p 0 4 O Lee Be and Bo Use b and bo 0 3 b fi0 000 Ye de b 30 000 Wo 0 1 I mA Output LP s a Frow 2 E Frerv ES Seu Ecom 100 000 mr Mb points 1 000 Moize Da 2 0 1 Ewe V Add noise Noize level H 000 8 p Fig 167 Output data for Linear Polarization simulation Fig 166 Corr Sim window for Linear Polarization 3 4 6 1 2 Constant Amplitude Sinusoidal microPolarization CASP In this technique a small sinusoidal excitation is applied to the system In order to prevent the polarization of the sample the intensity of the excitation Va has to be weak for example few mV The frequency of the sinus f is typically in the hertz range The simulated harmonic plot is given in vs Time 130 EC Lab Software User s Manual Corr Sim Parameters Ecorr 200 000 rev corr 3 0
52. the required circuit is not in the list then the user can create his circuit in the Edit window Click on Edit to display this window 111 EC Lab Software User s Manual Equivalent Circuit Edition Circuit 99 159 R1 01 R2 C3 R3 Add Al C2 A2 C3 A 04 A4 RA1l C2 R2 C3 R 34M 4 R1 C2 RA2 C3 A3 444 A RAC3 A dwdd A A AICA R20 aA 04 Ad RTHCA R G Ale Ree da R1 G1 Al G2 R2 R1 L1 R1 L1 C1 Al L2 A2 Rl h AlthM 22 R1 01 R1 01 R2 C2 R3 231A4 44 052R5 A1 01 R2 C2 A3 L4 R4 C05 R5 A1 07R2 C3 A3 Description O m m m Im 255 Display The Circuits With F 5 T Elements O lam 2c Element s All The Circuits Fig 147 ZSim ZFit Circuit Edition window The circuit base contains more than 130 circuits The user can create his circuits to be added in blue to the list The main circuits have been described on the right side of the window circuit scheme faradic impedance equation and impedance Nyquist diagram 3 4 3 2 2 Circuit selection To select a circuit in the list the user can select the displayed circuits according to the number of elements or the specific elements in the circuit number of resistances number of Capacitors 3 4 3 2 3 Description code If the required circuit doesn t appear in the list the user can create it He must write it in the first frame top with several rules 1 For elements in series the used sign is For example for R in serie
53. uV 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 at Range The current range has to be fixed by the user When the current is a measured value measured can be greater than the chosen Range without current overflow error message In this case the potential range is reduced to 9V instead of 10 V The maximum measurable current is 2 4 Range For example with Range 10 mA the current 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 5 2 1 page 166 21 EC Lab Software User s Manual Note with booster ranges and 1 A range of SP 300 and SP 200 this relationship is not available Bandwidth The VMP2 Z VMP3 VSP MPG2 SP 150 HCP 803 HCP 1005 and BiStat devices propose a choice of 7 bandwidths damping factors 8 for the VMP and MPG devices and 9 for SP 300 and SP 200 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 experiment before choosing the damping factor The following table gives typical frequency bandwidths of the control amplifiers poles for the VMP3 VSP MPG2 SP 150 HCP 803 VMP2 and B
54. window 3 The user can also click on the right button of the mouse and select New experiment in the menu ee Then click on 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 setting parameters In that case the following message is displayed When double clicking on a channel belonging to another user a warning message is displayed asking for confirmation of the user s name modification 17 EC Lab Software User s Manual 2 You must be in Modify mode to insert a new technique Switch to Modify mode Fig 25 Message displayed before to switch in Modify mode Click on Yes and the Insert Techniques window will appear with the different techniques available with EC Lab software Insert Techniques a Electrochemical Techniques Voltamperometic Techniques Open Circuit Voltage OLY lt lt Cycle Yoltarmmetry CY Chronoamperometry Chronocoulometry CA Chronopotentiometr CP 2 Staircase Yoltarimetry SW Impedance Spectroscopy fF Pulsed Techniques aa Technique Builder Electrochemical Applications Batteries Testing Corrosion ES Custom Applications Insert Technique Load from default Custom Applications as w Advanced setting W Cell characteristics Usas Fig 26 Techniques selection window Techniques available with
55. 0 000 Fig 32 EC Lab table During the run the active row of the table sequence running appears in color The default number of rows is 10 But the user can insert delete append copy and paste up to 99 rows by clicking the right button of the mouse lt can be a very interesting tool when the user wants to repeat an experiment with one different parameter in a sequence It is also possible to cut copy and paste only one cell of the table 22 EC Lab Software User s Manual Copy Row Ctri L Paste Row Ctt Insert Row Ctrl Delete Row Ctri O Append Row Ctrl Cut Cell Copy Cell Paste Cell Fig 33 Table right click with the mouse Note The user can define different current ranges for each sequence if an OCV period separates the sequences at the beginning of each sequence for example Itis possible to repeat a block in a sequence goto sequence N 2 2 5 Cell characteristics Clicking on the Cell Characteristics tab will display the cell characteristics window 2 2 5 1 Standard Cell Characteristics window 7 dvance 4 Cell Description Record settings Electrode material Au Pd Ecen Cell Initial state Ewe Ecesv ectrolyte Parameterz i al 0 2M Analog IN 17 Settings Comments Analog IN 4 Record external devices on Analog INH sia 1 04 Battery gt gt Files Electrode surface area oon cre oF E H Characteristic mass 0 001 g i E 1 _ WE Equivalent weight 10 000 greq
56. 00 pu s CorrSim mpr Use Be and B e Hee b and b s time 0 008 0 006 bo 10 000 NA b 30 000 Wed 0 004 Output 0 002 lt CASP E o0 ALLE F 3 F F E a petsciancaee 0 002 F E anteret com beg SUD 2 mol 0 004 Ma i 0 000 rn fs 10 100 Hz 0 006 HE points 1 000 0 008 A E E s l 0 20 40 60 80 100 Mose time s Add noise Noise level 000 P Fig 169 Output data for CASP simulation i O00 crit Fig 168 Corr Sim window for CASP Simulation 3 4 6 1 3 Variable Amplitude Sinusoidal microPolarization VASP The A determination is done at several sinus amplitude from Va min to Va max These measurements are typically performed at low frequency Variable amplitude EIS simulated plot is given in R vs sinus amplitude Regarding the settings the simulation required the range of frequency and the number of point 131 EC Lab Software User s Manual Corr Sim Parameters Ecorr 200 000 rei lore 3 000 ue CorrSim mpr Rp vs sin ampl O Uze B and Bo Use b and b 1 200 b s i 0 000 Ve b 30 000 Ve Output VASF En bee dk l 65 z SoL k 0 2 Bich 1 Ya mir 1 000 rei 200 Ta 400 Ve vamas 200 000 rr ol Nb points 1000 j 0 0 1 0 2 sin ampl V Noise Fig 171 Output data for VASP simulation Add noise Noise level 1 000 Ohm Fig 170 Corr Sim window for VASP Simulation 3 4 6 2 R Fit For E sufficiently clo
57. 0000 4 freq Hz log spacing SPEIS mpr D 3 N j F4 lt i cycle number o 2 1 100 1 000 10 000 100000 freq Hz log spacing Fig 79 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 80 Thanks to this menu it is possible to come back to the 2D representation or to display simultaneously 2D and 3D graphs As for the 2D representation it is possible to Copy and Print the graph as explained in section 3 2 7 page 70 The Graph properties menu for the 3D representation is the same that the Graph properties menu for the 2D graph and this menu is detailed in the following paragraph O wD 2030 Copy d E Print Ctrl P Graph Properties Fig 80 3D menu Note that to display a data file with the 3D function the number of points should be inferior to 15000 points 65 EC Lab Software User s Manual 3 2 5 Graph properties 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 The Traces window allows the user to define all the properties of the Custom Graph Style selected traces Select the trace you wish to ae 1 lt l gt vs Ewe CV Fe basique 1 mpr modify in the Trace Name
58. 200 and SP 300 5 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 2A for a short time t lt 1 ms followed by a step to a lower current l2 for a longer period t I L I 0 t to t Fig 210 Theoretical GSM pulse waveform 164 EC Lab Software User s Manual This theoretical pulse waveform can be easily programmed into EC Lab with the chronopotentiometric 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 l gt never exceed 400 mA dE mi E 0 000 m 0 000 m O 00 0 0000 pass 0 000000 0 00 0 0000 14 1 400 A 0 000 m s 0 00 0 0010 pass 0 000389 0 00 0 0002 14 0 300 A 0 000 m 0 00 0 0100 pass 0 000833 0 00 0 0002 14 Fig 211 Table of the experiments for GSM battery testing The result is represented on the following figure 1600 1400 1200 1000 800 600 400 200 14 times Fig 212 GSM pulse waveform generated by chronopotentiometric protocol 165 EC Lab Software User s Manual 5 2 Optimization of the potential control resolution 5 2 1 Potential Control range span Our potentiostats galvanostats are digital instruments The potential is applied to the cell via a 16 bit
59. 3 Peak analysis PAC SUNS AP 96 Peale AAV slotacsu O o est II rank seeks A 94 FeO lie COO RCI ale Scala 58 Polanzation FAC SISTAMCG unitaria a E Mascindvinckinat 132 FOlental COMIMONT CS ONION voiee i atrcat eens Weisner nido 21 Potential Range PAC LISTON CNN ess Actes Ss ec a Aa Sneek ns eas ae Bical Sc At a 166 Sl e e E OR R A E EA E AAEE E E 166 e e o o OOO INIA 24 26 PEE COPEC POE E cn tance RIO et tren SO eta ates eee a 71 Process Capacity and energy Der e Gian tall 146 Ot PEA act Sek mo acetate atta ache A a eae bath 143 145 Constant power protocol SUIMIMALY orniaini ETA EEE EHS PEREA PENTE EES ERICEIRA 148 delne CY CIS eisien iia a aa 143 ENOTO dc is 147 EXPO as Ola ts 143 _ erestcte aman A 152 A oan cece scene ett eee eee tel espe caren a are cetera sateen 176 Multi PUNO Slat SUC S asii 151 A dine tesebdttieadin des cbdigiesdiac a a 143 FOlablZallon resi io cios 149 ELE SC SE EE ENE ENE 143 SUIMIMANY DCF CV CIC sac c8 e ced oe e ade 147 AAA e O o PA 153 Process Dalai aaa deidades 142 PO eS SINC tetera editado 141 io leo A Ae o cs iets ah aelcnatoea cht oi ane ta eae ce abaeae cater aeenae ean 158 PSCUGO GADACITAINGS a case a tees 120 DN act Bae be ate Se eS a Se fc ae O Soa en 175 QUES taaan ad 17 Record CONAN Sins 44 o eerren nr ee ee 24 26 Recording conditions POLETU ete a che che cette ce sete A A 21 Reterence CISCO CC anta a ii 24 26 A TEE 155 A CS SHG nora aise fananais wanda fa
60. 4 642 kHz Mott Schottky curves The selection is the same for the 3 160 kHz 2 153 kHz time evolution of the impedance or of the phase 1 467 kHz 1 002 kHz M All frequencies Cancel Fig 159 Mott Schottky frequency selection window Then the graphic window shows one trace per frequency Use the shift key to display the frequency 123 EC Lab Software User s Manual Fig 160 Mott Schottky plot It is possible to set the surface area and plot a capacitance related to the surface 3 4 3 4 3 The Mott Schottky Fit The Mott Schottky Fit Ai is a graphic tool introduced with the SPEIS technique to determine semi conductors 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 C vs Ewe of the experiment must be displayed on the graph This plot shows one trace for each selected frequency 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 between 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 ca
61. 9 5 Reference electrode Options cococccccnccocnoccnnconnoconnnnnncnnnnonnnnonnnnnnnnonnnnonanennnnonons 50 2 30 TOOLDAS OPIONS arietta a ea 52 EC Lab software Graphic Display 0 ccccscsssssessssssscessssesseesssessseessenesseesesnesssneeeneeaas 53 3 1 Th Graphie WINGO Werscccintianicn codec ound aa aaa aa aaa aaa aei 53 3 1 1 The graphic window right click MO NU cccccceceseeeseeeseeeseeeseeesaeeseeeseeeseeeneeeneeenes 53 3142 Loading adata Te orcii i r aiii dai 56 3 1 3 EC Lab graphic display oocccnncnnnonicnonncnancnononaninonanannc cnn corno n anno nana n cana caninos 58 31d Crap WOO Da Sun ei ands ae eas ee 59 3 1 5 The data file and plot selection WINdOW cooocccocnccocnconncconnnoncnonononnononncnnnanonncnnnnos 59 3 2 Graphic ACIS Serrat 61 3 2 1 Cycles Lo0ps VISUAIIZATION cosita id neo 61 322 MO W TAOS DOMO sinea od 62 3 2 3 Add comments on the graph cccoccccccncccnncncnccnnnonononncnnnnnnnnnnonnnnonnnnonnnonannnnaninannnnons 62 3 2 4 Three Dimensional graphic oocccocccoccconcconnconncncnconncnnnnonnnonnnonnnonnnnnnnnnnnnnnnnnnnnnnnns 64 3 2 0 Graph Properes snini E EEA iia 66 32 6 TNE LOG ISTON Messi 70 32 COD ODON Lon eter eee e a a ee eee eee ee ee 70 due rel olanda CODY ODE ONS ccs acces ater eee tea cee eee ae crete 71 32 72 Advanced CODY ODUONS epris 71 SiO IRNOS cra Rae meer te ENT emery te RAT mer ie RATT tee 71 3 2 9 Multiple graphic WINKOWS moredi a AE E A
62. Al 02 R2 v Eai e param el sign value E Ohm 0 476 2 318286 Felal 6 71 5e 6 08103 0 548 8 f 81 58 Ohm 1 224 x Pseudocapacitance Equivalent circuit RA1 C2R2 OOOOOO8 8 Calculate Fit Ske sel Method Randomize Simplex hes Randomize Stop randomize on h o000 iterations weight i Ml wan i 14 37 lkerations 169 Simples Cycle susy Fig 156 Fit results and pseudo capacitance calculation 120 EC Lab Software User s Manual The results can be copied and pasted in another document 3 4 3 3 6 Additional plots C EC Lab Data Samples ZP0OT Fe_basique 1 zfit mpp Detta PhaselZ ws frey log spacing Detalj vs freq log spacing Delta Phase Z deq a Fa Zeus a 0 1 1 10 100 1 000 10 000 100 000 lfreq Hz log spacing Fig 157 Plot of the relative error on Z and phase vs frequency log spacing 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 Z meas calc x _ AZ Z x100 Alp lp meas lp calc Re Z Re Z Im Z Im Z A Re Z PZ AD 10 AlIm Z a Ds x 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 se
63. Axis AL Y2 Axis Fig 67 Plot Mouse mode selection and mouse auto scale options 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 the 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 Mouse Autoscale is made of different autoscaling functions according to each axis The second frame contains Analysis tools and allows displaying analysis results In this menu determination of Minimum and Maximum on a curve Linear Fit Circle Fit and also Integral tools are available This menu allows also the user to do a Peak and Wave analysis but also corrosion fits Rp Fit Tafel Fit CASP Fit VASP Fit and also Impedance analysis and simulation ZSim ZFit and Mott Schottky These tools will be described in the Analysis part see section 3 3 page 80 55 EC Lab Software User s Manual The third frame is dedicated to comments addition on the graph with the possibility to Add and delete a comment zone and paste a comment from the clipboard The fourth frame is to show or hide OC
64. Bode Admittance Nyguist Admittance Black Admittance rml rel cd log pacing Mame Representation Advanced Yl axis Ye ari k hn Phase 4 deg log separate traces SS treg Hz log spacing Fig 92 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 93 Nevertheless it is possible for the user to define his own processing function using the Custom menu Then in the window given Fig 93 the user can define an operation in the Variable box in this example it is the e box Mathematical functions are available ticking the box more 19 Graph Representations Black Impedance vs t Mott Schottky Bode Admittance Nyquist Admittance Black Admittance El Phase error wows t Ece vs t Ewe Ece vs t Bode Al cycle vs time Evel I vs freg Black Impedance odd B Hame Representation Advanced EC Lab Software User s Manual ES YT axis 41D lhm e freq ve time A amis 1 Yr2 II wz freg 1 z sort 2 i log spacing Ye ari Fhaseli deg a Y2 r2 hee log Y log spacing g custom expt exponential of a number sort square of a number sorte square ro
65. C Lab software protocols are made of blocks Each one is dedicated to a particular function When not activated a block is in gray color The user has to set parameters in the boxes to activate a block which becomes colored color for the repeat block is different when activated A box with an active value is white and stays colored when not activated The recording function Record in the first block can be used with either dEr or with dtp resolution or with both Data recording with dEr resolution reduces the number of experimental points without loosing any interesting changes in potential When there is no potential change only points according to the dtr value are recorded but if there is a sharp peak in potential the rate of recording increases In every technique with potential control the user can now choose the current recording conditions between an averaged value per potential step for a sweep and an instantaneous value every dt see the application section When a technique is loaded in the parameter settings window a small icon is displayed on the left of the flow diagram with the name of the technique and the number level in the experiment in case of linked experiments During a run this icon is circled with a green frame Notes E Range adjustment On the technique the user can define the potential range min and max values to increase to potential resolution from 305 uV 333 uV for SP 300 and SP 200 to up to 5
66. Channel menu permits the selection between Grounded and Floating mode for the used channel 33 EC Lab Software User s Manual 2 2 6 7 Ultra low current option This option is only available with the SP 300 technology and more especially 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 In these extreme conditions measurements may be distorted For instance a loop appears at the vertex Fig 48 The value of current scan where the correction must be applied depends on the intrinsic characteristics of the cell type of electrode distance between electrodes A correction is offered in the Advanced setting window This option is automatically selected when Ultra Low current option is connected Note that if the Ultra Low Current option box is ticked the data may be noisier especially for ranges below 1 nA Fig 49 It is possible to reduce the noise by filter the data available in the Math menu of the Analysis menu lt l gt vs Ewe UME 5Vs_sans compensation_1nA mpr cycle 3 UME_5Vs_avec compensation_1nA mpr cycle 3 i Z XI 0 5 Fg w r 1 1 5 TA AAA ra Ewe V vs SCE Fig 48 CV carried out with an Ultra Microelectrode of 10 um in a solution of ferrocene in EtOH with TBAP as supporting salt The range of current is 1 nA and scan rate is 5 V s Zoom at the vertex
67. D red if there is no experiment running or green color if the channel is running 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 channels EC Lab Software User s Manual e tech the experiment type once loaded e g CV for Cyclic Voltammetry GCPL for Galvanostatic Cycling with Potential Limitation PEIS for potentio impedance etc e status the running sequence if an experiment is in progress oxidation reduction relax open circuit potential or stopped e booster the booster type if connected 1A 2A 4A 5A 10A 20A 80A 100A a 500 W load or none for VMP3 technology or 1 A 48 V for SP 300 technology the p low current board if connected for VMP3 technology or low current cable for SP 300 technology The user has the ability to add several current variables on the global view such as Control l Ewes Ece EwerEce and time Right click on the channel and select the variable to be hidden displayed You may use Channels Global View to display the global channel view Double clicking on any of the channel window will replace the global view by the specific view of the selected channel 2 2 Preparing and Running an Experiment with EC Lab software This chapter is designed to guide users through the use of EC Lab software 2 2 1 EC Lab main window Double click on a cha
68. E ae dete a et ancl ce ect ne eet ect ee eae ae eae eee cr 59 LE E o gn 125 AO o AAA cit cee ect cet nected eel Ceol cm ate ce 152 Axis Mouse AA US ii e a a ol 67 lalo lo g PPP A 22 EFS eS em ee nr AR 95 AUG esis tee sacs eee Aaa A et 41 BIO LOIC WDS eee eee eee ee ee eee ee ee ere eee 17 GAD ACIOM A AE oeAQP P A 106 Gel ENaractenstOS tri 23 BC dira 27 Channel selection TOO Da uos a Gnas 10 Channels OD a A o NNA acoeuaeaeaaraaies 9 GMaAraClehiSUC Masia a 24 Gnearacteristic MaS Sia a 68 e a ee ee 86 So DA calco 19 GORMO ee acess a ceresiee eas aa sate see aec ene nie guia nae re Sots ae mnie eat hs ee eeneuane ence eneaes 62 Lo AER eE O PON fy eRe PN Ee 63 COMMUNICATION DOAN estar id lid sos 45 COMPA Emer A o O N ory eae ee ee CS 145 e eer eet eR ene MEE re ce EE Me Int Et EE 30 Config A A eee eee eee ere 47 LS OF wre nectunsais seatenciots naclensiais a o Ae 45 Connections E 1 3 0 21 gt gee am RIO eRe re Oe Oa RO er e Oe 31 aN Sah os A o a 32 Constant Amplitude Sinusoidal microPolarization CASP c cccccsecceeeeeeeeeeeeseeeseeeeseees 137 Copy CA lira rio edades alinean anida sae eabaaeeeeoaeaeebaeaeee se 62 CODY a eas ces teptciaatede satiaaademateee ce assensde A E anaes nated me eerseemteaee 71 Copy Ell Data CONE ela 71 COPY 10 AP ers eee ater ree we ee re eee ee eee ee 71 SOD Gla ACV ANC CC ce ea neto eta ee eta ee ect eel eee 71 Copy Z Data 2siMpPrIA iasiarastcacooa islas leds 71
69. E2 dEN 1 0 mv 01 3000 points per cycle 0 5 0 0 5 5 000 EwelV Re Z Ohm i ditatus Oxidation Time 0 04 20 Ewe 0 459 1 0 091 mA Buffer 20 Eoc 0 323 mW Q Qo O40pAh P 41 547 pw ne 0 IRange 100 pA v VMP3 JL 192 109 209 222 Channel9 Readmode 45 5 0 0143 8 272 bis Fig 203 Linked experiments window The linked techniques are displayed on the left of the window with their number in the experiment 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 a green color around the corresponding button lts number is displayed in the running experiment box see next figure as Run Tec The number of loops executed is displayed as Tec Loop As for a single experiment run it is possible to Pause Resume and Stop the experiment 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 Exp button 7 in the tool bar 160 EC Lab Software User s Manual Channel 1 values ES Oxidation Fig 204 Linked experiment current values Notes e The ZRA MUIC protocols and the manual controls cannot be linked e The Polarization Resistance process calculation can be per
70. EC Lab Software User s Manual Version 10 1x February 2011 ap BioLogic Science Instruments Equipment installation WARNING 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 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 accessories 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 resulting
71. EC Lab software settings 2 1 Starting the Program Double click on the EC Lab icon on the desktop EC Lab software main window will be displayed 9 EC Lab V10 00 Channel 1 no experiment rE Experiment Edit View Graph Analyse Tools Config Windows Help ERLE a E E E E E E E E M M O E E E ol O ee AE Turn to OCY between techniques lt lt Default settings No experiment loaded on current channel Cell Turn into Modify mode menu Experiment Modify I to unlock Characteristics the channel and define a new experiment set with Experiment E Parameters New or Experiment Load Settings 4itetus Time Ewe los Butter Eoc D o Range VMPS ETS Channel Read made 8 Fig 1 Starting main EC Lab window Immediately on the main window the following Username window will appear User name i o Use personal options Show window at startup Fig 2 User name window Type your username example My Name and click OK or press lt ENTER gt EC Lab Software User s Manual This username is used as a safety password when the instrument is shared with 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 become the owner of the channel for the duration of the experiment All users are authorized to view the channels owned by the
72. Fit Fourier Transform Corrosion simulation Corr Sim Filter Constant or Variable amplitude Sinusoidal micro Polarization CASP Fit or VASP Fit and Mott Schottky Fit within the Graphic display These analyses are available in the Analysis menu and the right click menu as described above They will be described below First of all before any analysis select the trace to fit if several traces are displayed on the graphic window or the cycle if a trace contains several cycles There are two different ways to make a fit on a trace with the EC Lab software Two steps must be considered the zone selection and the fit choice One can be made before or after the other The two ways to proceed are as follows 80 EC Lab Software User s Manual 1 In the main tool 225 click on Graph and then Selection or click directly on the selection button of the graphic tool bar On the graphic window select the zone which needs to be analyzed by holding the left mouse button The cursor will draw a rectangle around the chosen zone Once it is complete release the mouse button The part of the curve selected should be highlighted in red and ready for analysis Then select the required analysis either with the right click menu or in the Analysis menu or in the graphic toolbar y LO Dib 2 In the Analysis menu or in the graphic tool bar select one of the tools The mouse selection mode is automatically selected The user has
73. For both randomisation and fitting the user can define the number of iterations and for the fit he can also select a relative error Another option Weight is available with two choices either 1 or Z resulting in a different weight of data points at high and low frequencies During the fitting process the iteration number is displayed at the bottom of the window To start the operation click on Minimize 116 EC Lab Software User s Manual 3 4 3 3 3 Application Considering the previous example ZPOT Fe basique mpr the following result may be obtained using the Randomize Simplex option with the default parameter values Selection Results rez va Ret l Equivalent circuit e Im Z vs Re Z ZPOT_Fe_basique_1_zfitmpp R1 02 A2 42 47 57 Ohm 0 349 7 17 096 Fs la 1 3 167e 6 0 885 0 559 8 70 94 Ohm 0 7898 85 33 Ohm s 1 2 0 386 8 Calculate Fit Select curent v cycle s Method Randomize Simplex z S a E Randomize Stop randomize on 2000 iterations Stop fiton 5000 iterations v Weight 1 Y 1 25 42 Iterations 5000 Simplex Cycle xxxx 150 peice Fig 152 Fit results with a combination Randomize Simplex The randomization was stopped after 2000 iterations and the fit after 5000 iterations In that case the y value is related to a weight 1 for each point The more the number of points selected for the fit the higher the y value will b
74. MP3 3h 192 109 209 222 Channeli S EPs 0 449 0 116 12 284 b s Fig 71 Graphic window As can be seen the above window Fig 71 displays a loaded Cyclic Voltammetry mpr file On the trace a part of the curve is selected and displayed in red color 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 keyboard or clicking in the yA box This comment box contains the point number in the experiment and the point coordinates Origin axes can be displayed with another color on the graphic window Note On the button menu two buttons have been added to switch easily from the current graphic window to the current setting window 58 3 1 4 3 1 5 EC Lab Software User s Manual Graphic tool bars When the graphic window is displayed the graphic tools bar automatically appears at the bottom This bar is hidden on the parameter settings window Pe o Fig 72 Graphic tool bar This tool bar can contain all commands usable on the graphic window The five first buttons are for the different mouse modes The four buttons in the second fr
75. Main Tool Bar 2 New Experiment Graph Tool Bar gt Load Settings Settings Popup Menu 4 Fs Load Data File Graph Popup Menu hel Save As ES Insert New Technique a Save Experment s Custom Application E Insert Technique From File EP Print Move Technique Before Global View Move Technique After Curent Channel settings ie Remove Technique 50 Current Channel Graph Remove All the techniques Do Settings In Column 40th Flowchart Reset Settings To Default O Error Messages F Set Settings As Default 2 Modify Group Synchronize Current l P Cancel Modify i gt Lock Tool bars fe efec aer rat es oma Fig 6 Main Tool Bar menu to display the icons e Channel tool bar with buttons 1 to 16 depending on the instrument and on the number of channels that can be inserted into the chassis EC Lab Software User s Manual ES eee 1 A E A el aie E a A O E O Fig 7 Channel selection tool bar It allows the user to select the current channel s Clicking on one of the buttons enables the user to see the channel status The corresponding lights give the on off status of the channels red if there is no experiment running or green if the channel is running 2 2 1 2 The graphic tool bars e The graphics tool bar with short cut buttons including zoom rescale analyses and graph properties Report to the graphics tools part for more deta
76. 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 number processing function that allows the user to display on the graphic one or several 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 electrode linearly and measuring the current resulting from oxydoreduction reactions Cyclic voltammetry 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 address to be connected to the computer EC Lab software drives the multichannel potentiosta
77. P1 51 53 P2 for t gt 10 m IR Compensation Miscellaneous Text export El Filter 57 Edit C Smooth cr fo points Create one data file per loop linked techniques only Default Coulometry Ultra Low Current Option High speed scan Note the high speed rate depends of the current used totus l Time Ewe sP 200 MA Channel S ERs 8 948 Fig 41 Advanced settings window for SP 300 and SP 200 instruments Butter Eoc Q Go ih Note the Advanced setting window is available for all the protocols 2 2 6 1 Compliance The compliance corresponds to the potential range of the Counter Electrode versus the Working Electrode potential 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 ranges the control and measurement of the variables are available REF CE WE The default compliance of CE vs WE is 10 V For example while working with a 12V battery with the CE electrode connected 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
78. RO RE A Cre ener 170 SEIKO EG amp G QCM 922 circa iii 175 FC Lab is A A tr err rte 155 File PROC OSS esc cecsustnsnits tesxeners sey cestabeseamwaunlaamstsee axenic oak casabeaeeawiasnta santas vexeuccaueaanadesaaweaniecaxtatiecena 141 Resaca dci dci dci acid 178 A a o gen ee 70 A O II A A 33 92 EINItelengih Ine arms Md 108 AN PPP circ bacillus Gt cialis sahct cic sahety Scion clnsahe oleic insane Seca 19 EQU IaliSlOMMscess cocci sie oars cee o sec 90 EAS ree tere ree eee eee cee eee ee ener ee ee ene eee ener 109 Graph Back Or QUO sad 69 A oust crate teehee hee hie giahsiegse thoes ai ateeet gehen Giana eet nate nateus tenets 86 A ear rena em eee ian eae Mie einen mre rant cm ty Renny can tr Rent ee eer mee 89 ENERE A as See CO ce haces Beas aaa OO aa ee as oO Sec See haces eh O ace eee 85 A e E Er A S 84 Peak anal SIS iran andando 95 A A ne ada wo a Ga salacead wea teaea 59 186 EC Lab Software User s Manual TS 0 octet tare teh eal A teh naa ate oan teh need ath Gant O ace tend seta 59 TU Ma ii 134 TM ac ice al 69 Sap DIO DEMOS id 66 PN OO OE nO E eee ea ee cas ee ee es 67 AP tenssteU amen cemenaletomtgeecenuatethad 69 A A A A 69 MECO Station aro T E aia 66 A II II II A A 68 Graph Properties A O 53 Grape presenta Ss So a o a 74 Graphic ole mor secs suchas xe seens rr o E ees eos 59 Graphic TO OW DAN esterase cree cee ets alec ents seme etoile rete tic eat 11 A cr eeeem NA 39 o ee Mean come See 22 Impeda
79. Shift F5 Subtract Files Shift Fo Integral Shift Fi FIS Fourier Transform 5hift F8 Y Filter Shift F9 Ey Multr Exponential Sim ti Multi Exponential Fit Show Math Results Fig 100 Math Menu The Math menu contains the Linear and the Circle fits but also the determination of the minimum and the maximum on a curve This Math menu allows also the user to filter the obtained curve to substract curves to do Integral on parts of the curve or to do a FFT transformation 82 Pe Peak Analysis Fl f Wave Analysis F2 CV sim HE Process Data Cycles R QCM mass Ctri Fl summary Per Protocol And Cycle Cirl F3 Fig 101 General electrochemistry menu In this menu the Peak and the Wave analysis are available but also two processes to determine for example R or the cycle number Fit Fa Sim F7 Mott chottky FS ay Kramers Kronig F Fig 102 EIS menu EY This menu is especially dedicated to the analysis of EIS data It is possible to simulate various EIS diagrams with ZSim tool or to fit with various electrical circuits an existing diagram with ZFit tool Photovoltaic analyses E d Process Data Cycles R QCM miass Fig 104 Photovoltaic fuel cell menu This menu provides analysis tools for experiments done on photovoltaic components and fuel cells EC Lab Software User s Manual H Process Data Cycl
80. Total points 12 calculated when one of the circles is moved The coordinates of the first and last data points used for ion 0 982 7 Ohm O brn the fit are displayed as well as the number of points used Offset 113 1 Ohm for the fit in the Selection frame Correlation 0 9999 The results can be copied to the clipboard to be pasted in the print window comment zone or in a text file They can be saved in a text file Fig 108 Linear Fit window PEIS_Fe basique_1 mpr o mi vs Rec 130 120 110 100 30 ol TU BO zi Im Z Ohm 40 20 o o T 20 o a S0 100 150 200 Re Z Ohm Fig 109 Linear Fit on the graph 85 3 4 1 3 Circle fit When the zone to fit is selected click on Calculate in the circular fit window Fig 110 A part of a circle curve is displayed as a result of the regression between two green cursors with the Least square method fit Fig 111 Move the cursors with the mouse by holding the mouse left 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 fit are displayed as well as the number of points used for the fit in the Selection frame In the Parameters frame an iterative algorithm allows the adjustment of the results using a minimization with the simplex method The results displayed are the parameters of the
81. V points and abnormal artefact data points that the user wants to remove before an analysis or a print The Fifth frame is more dedicated to file selection with Load files Add files Selector LOG history The selector will be described in a following section The sixth frame is about the graphic display with the Active trace Add graph and Remove graph Ewe vs time aj_03 mpr This option shows the active trace that can switch gt Tvs time faj_O4 mpr to the one of the other trace with a click The frame Copy and Print includes interesting tools r fe Copy Data Alt D Copy Graph Advanced Copy EIT Data Condecon Fig 68 Mouse copy mode The copy mode contains the graph copy the data copy and the Z data copy e Copy graph is a copy of the graph to the clipboard in a bitmap format e Copy data makes a copy of the active data plot X Y1 Y2 displayed variables e Copy Z data copy data in ZsimpWin compatible format in order to paste data directly in this software The Graph properties frame offers every graphic parameter 3 1 2 Loading a data file The EC Lab software is provided with sample data files The user can load data file in Experiment Load Data File or in the graphic window with the mouse right click select Load Files The following window is displayed 96 EC Lab Software User s Manual Look ir Samples d 4 Ej 159650_cyclage_ 260504 GCPL_1
82. Y YA Ewen A GPES CM Time s 14 GPES PSA Ewer dtfde 2 Times GPES ECN Time z Ewe 174 PowerSuite PowerLorr 144 Ewe Powerly Ewes 158 PowerPulse 144 E we Powersine Reli Ohm Imie Ohm PowerStep T imes 174 Voltamaster 154 Custom Variables EC Lab Software User s Manual Fig 197 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 separator 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 unchecking the box Then define the number of columns and for each of them select the variable 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 anal
83. _Fe_basig E Steel grade name NA Steel grade ee Manuactured by hi Type of product PO Material o Thickness PO Surface treatment SS of product Special treatment Nokes Fig 199 Report window OK saves modifications done to the report Cancel discards modifications done to the report Delete automatically sends the report to the recycle bin Report configuration The structure of each new report is based on the read only text file Defau tReport rep in the same directory as the EC Lab software which is given as an example However the user can change the sections and keys to customize the report to his needs For example the changing of the content of DefaultReport rep into Section1 Info1 Info2 Section2 Info10 Info20 will result in the new report 156 EC Lab Software User s Manual Report C vmp Files aze rep Report C vmp Files aze_rep Fig 200 New Report 157 EC Lab Software User s Manual Linked experiments 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 up to 20 techniques When created the linked experiment 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 L
84. a The system must be causal stable linear and invariant in time and the impedance must be finite when w 0 or wosw This transformation is sometimes used in electrochemistry for the validation of experimental results For example the impedance imaginary part can be calculated from the real part or conversely with the equation Im Z sel a E ee x o The Kramers Kronig transformation can also be verified in an admittance plot lf we consider the previous data file ZPOT Fe Basique mpr the Kramers Kronig transformation applied to the whole point series gives the following results 126 EC Lab Software User s Manual POT Fe basique_1 mpr ImJ vs freq log spacing SPOT Fe_basique_1_kk mpp Im vs freg loq spacing SPOT Fe_basique_1_kk mpp Deta Im lt 0 vs freg log spacing 1Im 2 0 hm aiiz iu eB 0 0 1 1 10 100 1 000 10 000 100 000 lfreq Hz log spacing Fig 164 Result of the Kramers Kronig criterion applied to the data points with the experimental Im Z part the calculated one and the relative error One can see that the Kramers Kronig criterion is not applicable to this system because in the low frequency range the impedance doesn t tend towards 0 For the high frequency range the imaginary parts tend to 0 So the precision is not significant Kramers Eronig Resulta A Reli A Imie lt A El lt A Phasel The results of this test are displayed as an averaged re
85. a sale arte reconnect the cell as follows P1 and S1 leads to the working electrode Py S2 lead to the reference electrode 31 WE GROUND and S3 leads to the counter electrode E CE Sa EE ground Fig 45 Configuration CE to ground N Stat for SP 300 technology 31 EC Lab Software User s Manual To set the standard connection proceed in the same way disconnect the electrodes from the cell select Electrodes connection standard and set the next connections Refi and WE leads to the working electrode for VMP3 technology or P1 and S1 leads to the working electrode for SP 300 technology Ref2 leads to the reference electrode for VMP3 technology or S2 leads to the reference electrode for SP 300 technology CE and Refs leads to the counter electrode for VMP3 technology or S3 and P2 leads to the counter electrode for SP 300 technology Refer to the Installation and configuration manual for more details on the CE to ground connection Warning it is important to disconnect the electrodes from the cell before changing the electrode connection because of the difference between the leads assignment the OCV may not be properly applied Note with CE to ground connection CE vs WE compliance is set to 10 V The CE to ground option is not available with the ZRA protocol Zero Resistance Ammeter 2 2 6 2 2 WE to Ground connection mode In addition to the CE to ground mode a WE to ground connection mode i
86. ab 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 equilibrium state establishment deaeration period accumulation of electroactive species on the electrode surface or pretreatment 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 182 EC Lab Software User s Manual 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 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 loosing any interes
87. al 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 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 Rp 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 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 EC Lab Software User s Manual WHEN AN USER RECEIVES A NEW UNIT FROM THE FACTORY THE SOFTWARE AND FIRMWARE ARE INSTALLED AND UPGRADED THE INSTRUMENT IS READY TO BE USED IT DOES NOT NEED TO BE UPGRADED WE ADVISE THE USERS TO READ AT LEAST THE SECOND AND THIRD CHAPTERS BEFORE STARTING AN EXPERIMENT EC Lab Software User s Manual 2
88. 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 Device in the Config menu The following window is displayed External Devices RDE Configuration Channel Device Type Device Name 1 el Other le Analog OUT Analog IN 1 e Convert EM DeltafFreq Hz v 100 with 110 y 2000 max E 1 O Y 2000 min Manual Control Analog IN 2 TC 10 0 Convert EM to Delta A 0D hm hl with fO v pod max 10 w OO min Fig 219 External device configuration window 170 EC Lab Software User s Manual The user must define several parameters to configure the external device to either be controlled via the analog output left column or record measure data via analog input 1 and 2 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
89. ame concern rescaling Data transfer from the instrument to the PC leads to immediate display in an automatic scaling mode The graphic window is always rescaled These buttons allow rescaling on X axis Y1 axis ds Y2 axis A and every axes E at the same time Analysis tools are the Tafel fit X the available such as the Meal fit the circular fit the R fit integral calculation the Min Max determination the peak analysis ay the wave analysis dynamic fo ar the linear interpolation yh the filter Y the ZFit the Mott Schottky fit E The buttons available on this bar can be configured Several buttons can be added to the bar i in the menu config options tool bars Another tool bar is available with EC Lab graphic window On the left a scroll menu allows for quick plot selection among several defined representations The available plots are dynamic and depend on the file type time evolution or frequency evolution ToolBarGraphaAdy Fig 73 rapid 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 see the section below The data file and plot selection window Right click on the mouse and select
90. analog inputs 1 and 2 The user must tick the box to activate the input output 4 In the 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 variable he wants to display Click on Custom Variables The figure below is displayed Custom Units absorbance U A resistance Ohms Edit Remove OF Cancel Fig 220 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 d 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 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 variables are displayed and can be plotted These auxiliary variables can be used in several protocols as conditional limits of an experiment 171 EC Lab Software User s Manual Note The parameters set in Analog In1 and Analog In2 to define the linear slope can be inverted to h
91. analysis results All the fits described above can be saved in a text file Click on save to create a fit file fit in the same folder as the raw data file When the data file is displayed a function Show Analysis Results is available on the right click menu Select this function to display the fit results window 125 EC Lab Software User s Manual Analysis Results File SPEIS diode mpr Mott Schottky Analysis 12 02 05 15 31 parameters Temperature 5 0 C Dielectric constant 1 000 Surface Area 0 001 cof results File LA EC Labtec lab vi 100 atas S FEIS diode mpr Range 0 020 05 0 300 1 Y Frequency 100 000 kHz Flatband potential 0 756 5 Donor density 0683 5ez1 cm 3 Frequency 31 622 kHz Flatband potential 0 750 2 Donor density 0 685 1ez1 cm 3 Frequency 10 000 kHz Flatband potential fee oy Donor density 0 657 be21 cm 3 gt wh 2 By xX Fig 163 Analysis Results window 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 3 4 3 5 Kramers Kronig transformation According to several conditions on the studied system it is possible to determine the imaginary part of the impedance from the real part and vive vers
92. annel selection Grouped Synchronized or stack experiments This section is dedicated to potentiostats galvanostats units including more than one channel in the chassis 3 7 EC Lab Software User s Manual 2 4 1 Grouped or synchronized experiments It is possible to run the same protocol with synchronized start on several channels this is what we call to group channels or to synchronize different techniques start on several channels this is what we call to synchronize channels Note in Group mode it is possible to choose to begin the experiment with the average potentials value of all the selected channels by ticking the box Start grouped channels at averaged potential or to begin the experiment on each channel with its own potential 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 select this option in the right click menu The following window appears Group Synchronize Stack Set group mode for the channels 1 2 Vi 10 ZN 13 14 15 Select all Start grouped channels at averaged potential Fig 52 Group Synchronize Stack window According to the selected channel here channel 1 because the corresponding box is locked the user can add other channels to either be grouped with channel 1 or be synchronized with channel 1 In this example channels 14 15 and 16 are grouped with channel 1 For synchroniz
93. aous 2 2 6 4 1 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 2 2 6 4 2 Filter 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 as the raw data file but with an mpp extension This Filter tool is described in the paragraph dedicated to Analysis tools Cutoff frequency 10 000 Hz gt ok cancel Fig 47 Filter window 2 2 6 4 3 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 2 2 6 4 4 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 2 2 6 5 Filtrering This option is only available for the SP 300 technology It is possible to filter potential E and current I by hardware Three filters exist 5 Hz 1 kHz and 50 kHz It is also possible to obtain the raw data by selecting No filter None 2 2 6 6 Channel This menu is only available for the SP 300 technology The
94. are used for the polynomial fit at the beginning and at the end of the selected zone twenty first points and twenty last points of the selected data zone The selected data zone and the polynomial fit are limited by two cursors that can be adjusted for a better fit The polynomial fit used is defined as follows y ax bx cx d The results of the fit are automatically calculated when a cursor is moved EC Lab Software User s Manual Peak Analysis Baseline Peak B aseline e Linear 3 Regression f Polvrornial Results From Port ae Ie To Point a ie Aes Total points 2 Slope 0 120 9 m Offset 0 04 1 m Correlation 1 Polyrome Fig 124 Baseline selection tab In the manual mode the baseline is defined by two points represented by circles and set on the curve at the extremities of the zone of selected points In the regression mode the regression straight line determination is made with the least square method Data points used for the regression are automatically selected in the first 25 percents of the total point number between the beginning of the selected zone and the point corresponding to the max current value The results frame displays the baseline equation and the data point zone used for the regression 95 EC Lab Software User s Manual 3 4 2 1 2 Peak analysis results Peak Analysis Baseline Peak When the baseline type is selected click on Calculate
95. ase refer to the previous section In the equivalent circuit frame the table presents each parameter in raw and for each of them offers the ability to select it in order to be adjusted during the fitting the ability to define the sign of the value between by double clicking in the box the unit and the standard deviation calculated when the Levenberg Marquardt algorithm is used When the selection box is not ticked the parameter value set in the cell will be considered as the correct value It will not be modified during the minimization The Calculate button will calculate and plot the data points for the parameter values set in the table without to randomizing or fitting 3 4 3 3 2 Fitting methods The Zfit 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 to do the minimisation either one fit made on the current cycle displayed on the graph or the successive fits made 115 EC Lab Software User s Manual on ALL cycles of the experiment Default values are set for every parameter but they never fit properly with the real experimental values Before to do the fit and in order to help the algorithm to find the best values it is necessary find a couple of values as close as possible to the real one Default values too far off will result in a divergence of the algorithm A randomization has been added before the fitting to select t
96. ate 113 EC Lab Software User s Manual ajaj Set Frequencies C EC Labw9 30 Data sim mpr e ImiZ ws Felt l i EE with hoo o paints Ta spacing Equivalent circuit FM 02 A240 2 v Edit ph parameter Ohm Fis a 1 Ohm Ohne 1 42 hl Fig 149 ZSim Circuit Edition window with adjusted parameters Re Z Ohm The results can be copied to the clipboard and saved in a Zsim mpr file The user can modify parameters as much as he wants in the table The new parameters will be implemented when clicking on Calculate To store this simulation the user will have to give another name to the data file because a simulation is always created in the Zsim mpr file 3 4 3 3 Fitting ZFit When the correct equivalent circuit is defined with ZSim the user can set it in the ZFit window to identify parameters of the elements with the experimental data points 114 EC Lab Software User s Manual 3 4 3 3 1 Zfit selection window Selection Results Equivalent circuit unit dew Ohm HRN F s a 1 MMN HHHH Ohmi hat Ohm 1 2 sex Calculate Fit Select Method Randomize Simplex Randomize Stop randomize or 1 0000 iterations vei E E AAA Iterations HHMH Cycle sexx Fig 150 ZFit Circuit selection window As for the Zsim selection window the Zfit selection window enables the user to edit and create a circuit For more details about the circuit editing window ple
97. ation 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 measured corresponds to 2 4 times the chosen current range In other words for the 10 A range on the figure below the user can apply potentials from 10 to 10 V and he can measure currents going from 24 to 24 UA with no restrictions 30 2d 20 HA Fig 216 Current versus Potential available domain in the potentio mode 5 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 following part 168 EC Lab Software User s Manual from the others please refer to the part 5 1 page 163 for more details Usually the controlled current value cannot bypass the range If the user wants to apply 15 WA current to the cell he must choose the 100 A current range But 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 potential range is red
98. ave an opposite variation of the recorded value with the plotted value The configuration of external devices that can be controlled by the potentiostat analog output are described in detail in the corresponding sections of the manual Amanual 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 5 4 2 Rotating electrodes control The standard instrument equipped with channels delivered since November 2004 with or without 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 electrodes ring disk electrodes A bipotentiostat is necessary for the measurement of the working electrode potential of both electrodes The VMP3 using two channels VSP SP 300 or the BiStat are appropriate instruments for this kind of experiment Fig 221 RRDE Rotating Disk electrode ALS RRDE 3A 172 EC Lab Software User s Manual 5 4 2 1 Control panel Before running any experiment with a rotating electrode one must first choose the rotating unit Select Config Y External Device RDE in the EC Lab main menu E User Ctrl U
99. be used is detailed in the section Fourier transform 3 4 1 7 page 90 Example of electrochemical Noise Analysis is given in Fig 182 140 EC Lab Software User s Manual CA R 100mHz_01mpr Moise Analysis Ewe vs time Iys time s 01 Selection Trace les Hime Cycle a aaah AAPP ARPA ae Y ES J d J Ay LEAP AP AP AP AP AP AP APA VV j j 002 y f 0 Se 0 02 Total points 11 50 100 Parameters Select all s cucle s CA R 100mHz_01_ena_psd mpp Ewel vs freq l vs freq Ewe trend removal 0 02 EwelV yu 0 timels trend removal Method PSO with DFT Ww MEM order Ewel V na vn freqiHz Results Ewe average 2 4406 3 average 0 473 5e 6 A o Ewe 0 935 7e 3 W ol 0 184 9e 6 A Rn 5 061 Ohm Fig 182 Electrochemical Noise Analysis on system with a 100 mHz electrochemical noise 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 3 4 6 7 Other corrosion processes Two additional processes are available with the corrosion techniques polarization resistance and multi pitting statistics They are both described in the section below 3 5 Data and file processing The st
100. by the software or manually with a definition by the user of the number of columns and of each variable In the Tools menu select Import from text or click on the import icon the following window Import From Text Input Text File File 168650_ cyclage_260504 GCPL_1 mpt Load Directory CAEC Lab Datat S amples Size 613 666 bytes 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 4 Importation Parameters to display Show Tab and Space 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 1 lt Tab gt 0x lt Tab gt 0 lt Tab gt 0x lt Tab gt 0 lt Tab gt 0 lt Tab gt 137858 1 lt Tab gt 0 lt Tab gt 0 lt Tab gt 0 lt Tab gt 0 lt Tab gt 0 lt Tab gt 137976 1 lt Tab gt 0 lt Tab gt 0 lt Tab gt 0 lt Tab gt 0 lt Tab gt 0 lt Tab gt 1380398 41295 lt Tab gt 135 lt Tab 41297 lt Tab gt 135 lt Tab 41299 lt Tab gt 135 lt Tab 41301 lt Tab gt 135 lt Tab _ p Text file format FE Lab Columns Separator Tab r Colums Automatic detection Number of columns 1 Columns type Column Vanable Time s Input file current polarity convention 0 Positive oxidation standard IUPAC convention gt Positive reduction inverted convention Iriportatior Imported File s Display Text file format CONDECOR CONDECY Ewe 18 CV ew Vien FC Lab FE Lab log FRA Gamy GPES GPES C
101. cies at the electrode surface solution interface Indeed this process is assumed to be represented by an equivalent circuit of resistors capacitors inductors and diffusion elements The total current is in most cases the sum of distinct contributions from the faradic process and double layer charging 104 EC Lab Software User s Manual 3 4 3 1 1 Electric equivalent elements description The impedance analysis tool contains currently 8 different electric components These components are R resistor L self inductor C capacitor Q constant Phase Element CPE W Warburg Element simulating the semi infinite diffusion Wd Warburg Diffusion Element simulating the convective diffusion M restricted Linear Diffusion Element G Gerischer Element 3 4 3 1 2 Resistor R Description Resistor Impedance 2i R Noguet Diagram Imi vs Reli o Fig 137 Resistor element description The resistor element is defined as a passive component with a constant value when frequency varies Fig 137 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 to zero Im Z 0 105 EC Lab Software User s Manual 3 4 3 1 3 Inductor L Description Inductor Ly ees e Impedance Z H L 2xf Nyquis
102. created as follows Filename __ technique number in link _ technique name _ channel number _ loop mpr 4 2 Applications 4 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 159 EC Lab Software User s Manual EC Lab 10 00 Channel 9 experiment test manuel_01_CA technique 3 6 Cyclic Voltammetry Experiment Edit Yiew Graph Analysis Tools Config Windows Help E B gt E il IN Wk Km YX Tr WS Show ll al al gt AS 6 9 E range min Y max Y res 100 p Turn to OCW between techniques lt lt Default ml Advanced Settings SetEwe to Ej Vo ys Ewe vs time gt test manuel_01_C4_01_0CWY mpr test manuel_01_C4_02 C4 mpr Cell Characteristics 0 1 AAA ANA AAA OOF Scan Ewe with dE dt mues ar e cid to vertex potential Eq Y ys 7 ol Reverse scan to vertex Ep Yo ys CY Repeat ng time s P5 C Measure lt I gt over the last of the step duration 1 2 3 4 5 6 PEIS Loop Record lt l gt averaged over N voltage steps E Range 30 Fes 7 ay i Range time s Bandwidth lt I gt vs Ewe test manuel_01_CA 04 PEIS mpr test manuel_01_C4_03_CV mpr X m Z vs Re Z test manuel_01_C4_05_C mpr Endscanto Ef Yo ys 02 dE dt 100 p 45 0 ms Force El
103. ct Mechanizm EE 5 000 7 Reaction Reduction A ze E 0 z 11 0 3 W 5000 ko oom cm s af 10 5 10 000 Species Ca intial fel Da eA 15 000 Dp Seb 20 000 Calculate Copy Save Close 0 5 0 05 Ewe V Fig 133 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 102 I mA File Selection Variables C Users ocuments EC Lab Express Datas C sim mpr Representation Custom z E Pi times E wer m cycle number CA mol L 1 CB mol_L 1 CC mol_L 1 pooo SISO Same selection for all files Hide Additional Varnables keep previous axes Process T keep previous zoom Ur Fig 134 Variable selection window to display concentrations CVsim mpr vs Ewe CA vs Ewe CBvs Ewe CCvs Ewe 3 14 10 000 12 5 000 N 10 0 8 5 000 6 10 000 4 15 000 2 20 000 0 Ewe V Fig 135 Interfacial concentration variation versus electrode potential EC Lab Software User s Manual L T1OW D9 103 EC Lab Software User s Manual Several examples are available in the CVsim window To display an example one has to click on the select button on the top of the CVsim menu Then CVsim examples window appears to select the mechanism of interest CVsim Examples 1 E DLSI
104. ctivity constant Kcell 11 000 cm Use Default Units C User s Units ret mcn m htg Couche Voltaninetry DigiElch Format Export all files into a single Ext file Number OF Digits Fig 195 Text File exportation select one or more files with the Load and Add butions 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 format Absolute Time mm dd yyyy hh mm ss sss option For impedance data files an export text in ZSimpWin or Zview 152 EC Lab Software User s Manual formats is available and allows to paste directly data into ZSimpWin or Zview software An export text in Bio Kine conductivity 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 While running experiment it is possible to export files To do so the user must check the Text export option into the Cell Character
105. current plot 145 EC Lab Software User s Manual MO E AA Vara mara os gt C o A N eee me UL ma Zz E Al E E oi L P dodo d A E AAA ETT TT TTT i Sp ie Non compactec 520 l I l l l l 0 FOO 1000 1500 2000 2500 times Fig 186 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 3 5 1 5 Capacity and energy per cycle and sequence Capacity and energy per Cycle and sequence Calculates the capacity energy and capacitance per cycle for the Galvanostatic Cycling with Potential Limitation GCPL Chronoamperometry Chronocoulometry Chrono 1 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 the data points are recorded every sequence or every cycle He can set the cycle definition to be done automatically or every loop or every charge discharge alternance 146 EC Lab Software User s Manual Raw File Experiment Procezzed File Record one point at the end of each Processed file variables cycle number E charge h Cycling rate charge 0 charge m h E dicharge
106. d click on Calculate Freq Maxo Hz Once the zone selected it is possible to choose the shape of the window where the calculation will be done In signal MB Foints processing a window function also known as an apodization function or tapering function is a function that lc aculate Copy Save Close is zero valued outside of some chosen interval When ere A EN another function or a signal data is multiplied by a window function the product is also zero valued outside the Rectangle interval Barlett Hann The 6 windows possibilities are described below ee relationship only valid within the interval 1 1 and 0 Welch outside Fig 117 Fourier Transform window Rectangle w t 1 Barlett w t 1 f Hann w t 0 5 0 5cos zt Hamming w t 0 54 0 46 cos zt Blackman w t 0 42 0 5cos 1 5 0 08cos 2nt Welch w t 1 t 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 90 0 1 EwelV ae 0 1 EC Lab Software User s Manual CA R 100mHz_01 mpr Ewe vs time vs time AAAA AL A AA VV VV VY VV V pm VA 0 02 100 yu time s CA R 100mHz_01_dft mpp ll mA vs freq Fourier Transform Selection Trace Ives time From point O PI Os bie O m To point 113 uN 1114 ie 0 015 42 m Total points
107. d the atomic weight of the intercalated ion Li is 6 94 g mol The user also has to define the intercalation rate xO when the acquisition starts and the number of electron ne transferred par intercalated ion molecular weight xf x atomic weight t EO ne x mass x 0 001 x F With all the parameters the charge variation AQ Q Qo is calculated for Ax x x0 1 e The electrode surface area and the characteristic mass can be added set the reference electrode used in the experiment either chosen in the list or added while clicking on the corresponding tab record the counter electrode potential Ese calculate Ewe Ece V and store the values into the data file record the power Ewe l calculated in the instrument record external signals pH T P using auxiliary inputs 1 Analog In1 and 2 Analog In2 e access the external device configuration window using the link in blue 26 EC Lab Software User s Manual Channel 1 running files Acquisition started on 08 02 2010 host 192 109 209 146 directory CAEC LabiSamples fle s Cv iron_10 mVis mpr cy Fig 38 Cell characteristics Files window All boxes Acquisition started on host directory and file are filled automatically when the experiment is started 2 EC Lab Software User s Manual 2 2 6 Advanced Settings The advanced settings window includes several parameters that can be adjusted on the instrument These parameters such as co
108. displayed in log 1 VS Ewe Two linear regressions are automatically 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 logt elk J vs Ewe LP_01 tatelmpp 5 1 5 2 9 log lt I gt pA 2 9 4 5 EwelV Fig 176 Tafel graph Results of the Tafel Fit are calculated whenever a marker is moved The default positions of the markers are 80 mV and 200 mV around E o The software deduces the open circuit potential Eco to linear regressions intersection the corrosion current value leor and the Tafel constants Ba and e The Fit accuracy can be estimated with the x The Tafel Fit also works with the plot Ewe vs log I 135 EC Lab Software User s Manual Ewe vs log lt I gt Ewe vs log I LP iron corrosion_tafel mpp 4 log lt 1 gt mA Fig 177 Tafel Fit on the Ewe vs log I graph 3 4 6 3 2 Corrosion rate Finally the corrosion rate CR is calculated according to the next equation I KEW mm CR MFTO in millimeter per year mmpy or milliinches per year mpy Lear corrosion current in A K constant that defines the units of the corrosion rate EW equivalent weight in g equivalent 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 milliinches year mpy 3 4 6 3 3 Minimize option Unfortunat
109. e Copy Graph Copy Data Copy Graph Advanced Copy Z Data SimpWin Copy EIT Data Condecon Fig 17 Edit Menu The Edit menu concerns building an experiment insertion move up or move down or removing techniques from a setting already loaded in the parameter settings window A Group and synchronize window is also available in this menu The second frame is for sequence addition or removal from a technique when this is possible and the two last ones offer copy options Graph Data ZSimpWin format on the graphic display Global View s Ctrl W Current Settings Graph Description Channel 1 Graph Ctri 6 Settings With Flowcharts Channel 1 Channel 2 Channel 3 Channel 4 Channel 5 Channel 6 Channel 7 Channel 8 Channel 9 Channel 10 Channel 11 Channel 12 Channel 13 Channel 14 Channel 15 Channel 16 b0000000000000000000o0000a sd El Tool Bars Status Bar SA Error Messages Fig 18 View Menu This menu is for the Settings or Graph display and to select a channel In the last frame tool bars or error messages can be displayed 15 Graph Plot Mouse Mode Autoscale Representations Hide OCV Points Hide Selected Points Show All Points Load Files Add Files Alt 0 OD Remove Trace Alt R Reload d LOG History Edit Surface and Mass Load Settings On Channel d qe Active Trace Add Graph a I Remove raph Li Alt P Graph Prop
110. e In case of a weight Z the results are as follows 117 EC Lab Software User s Manual AORE a ITA Selection Results Im Z vs Re Z E x e Im Z vs Re Z ZPOT_Fe_basique_1_zfitimpp Equivalent circuit FAl Q2 R2 W 2 param sel sign value Ohm F s a 1 Ohm z E 2 N T Calculate Fit Select curent W cycle s Method Randomize Simplex Randomize Stop randomize on 2000 iterations Stop fiton 5000 iterations y Weight ZI wi ra z E E 3 644e 3 Iterations 5000 Simplex Cycle xxxx 150 Fig 153 Fit results with a combination Randomize Simplex and Z as weight In the case of a weight Z considered the y value tends toward zero In any case the value must be the smallest possible 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 3 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 at left hand corner on the figure below The potential was
111. e a data file with the name for each source file y 3 4 3 number in the batch list source file name channel number mpr Batch name For the user information the technique used in the selected file is displayed Several functions 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 41 EC Lab Software User s Manual During the Run the user can pause the experiment and go to the next settings file Note if the number of techniques is lower than 20 it is often more convenient to use linked techniques 2 6 Data properties 2 6 1 Type of data files Several files using your filename with different extensions mp are created mile description extension p mor Raw data binary file which contains the current parameter settings refreshed at each modification of the detailed flow diagram and cell characteristic windows This file includes all the information of the mps file Setting file which contains all the parameters of the experiment The settings 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 techniques Text file which contains the experiment conditions the instrument IP number the channel number the username the filename and its location the parameter settings and the c
112. e electrode is calculated from the value of the radius of the electrode Geometry Linear Semi infinite neue i em e Experimental conditions Surface 3 142 crf Temperature in degree Celsius Ro the resistance in Ohm Experimental Conditions Temperature 25 Double layer capacity in uF Ro E 0 Double layer oO pr e Potential scan capacity Potential Scan Scan type linear or sinusoidal scan respectively eae Linear m for CV or LASV simulation en Scan rate in V per second eects a a The initial and the two vertex potential in V E init o5 Y Number of scans performed for the CV or LASV Mentes 1 as Y simulation Vertex 2 0 3 y M Sampling Number of scans 2 o The user defines the number of points needed per scan to perform the simulation The total Humber of points 100 number of points the resolution in time and in per scar lt indicated Total number 1939 o Le of points Sampling time 80 808 ms e Noise Potential steps 8 067 m Moise Some noise in current or in voltage can be superimposed to the simulated curve Add noize Noise level 000 000 pu s 10 000 mi Calculate Copy Save Close Fig 132 Setup tab of CVsim 101 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 CVsim mpr l vs Ewe 10 000 Example Sele
113. e general options window is made with two frames The first one is for the files and the second one is for the Graph In the files frame several options are offered to the user e Save data every s defines the data transfer rate 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 filenames e Erase the Log file automatically on stop e Create an automatic data saving The user has to choose the directory to save the data file He must define the prefix name 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 In the Graph Optimization frame e Draw only lines over 1000 points can be used in experiments with big data files This display mode shows only the lines on the curve and hide markers for a fast display e Undersample traces over 1000 points accelerate the graphic display of large data files with the following undersampling 47 EC Lab Software User s Manual no undersampling for data files less than 10 000 points 1 point on 2 for data files from 10 000 to 20 000 points 1 point on 3 for data files from 20 000 to 30 000 points ete
114. e material Initial state lt Fig 87 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 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 70 EC Lab Software User s Manual 2 Copy Graph Advanced Picture Format Options Size as Bitmap as GIF as JPEG Colors Default ye as Metafile Dista Copy Graph AIE G fA Copy Data Alk L as PostScript as Sits l Copy Graph Advanced Preview Pri Copy EIT Data Condecon Fig 88 Copy option and copy graph advanced menu 3 2 7 1 Standard copy options On the top of the menu two standard options permit copying either the graph or the data The Copy Graph option will copy the graph to the clipboard as displayed on the computer screen in an enhanced metafile format emf The user can paste the file in the software he wants The Copy Data option will copy the data 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 7 2 Advanced copy options Three advanced copy options are also available The Copy Gra
115. e standard and common in every technique and application in the software Every data file contains state bytes that can be hidden in the selector Several additional variables are dependent of the technique used cf additional variables Depending on the techniques some processed variables can be created either automatically or by the 42 EC Lab Software User s Manual user For EIS techniques the variables are related to Z and admittance variables are processed Variable description Variable name Time in s time s I current in mA mA Ewe WE potential versus REF in V Eyal V dq charge increment between two recorded values in mA h dq mA h Ean potential control in V control V lc Current control in mA control mA Ectr l oi potential or current control in V or mA control V mA Ese CE potential versus REF in V E V lt l gt average current calculated from dQ dt in mA lt l gt mA Mode Intentio Potentio Relax State byte bits n 1 and 2 mode Oxidation Reduction State byte bits n 3 ox red Error bit State byte bit n 4 error Control changes State byte bit n 5 control changes Changes of N State byte bit n 6 N changes Experiment counter value has changed bit n 8 counter inc Temperature control in C control C Temperature measure in C T C Rotating electrode speed control value in rpm speed rom User defined recorded variable with its unit set as additional analog Us
116. econd current peak A polynomial baseline could lead to a more significant fit On the following figure a polynomial baseline has been used to do a peak analysis The oxidative 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 oxidation The result variables are the same as for the analysis with a straight baseline 98 pyr4 1 nod mpp ale wa Ewe cycle 16 lt 1 gt mA 0 2 0 0 2 0 4 0 6 0 5 1 EweV Fig 127 Peak analysis on a cyclic voltammetry experiment using a polynomial baseline EC Lab Software User s Manual 3 4 2 2 Wave analysis The wave analysis F is the most useful tool for the analysis of experiments performed in a hydrodynamic Wave Analysis regime specially a rotating disk electrode Selection Results When a data point zone is selected click on Results Calculate E172 0 4001 Y The wave analysis is made according to two straight lines These lines are defined using a linear regression fit The software will automatically find the two parts of the curve with the weakest 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 selected data points are taken into account for the second regression The data point zone for the analysis is shown in the Selection frame by the extreme points ha O23 me le The Re
117. ed Settings Cell Characteristics Parameters Settings title gt e de vs Ewe PITT_2300604_1_calx mpp al ys Ewe CY Fe_basique_1 mpr 0 0 5 Ewe V vs SCE Im Z 0hm 100 Re Z Ohm Fig 91 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 92 the Bode impedance 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 74 EC Lab Software User s Manual Graph Representations Ewe vs t is Bode Impedance Ewe vs Ewe vs Representation Advanced lve Ewe delta vs Estep Lodlll vs Ewe arts Y2 anis Ewe vs Lagll k hn Phase 2 deg G vs t log Y Ap vs t Bode Impedance _ separate traces Nyguist Impedance Black Impedance el ws t SMS Mott Schottky freqHz
118. ed and run synchronously for example to perform multi pitting experiments using a common counter electrode in a single 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 instruments are modular versatile and flexible multi user instruments Once the protocols have been loaded and started from the PC the experiments are entirely controlled by the instrument s on board firmware Data are temporarily buffered in the instrument and regularly transferred to the PC which is used for data storage on line visualization 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 corrosion batteries super capacitors fuel cells and custom applications Usual electrochemical techniques such as Cyclic Voltammetry Chronopotentiometry etc are obtained by associations of elementary sequences Conditional tests can be performed at various levels of any sequence on the working electrode potential or current on the counter electrode potenti
119. ed channels the user can choose whether or not to stop channels together at the same time Channels belonging to the same group appear with the same colour One can see that other series of channels are grouped or synchronized together To know if the other channels are grouped or synchronized the user must show the global view in the View menu 38 EC Lab Software User s Manual Global View ar a hs Lo channel UZET tech status amplifier l Ewe WW 1 channel UZET tech status amplifier l E we Show window at startup Fig 53 Global view to show the Grouped and synchronized channels Grouped channels are marked with a g in the 16 channels global view window and synchronized channels are marked with an s Now one can see that channels 1 2 and 3 are grouped together Channels 4 and 5 are synchronized Channels 9 10 and 11 are grouped and channels 13 14 15 and 16 are grouped To ungroup or unsynchronized channels the user must select one of the required channels before opening the group synchronize window to unselect the channels For example for channels 1 to 3 the user must select one of these channels and then uncheck the boxes Note another way to group or synchronize channel is with keyboard shortcuts 1 To group channels first click on the Modify button and then select the channels while pressing the SHIFT key El e To deselect a channel from a group click on the Modi
120. ed 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 occurred 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 instrument G eneral safety considerations Y Class WARRANTY 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 personal injury Gua
121. eeseeeaeeeneesaeeenaes 96 3 4 2 1 3 Results of the peak analysis using a linear regression baseline 96 3 4 2 1 4 Results of the peak analysis using a polynomial baseline 98 SA22 Wave MaS Sais a 99 SAS OV Mis 100 3 4 3 Electrochemical impedance Spectroscopy MENU cccseececeeeeeseeeeeeeeeeneeeeeaaees 104 3 4 3 1 Impedance data analysis Simulation Fit and Kramers Kronig criterion 104 3 4 3 1 1 Electric equivalent elements description ooocconccconcccnocccconcnconcnnnnncncnnon 105 A RESISTOR ac E ened aneueetahe SS 105 AS A O e o 106 SA 11d Capacitor Cnet ieee See Ss eG ee eee Al do es 106 3 4 3 1 5 Constant phase element errire a 107 3 4 3 1 6 Warburg element for semi infinite diffusion W ooooncccocincniccncnoncnanonnno 107 3 4 3 1 7 Warburg element for convective diffusion Wa oooccconnconcnconccnonnconcnnnno 108 3 4 3 1 8 Linear diffusion element M ocooccccnncccncccncconoconoconononocononononanonanonanenanos 108 SAO Genscher elenen a a aa de 109 343 2 o o dean E a a aea 110 34321 ZOU WINGOW di EA 110 3432 02 CNCUIRSCIECION nui eco e 112 39 43 29 DesSc ipuOA CON iaa 112 Sac EUO A Ge eee re ne ee ee A 114 343 01 Zit Selecion WINDOW ai 115 D3 O52 lalo ios AAA eect A A A 115 boo APPICCIU Nissan cana al 117 3 4 3 3 4 Fit on successive GY CIOS esvicin ici lila iio ela id 118 34930 PSU CADA coisas eet eat oa tt ated aueh i osioae aba tiae las 119
122. eka areal 10 22 12 WME graphic TOO Dal Serie d5cct secs acu tan dcccd e aacwiane 11 2 2180 Status TOO DAN race E eeuatasiatenad sacatagentanadskenatansaawencuseed 11 22 14 Currentvalues TOO Dal israelita 11 2 2 1 5 The parameter settings TAMe cooccconcconcconcconiconoconoconocanonanonanonanonanenanenones 13 2 2 1 6 Right click on the Parameter settings WINCOW cccsecceeeseeeeeeeeeeeeeaeeees 13 222 A lo o aldo 14 2 2 3 Selecting a technique ecc anced dacdenseeeleanct EEEE 17 224 Parameter Set Susa 19 2 20 Gellcharacion SOS criticadas Meadanctaaadas a eaddeneleacces Meaheansteadeia deeded 23 2 2 5 1 Standard Cell Characteristics WINGOW ccccccscceeeceeceeceeeeeecueeeeeseeeeeeees 23 2 2 5 2 Cell characteristic window in column format ccceeeeeeeeeeeeeeeeeeeeeceeeeeaeeens 25 2 2 5 3 Battery Cell Characteristics WINGOW ccocoocccoccccncococoncococanoncnnanonnonanonnnnanons 25 2 2007 AQVAncea SENGS nee ee ene ner ee ee ee eee 28 22 01 GOMPIANCE ni ia cloaca cid 30 22 0 2 Electrodes CONNCCIONS cossiran 31 2 2 6 2 1 CE to Ground CONNECTION MON ccccoccncccncnccccnnccncnccnnononncnnnnnnnnnnnnonanononanoos 31 2 2 6 2 2 WE to Ground connection MOE occcoccncnccncccccnccncnccncnnnnnnncnnnnnnnnnncnnnnonanoss 32 2 amp 0 A in Daan eo eae bee 32 2 2 6 4 MISCCNANCAOUS susi nr AAA 33 od VOTO O sti IA AS 33 LLO A A ene em eed ree eee Ae ee ee rE a tee eee Ree eee ee ree Ce
123. el 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 techniques 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 start or stop the run 183 EC Lab Software User s Manual Units graphic function used to modify the axis units 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 184 EC Lab Software User s Manual Index o e A AA reee Eo E E NS 161 mpr mpl mps mpp mpt mgr F MQp fit aeneae e a EE 42 O 37 A 69 Advanced Seting Sisri ods Set hac eh Same Sah ann ett and lem hacn seth 28 Advanced setings tool DAM siria ii id di 13 Analog Input o TN 24 26 PRIVY SIS E
124. el coefficients into a log I versus E representation Tafel Graph On a linear polarization trace select the Tafel Fit with Tafel Fit the Tafel Fit button or the mouse right click and Results the data points where the fit will be performed The Trace log clo ve Ewe Tafel Fit analysis window appears Fig 175 The user F Ecom 324 668 m will receive a warning message to switch to the log I E leo 0 343 pA versus Eye graph representation 90 5 mi 117 7 mv 10 101 7 Equivalent A Can not do Tafel Fit with the units selected Weight 0 000 greg Density 0 000 gema Surface rea 0 000 cr Corrosion Fig 174 Tafel Fit warning message to switch the Rate _ mmpy graph representation Switch the representation to log I vs Ewe Answer Yes to the previous message The fit can be minimized with a simplex method The results can be copied to the clipboard to be Fig 175 Tafel Fit window 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 ll versus E representation In graph properties axis axis processing select log 1 for Y1 134 EC Lab Software User s Manual 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 characteristics window The Tafel graph Fig 176 is
125. ell characteristics at the beginning of the experiment 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 experiment the average current between two recordings chronocoulometry mp The mpt file is a text format file generated when the user exports the raw mpr file in text format mgr Hidden file including the graphic properties of the corresponding raw mpr file _ mp As with the mgr file the mgp file is hidden and includes the graphic properties of the processed file mpp 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 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 unserviceable by the EC Lab software 2 6 2 Variables description Several variables ar
126. ely results may be different from what is expected for two reasons 1 The linear parts of the plot are not recorded 2 The potential scan range is too large and an additional electrochemical reaction appears that does not fit the Stern Geary model In these cases it is possible to reduce the error between the model Icai and the measured data lmes in minimizing the next value N X Us o lanei y i l This is obtained in clicking on the Minimize button The Nelder and Mead Simplex method ref 2 was used to minimize the y value Keep the button pressed lt Enter gt or lt Alt M gt 136 EC Lab Software User s Manual keys until the Stern and Geary parameters Egor lcor Ba and Be have stabilized Then a theoretical Tafel graph is displayed this graph is displayed in agreement with parameters obtained with minimize button Note that the Simplex method may not succeed if the initial values are too much different from the minimum ones it may fall into a local minimum of y Ecorr corr Ba B or If the I Ewe curve Is linear around E o In that case the following message will be displayed The trace KE appears to be linear within the selected zone The minimization may Fail Do you want to proceed anyway Y Fig 178 Tafel Fit minimization message For this reason it is possible to enter directly Egor lcorr Ba and Be values and then continue the minimization Unchecking the boxes around Egor
127. emical measurement The nature of these stages is related to the electrochemical system to study and the electrochemical technique used mainly analytical or plating electrochemistry We will consider in this chapter the equilibration and preconditioning steps in the electrochemical cell electrode polishing sonication steps or other surface treatments are not considered 5 5 1 Equilibrium state establishment The equilibrium state establishment is considered a stage where no constraint is applied to the system neither in the electrochemical cell solution nor on the electrode surface The usual protocol for this consists of applying an Open Circuit Voltage period This period can be seen as a waiting duration until the electrode or the cell has come to equilibrium with the ability for potential recording for example to follow the equilibration of a battery The user can set a limit to the OCV period with a minimum potential variation in time that can be compared to the equilibrium 176 EC Lab Software User s Manual 5 5 2 Preconditioning methods The preconditioning steps can be divided into two different categories The first one is to carry out a mechanical modification without applying any electrochemical signal The second one is to apply an electrochemical signal in order to modify the working electrode surface 5 5 2 1 Mechanical modification Mechanical modifications gather all the preconditioning steps of the electrochemica
128. emists D T Sawyer A Sobkowiak J L Roberts Jr 274 Ed Wiley New York 1995 Handbook of Analytical Chemistry L Meites Ed McGraw Hill New York 1963 91 2 9 6 Tool bars options Options default EC Lab Software User s Manual Text export References Tool bars menus Select the items that are displayed into 12 New Experiment da Load Settings E el Import Settings From Text GA Load Data File El Es Load Report m Save As E Fa Save Espernment 4s Custom Application pe Print Global view E Current Channel settings E 50 Current Channel Graph E i Settings In Column with Flowecharts E ry Error Messages 4 in rr Tool Bar 3 Modify PP Cancel M oddity P Run Stop I Pause Resume A Nest Technique E Insert Mew Technique E ia Insert Technique From File PE Move Technique Before Pl Move Technique After E e Remove Technique E E Remove All the techniques E Reset Settings To Default C E Set Settings s Default Lock Tool bars fife SR JA ARA AO AAN x Fig 65 Option window Tool bars tab The tool bar option is made for the user s convenience He can select icons he wants in the main tool bar and the graph tool bar from all icons available in EC Lab software Both tool bars can be locked to the place chosen by the user But this is effective only when the software is restarted It is also possible to select the functions available on the graphic
129. er Unit inputs Variable description Variable name Additional analog input 1 in V Analog In1 V Additional analog input 2 in V Analaog In2 V Additional analog input 3 in V Analaog In3 V dQ charge on a potential step in mA h dQ mA h AQ charge on a cycle in mA h DQ mA h forward in pulsed techniques current measured at the end of the forward A pulse reverse in pulsed techniques current measured on the reverse part l reverse A delta difference between forward and reverse delta A E step in sweep pulsed techniques potential step increment E step V 43 EC Lab Software User s Manual Variable description Variable name log lt I gt A Q Q charge from the beginning of the experiment in mA h Q charge Q for a charge cycle reinitialized every cycle Q discharge Q for a discharge cycle reinitialized every cycle x normalized charge Ohmic impedance in Q Ewe Ece WE versus CE potential in mV Cycle number Power in CPW calculated by E l Energy in CPW calculated by E l t R polarization resistance in corrosimetry Icorr corrosion current resulting from R calculation E corr Corrosion potential resulting from R calculation C Inverse of square capacitance for Mott Schottky plot C Capacitance for Mott Schottky plot Frequency in Hz Ewe module of Ewe V I module of in A Phase of Z in degrees Z module of Z in Q Re Z real part of Z in Q Im Z Ima
130. er cycle 0 1 0 5 0 0 5 EwelV vs SCE Status Oxidation Time 0 04 15 Ewe 0 760 Y 1 0 152mA Buiter 19 Eoc 0480mv 000 1 98 yA P 0 116 mw VMP3 JL 192 109 209 222 Channel9 Read mode e 1 15 0 126 25 432 b s Fig 206 Linked experiments example with ohmic drop compensation technique 162 EC Lab Software User s Manual 5 Advanced features 5 1 Maximum current range limitation 2 4 A on the standard channel board 5 1 1 Different limitations VMP2 BiStat 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 150 is 800 mA and 500 mA the SP 200 and SP 300 In particular conditions of current and time this limit can be passed Then the following message is displayed Warning ls 2400 000 m is 1 The VMP is designed to accept a maximum continous current of 400 m In certain conditions this limit can be passed Please consult the manual For more information Fig 207 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 It lt 4 8x10 A s For example
131. ernal files processing So the option Hide Additional Variables is checked by default Unchecking the option will add the state byte variables to the file selection window It 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 e Remove remove the selected file from the list e Undo undo the last operation done e 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 60 EC Lab Software User s Manual 3 2 Graphic facilities 3 2 1 Cycles Loops visualization Since version 9 20 of the software the cycles in the CV CVA and SV techniques are automatically generated with no action by the user But 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 linked experiments loo
132. erties Fig 19 Graph Menu This menu includes all the graph tools Zoom in and out point selection auto scale selection and graph properties and the graph representation menu This menu allows the user to load or add new files to the graph 16 EC Lab Software User s Manual Analysis Math j General Electrochemistry Electrochemical Impedance Spectroscopy Batteries d Corrosion Show Analysis Results Fig 20 Analysis Menu The analysis menu contains various Analysis techniques These analysis tools are grouped depending of the application general electrochemistry EIS batteries and corrosion m 3 a Modify Cell Characteristics Extract Cycles Loops Split file Under Sampling dad Channels Calibration Retrieve Data From The Instrument Batchs 3 Repair File Repair Channel Tera Term Pro Calculator El la Notepad Fig 21 Tools Menu The tools menu is made of three frames The first one is for the data file modify cell characteristics export as or import from text split under sample repair file The second one is for the channels calibration repair channel The last one concern tools such as Tera Term Pro used to change the instrument configuration calculator and Notepad 2 2 3 Selecting a technique EC Lab Software User s Manual c User Ctrl U Je Connection Virtual Potentiostat JH External Devices Thermostat RDE
133. es R QCM mass Ctrl Fl Hi Capacity amp Energy Per Cycle or Sequence Ctri F2 summary Per Protocol And Cycle Ctrl F3 Constant Power Protocol Summary Cirl FS Fig 103 Batteries menu The Batteries menu is composed of processes allowing the user to add some variables such as 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 sf Tafel Fit F4 E Rp Fit F3 re Corr Sim es VASP Fit lt CASP Fit hh Electrochemical Noise Analysis F3 Polarization Resistance Ctri Fb La Multi Pitting Statistics Ctrl F7 Fig 105 Corrosion menu This 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 dedicated processes are available 83 3 4 1 Math Menu 3 4 1 1 Min and Max determination On the graphic display select Min Max with the Min Max button or the mouse right click and the data points where the fit will be performed 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
134. eseeeseeeneeenes 139 3 4 6 7 Other corrosion PrOCESSES cccccsscccesececesceceueecceeeeceucecsueeecegeessueessaeeessaees 141 3 5 Dala and file Process 141 Se O o 0 MEA A a ted ene edb ed antares ease 142 Sell PROCESS WINDOW airada rai ai dic 142 3 5 1 2 Additional processing OpllONS uri riel 143 ana Thedervatve DICES e doo 144 7 EC Lab Software User s Manual 39 14 Thecompa t POCO sitiada 145 3 5 1 5 Capacity and energy per cycle and sequence oocccccoccccccnccnconoconcnnncnconanininnns 146 3 5 1 6 Summary per protocol and Cycle isisisi a aa eters tant 147 3 5 1 7 Constant power protocol SUMMALSY ccccooccncccoconcconcnconncnnonnncnnonanononnncnnnnnncnnnnos 148 294 POMMZATON TESISIANCE ninia iaa 149 3019 Mu ltipPItUNO StAlS UCS anat 151 3 5 2 Data File import export fUNCHONS ooocccoccccccncocnccncnconcncnnnooncnnnannonrnnoncnnnnncnncnnnnnonos 152 3 5 2 1 ASCII text file creation and exportatiON ooccccoccccoccnccocncconcnonanonconcnonanonnnons 152 3539 22 ZSMOWINexporntaUON iiit a EA EAE A 153 3 5 2 3 ASCII text file importation from other electrochemical software 153 3 5 2 4 FC Lab data files importation cccccsscccsecccseeceeeeseeeceeeeseeeeseeeseusesseesseeess 155 3 6 POPO aa E 155 Linked APENAS a 158 4 1 DESCAPIOn ant Settings cat aa 158 4 2 APPIiCatTONS oreina unnan eua AE pr 159 4 2 1 Linked experiments with EIS techniques ccoocccococococcncococononcnconano
135. 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 Eye 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 the 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 designed 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 L
136. f each axis done it is possible for the user to define the Graph style but also the techniques to which apply this process The selection of the Graph Style can be done on the Advanced menu as shown in Fig 94 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 94 Graph Representations Eg lve Ewe Name delta vs Estep wert sd Logll we E we hiba Ewe vez Lodil O vs t Ap vs t Bode Impedance Hyguist Impedance EE_E__ A Representation Advanced Graphic style association Technique MATE Line Markers style Y prop style Monochromatic style Style Black Impedance 7 ws t Moott S chottky Bode Admittance MNuquist Admithance Black Admittance El Phase Z errar Select Batterpllzer Voltage control Add fF Voltamperometic Techniques C Open Circuit voltage OC Cyclic Y oltammetr C C Cyclic Yoltammety Advanced CA Chronoamperomety Chronocoulometry CA C Chronopotentionetry CP C Staircase Yoltamme
137. ffers the possibility to link a lot of experiments as a Series of settings files In this configuration the computer is the master of the experiment sending one settings file after the other when this previous experiment is finished The instrument is not autonomous 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 Channel 1 Batch Ea lx Batch List 5 7 CNEC Lab Data amples 4PGC GSMdischarge_1 mpes LC EC Lab DatasS amples 04 _ loop Fe 1 mpz CAE C Lab D atas amples OPV Fe basique_1 mps L EC Lab DataS amples FITT 2300604 1 mps CAECL LabiDatar5 amples potB omer mps CAEC Lab D atas amples 18650 cyclage 260504 GCPL_1 mps LCNEC LabsD atasS amples 6650_GITT_US0604_1 mpe Output Folder C 4EC Lab Data Samples Ouput File s CoNEC Lab Data Samples Batch 1_5 potBormiert U1 mpr Technique s FEIS SeHert x ti Fig 56 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 generat
138. for VMP3 SP 150 VSP instruments 28 Cell Characteristics Parameters Settings Compliance Modify on disconnected cells only Ewe from 10 aes A AA 10 Y Ece from 10 Y IA o 10 Y Less information y ee Ex i Ewe 10 00 y fe 0 then Ece must be between 5 ae A 10 000 and 10 000 10 10 5 0 5 10 Ewe Experiment Limits Eye marx 0 00 pl E nemin 0 00 Y Ill 0 000 m IQ Gol 0 00 m h Analogic IN 1 0 00 y Analogic IN 2 0 00 y for t gt io me Miscellaneous Text export Filter 7 Edit Smooth on lo points Create one data file per loop linked techniques only cr 1005 PT Cac S EEA B EC Lab Software User s Manual XE ent lt no name gt technique Galvanostatic Cycling with Potent Electrodes Connection Modify on disconnected cells only a ref refs Fig 40 Advanced settings window for HCP 1005 instrument 29 EC Lab V10 00 Channel 1 Tum to OC between techniques lt lt Default 21 Advanced Filtering Cell Ewe l 50kHz gt Characteristics Experiment Limits P E yemas oo E Epemin 000 y i 000 m C id Gol 000 m h E Analogic IN 1 max 000 Y E Analogic IN 2 max 000 Y Parameterz Settings EC Lab Software User s Manual Channel Floating Grounded Electrodes Connection Modify on disconnected cells only standard WE O LE
139. formed on the protocol linker loops separately Linked experiments settings can be saved with Experiment Save As or on the right click menu with Save experiment 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 settings files Be careful with the auxiliary signals recorded on Analog In1 or Analog In2 during linked experiments Impedance techniques do not allow the recording of external signals So if external signals are recorded during a linked experiment including impedance measurements no external data points will be recorded during the EIS measurement period When the user accepts such an experiment settings the following warning message appears A Warning itis not possible to record Ece and the additionnal analog inputs with the impedance techniques Selectecting these recordings will have no effect For the impedance techniquets Fig 205 Warning message on Analog signals recording with EIS techniques 4 2 2 Application of linked experiments with ohmic drop compensation The following experiment is given as an example of linked experiments 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 experiments is dedicated to illustrate the ohmic drop compensation Indeed to compensate the ohmic
140. fy button and deselect the channel 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 oe ee ee ee ee oda E 3 Channel with linked experiments can either be grouped or synchronized 2 4 2 Stack experiments Our multichannel units can be used for measurements on a stack of cells in series for example batteries fuel cells or solar cells In this case one channel is used as a master channel to control the whole stack and the other are managed by the master and used to do measurements on each element of the stack In series the current crossing each element is the same and it is the current of the full stack But the voltage of the stack in series is the sum of the voltage of each element of the stack The slave channels are used to measure 39 EC Lab Software User s Manual the voltage of each element The master channel controls the full stack Of course to do that a current booster or a load box must be coupled to the master channel When launching the EC lab software if a multichannel system is detected the opening window will propose to create a New Stack experiment or to Load a Stack Setting Mo experment loaded on current channel To create an esperment please select one of the following actions New Load Settings a mw Hew Stack LJ Load Stack Settings Fig 54 Experiment selection When clicking o
141. ginary part of Z in Q lt Ewe gt averaged Ewe value for each frequency lt l gt averaged value for each frequency Range current range Y Admittance magnitude in O Admittance phase in degrees Re Y real part of Y in Q Im Y imaginary part of Y in Q 2 6 3 Data recording log lt l gt A Qcharge mA h Qdischarge mA h X R O Ewe Ece V cycle number P W Energy W h R O loorr A Ecorr V C F C F freq Hz Ewel V IIA Phase Z deg IZ O Re Z O Im Z O lt E gt V lt l gt A Range YO Phase Y deg Re Y Q Im Y Q In all the technique sequences the user is able to define different modes for data recording The main mode corresponds to fix the recording resolution of the measured variable potential current charge with at least a recording every predetermined time interval dt from 0 1 to 9999 s This last condition gives a minimum 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 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
142. h a better fit by clicking on Minimize This minimization is only possible when the box associated to the value to minimize is ticked The Multi Exponential Fit is able to perform a fit on every data displayed in EC Lab software The combo box in the Fit block offers two possibilities to initialize the fit from the Auto estimate values or from Current parameters Note that the x0 value cannot be fit and must be set manually by the user 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 EC Lab Software User s Manual Multi Exponential Sim Parameters N 1 ale m b 2 qe param walue S cr 1 Js S cm 1 S cm 1 3 5 cm 3 A anig times w Y anig Conductivity S cm W 4 ml 1 000 X MX 110 000 Mb points 1 000 Noise Add noize Noite level 10 1 on S cm 1 Fig 121 Multiexponential Sim window Multi Exponential Fit Selection Trace Conductivity vs time From point 0 E 1s Te 43977 S cm 1 Topomt 999 PS 10 a 2 172 5 cm 1 Total points 1000 Parameters N Taf th a 2 29 param sel value F S cm 1 4 5 cm 1 S cm 1 3 1 S cm 1 3 1 Fit Init Auto estimate w y7 1 574 Iterations 321 Fig 122 Multiexponential Fit window 93 EC Lab Software User s Manual Conductivity vs time MExpSim_mexpfit mpp MEx
143. h 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 Then a processed interpolated data file is created with the following name filename_intpl mpp This tool is very useful to subtract two data files Indeed subtraction between two file is only possible when the files present the same regular distancing between each point Linear Interpolation Selection Trace Ewe ve time From point ai ee To point me aj Total points Sampling Ouput file e Hb Points 86 Sampling Fig 112 Linear interpolation window 87 EC Lab Software User s Manual 3 4 1 5 Subtract files Subtract Files A tool for subtracting curves is available with selection EC Lab The raw data files are not changed after this File 7 anal yS IS A A E a fa Indeed for some applications it could be interesting to File 2 subtract two curves The Subtract Files tool is available in the Math menu or via the right click of the mouse 2 CY 1 10 ckoground mp File 1 File 2 sampling The two files to subtract are selected as File 1 and File Same as File 1 2 Then the resulting file File 1 File 2 is displayed The sampling rate of the resulting file in _filter mpp Same as File 2 format is defined by O Same as File 1 and File 2 e the sampling rate of file 1 or and file 2 Ooo points e the total number of
144. he 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 always running properly in the Tera Term Pro window type r or R this will restart the Ethernet connection program 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 enabled the power save option for his hard disk he risks being unable to record the points In order to avoid this we advise the user to remove the power save option from his computer in the settings panel 178 EC Lab Software User s Manual 7 Glossary This glossary is made to help the user understand most of the terms of the EC Lab software a
145. he corrosion current is then i fs 0100 He 2 lor CA Outputs 4 3 J l 206l Sh 3513 All 88 17e 6 m 612 0 884 Se 6 mA r 2 V3 dl 201 dh 3013 lz Bile Ws eee at SE Sh 36l Icon 0 580 6 p ba 4501 1 feet V3 dP 261 dh 361s l a ee OE Oh 36h Ba 47 6 mv Be 823 7 mv error O 092 21 Fig 179 CASP Fit window 3 L Meszaros G Meszaros B Lengyel J Electrochem Soc 141 8 1994 4 J P Diard B Le Gorrec C Montella Comments J Electrochem Soc 142 3612 1995 This fit is performed with the equation described previously in the Corr Sim tool The amplitude and the frequency sinusoidal excitation applied to the sample can be set manually or automatically as input parameters in the second block of the window Note that this analysis is automatically launched after a CASP measurement 138 EC Lab Software User s Manual 3 4 6 5 Variable Amplitude Sinusoidal microPolarization fit VASP fit In non linear EIS the amplitude of the AC voltage exciting REA signal is higher than in CASP technique so the non linear Selection terms of the Taylor series are significant 5 6 Then this Tian Ap vs sin ampl yields to the following relationship From point 0 2k 1 2k 1 Ik x 0 01015 l hrf ba b JE Y 519091 Ohm a LNA lt Topoint 29 Rp a 2 k k 1 X 0 202 54 Ya 6 273 Ohm VASP Fit allows user to fit data from VASP Total points 30 measurements The
146. he measurement At that time a binary version of the mpl file is appended to the mpr file A raw data file is then obtained which contains all information on the experiment The user can decide to clear the mpl Log file to save place or to keep it in order to continue the Log of the experiment using a word processor Clicking on the Pause button M will lead to a suspension 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 de and clicking on this button continues the experiment with a gap corresponding to the pause time 2 3 2 Modifying an experiment in progress 2 4 The Modify button enables the user to modify most of the parameter settings while the experiment is running The new set of parameters is sent to the instrument when clicking on the Accept button 7 l It is taken into account within 200 us for instruments of the VMP3 family and SP 300 and SP 200 and 20 ms for the VMP and the MPG 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 70 Note that a warning message could appear before accepting 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 lrange Erange and Bandwidth Multi ch
147. he most suitable couple of parameter values with the lower y value The y equation used in this method is defined as follows 2 x Z meas Z roaa F param o i O l with Z i is the measured impedance at the fi frequency Z nos f param is function of the chosen model f is the frequency param is the model parameters ex R1 R2 C1 Q1 o is the standard deviation It can be assimilated to the weight of the impedance data points It can be selected by the user to be 1 or Z Moreover two fitting algorithms are available and the user can select between the Downhill simplex algorithm and the Levenberg Marquardt algorithm Both of them can be tried successively to choose the best results In the fitting method the user can select between different combinations only Randomize only Simplex fitting only Levenberg Marquardt fitting combination of randomize followed by Simplex fitting combination of randomize followed by Levenberg Marquardt fitting Fit so eh Method Randomize Simples Ww Randomize Simples Randomize Levenberg M arquardt ee Randomize Simples stop randomize on 1 0000 erations Randomize Levenberg Marquardt Weight 1 w wn 1 i tt lterations xa Cycle at Fig 151 Fitting method selection lf ALL cycles are selected for the fit the user will have the possibility of selecting the randomization on the first cycle only or on every cycle
148. iStat Bandwidth 7 6 5 4 3 2 11 680 kHz The following table gives typical frequency bandwidths obtained with a 2 kQ resistor connected between the working electrode and the reference electrode coupled with the counter electrode 2 points connection for the VMP and MPG Bandwidth 8 7 6 5 4 3 2 1 600 kHz _ 200 kHz 60 kHz 600 Hz Note refer to the SP 300 or SP 200 installation and configuration manual for details about bandwidth definition for SP 300 and SP 200 instruments When the mouse pointer stands for several seconds on a box a max 100 hint appears The hint is a visual control text that gives the user min 0 l information about the box It shows the min and the max values ETA of the variable as well as the value that cancels the box Fig 31 Hint For several protocols in the flow diagram mode a table appears automatically It allows the user to make an experiment with several sequences different parameters that will be executed one after the other N defines the sequences of the protocol 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 0 00 0000 0 0 1 0000 0 350 None gt 0 00 10 0000 0 000 m 0 01 0 0000 0 0 l 0 1000 0 300 None gt 0 01 0 0000 0 000 m m pe hens ea CIC Ys ee Yo ze 00 1 0000 0 0 D 0 1000 0 300 lt None gt 0 01 0 0000
149. ils Graph Tools Prag q EO at he Fig 8 Graphic tool bar e The fast graphic selection tool bar with choice of the displayed cycle ToolBarGraphaAdy Ewe hal Fig 9 Fast Graph selection tool bar 2 2 1 3 Status tool bar Atthe bottom the status tool bar shows VMP3 192 109 209 227 Channel 1 Read mode My Name 30 6 5 081 Fig 10 Status tool bar e the connected device SP 150 SP 300 SP 200 VMP 16 20 16 channels and 20 ms acquisition rate VMP2 VMP3 VSP MPG or BiStat e the instruments IP internet protocol address if the instrument is connected to the computer through an Ethernet connection or USB for an USB connection e the selected channel e a lock showing the Modify Accept mode in relation with the box near Read mode or Modify mode e the remote status receive or disconnected e the user name e the mouse coordinates on the graphic display 2 2 1 4 Current values tool bar On the left side or in the bottom a tool bar shows the current values of the electrochemical cell connected to the channel 11 EC Lab Software User s Manual Channel 1 values EJ Fig 11 Current values tool bar e Current Ewe and Time are the current the working electrode potential and the time from the beginning of the experiment e lo or Eo lo is the initial current value obtained just after a potential step in potentiodynamic mode Esc is the potential value reached at the
150. in the File menu Load data file The following window will be displayed C EC Lab Data Samples ZPOT_ Fe basique_1 mpr Iimf vs Retz Im Z V0 hm 50 100 150 200 Re Z 0hm Fig 145 Experimental Nyquist impedance data file This is a typical impedance data file performed in a pure diffusion regime in a solution containing both Ox and Red species of a redox system 3 4 3 2 1 ZSim 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 Analysis ZSim Then the ZSim selection window appears with the corresponding graphic window This window shows the simulated graph of the circuit with the values selected 110 EC Lab Software User s Manual CI EC Labw 30 Data sim mpr gt Imi vs Rete Set Frequencies from F 500 000 o t fo with 10 points Equivalent circuit R1 01 R2 C3 A3 v Edit 4 parameter walue Ohm F s a 1 Im 2 0 hm Ohm F Ohmi ho 1 000 1 080 1100 Re Z Ohm Calculate Fig 146 ZSim menu and the graph corresponding to the selected circuit Note the default opened simulation circuit is the last one used in the previous simulation 2 step In the frequency frame set the frequency range between 500 kHz and 10 uHz with the number of points per decade and the spacing logarithmic or linear Select an equivalent circuit in the list If
151. indow Note the date is displayed and printed automatically in the top right corner 3 2 9 Multiple graphic windows 3 2 9 1 Multi graphs in a window The EC Lab software graphic window is capable of displaying several different and independent graphs Four graphs can easily be displayed in the same window 72 EC Lab Software User s Manual title GITT elo vs Ewe CY Fe basique 1 impr Ewe ve x 16650 _GITT_O30604 1 lQx mpp Ewe V ws SCE o miZ Ys Rell 2ZPOT Fe basique_1 mpri vs time CA _loop_Fe 1 mpri 50 Re Z Ohm time s Fig 90 Multigraph 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 2 Multi windows When several windows are displayed in the EC Lab software the user can either show windows in cascade or tile the windows on the screen Choose Windows Tile to display several graphic windows at the same time 73 EC Lab Software User s Manual Channel 2 experiment CV technique Modular Galvano gt e vs time C4_Fe_1 mpr Next sequence or Goto sequence N lo for n lo time Advanc
152. inked experiments can be made using the technique builder in the technique window The WAIT and LOOP options have been designed specially 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 New Experiment Ctrl M 2 Load Settings Ctrl L i Save Experiment Chrl 5 Print Experiment Ctrl F ES Insert New Technique Ctrl I ae Insert Technique From File Ctri F Move Technique Before Move Technique After E Remove Technique ER Remove All The Techniques 2 Accept Ctrl FS Cancel Modif b Run Ctrl F a Channel 1 Graph Ctrl G Fig 201 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 experiment The user can select where he wants to add the new technique into the settings according to the activated selected technique green frame around the technique name in the parameter settings window at the bottom left corner frame of the technique selection window lnsert Technique Before le After Fig 202 Insert before after option of the technique selection window 158 EC Lab Software User s Manual If the technique is not in the correct position in the series of experiments the user can
153. istics 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 Cycles loops selection W Same selection for all files Export cycles 13 r Esport all files into a single txt file Fig 196 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 gt 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
154. ith 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 169 EC Lab Software User s Manual For example in a 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 A WARNING several I ranges found within technique 1 GCPL Ensure that each I range changes Follows an GC period else the changes will have no effect this is not tested by the software Fig 218 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 between sequences It is the user s responsability 9 4 External device control and recording 5 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 O to 5 V range The figure below shows the external device window where the user sets parameters Many instruments are
155. just to start a zone selection as described above Now a zone is selected on the trace and a fit window is displayed 3 3 1 Zone selection On the graphic display the zone selection can become very complex when several cycles or loops have been made during the experiment or when several zones are selected at the same time In such a case the software will ask you to select only one trace before doing a fit CV platinum 10 ycles mpr ale vs Ewe Selection Points Selection Select zone E 12 lt I gt HA 0 0 5 1 EwelV vs SCE Fig 98 Zone selection on the graph 81 3 4 EC Lab Software User s Manual In this example the user can show one cycle right bottom corner In that case he will be able to select only one trace If several discontinued traces are selected in the zone the selection window is displayed to choose one trace for the fit Select the zone and click Ok Analysis Menu The analysis menu is separated in six analysis sections depending on the application Mathematic General electrochemistry EIS batteries photovoltaic fuel cells and corrosion Tools Config Windows Help Yi Math 4 General Electrochemistry j Batteries Photovoltaic Fuel Cells j amp Corrosion i Electrochemical Impedance Spectroscopy Show Analysis Results T Fig 99 Analysis menu Wi Min Max Shift F1 ef Line Fit Shift F2 Sy Circle Fit Shift F3 Flo Linear Interpolation
156. k menu The graphic window contains a right click menu different from the Parameter setting window right click 93 dd Eep Os gt Es ih EC Lab Software User s Manual Plot b Mouse Mode d Autoscale d 3D Analysis d Show Analysis Results Comments Hide OCW Points Hide Selected Points Show All Points Load Files Alt 0 Add Files Remove Trace Alt R Save Data File As Ctrl S LOG History Edit Surface and Mass Load Settings On Channel d Add Graph Remowe Graph Copy b Print Ctrl P Graph Properties Alt P Fig 66 Mouse right click on the graphic window On this right click several frames are separated In the first block four menus are available 94 Plot for the selection of variables displayed on the graph Mouse Mode for the selection of graphic tools Autoscale for resize one axis or all axes 3D for displaying the graph with a 3D mode 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 Ctri S LOG History Edit Surface and Mass Load Settings Un Channel LA Add Graph Remove Graph Copy Print Ctrl P ii Graph Properties Alt P EC Lab Software User s Manual gt Scroll de Cursor ae Selection E 00m 00M EE al SS As Ta 1
157. l bar Channel SClSCHON scada EET EEO A O EPET 10 Current vale S ti a aaa a 12 Fastoraph cl codi 11 Elo Sea PA ee eee 11 o APP o e A amnion T ammo ae ate ean 11 Tool Bar LOCK AAA AA vcs te cesta aaa cts eee reac tee ete asec ae 12 Woe peel a2 aU gt Ree ee eet a eo ene ee Te 17 Variable Amplitude Sinusoidal microPolarization VASP ccccssecsseeeseeeeseeeseeeeseeesaeeens 139 Y gfe le mo ens Ce eee 43 processed VA AS e ee o eae 43 Warburg for Convective diffusion Wd oocccocccccocnccccnnccncnnonncncnnnnnnnncncnnnnononenonnrnnnnnnnnnos 108 Warburg Wisconsin pa odo re tant 107 Wave analysis A A AE ere oer AE ee ero E A E eee A Oe ee ene eee ee oe E me ae 99 7A HCAS eR e a a a ee eee eRe en eee S 114 DeSCription COde SYNtAX c cccccecesceeesceeeccsecescseeeceeecccucessseeecceeeecucesscentcceasessetsceeteseus 112 SUCCESSIVE CY CLO Mrs 118 A Metso esti a E A na 110 DESCHIDTON COGS SV MAX eee ico idas 112 EC Lab Software User s Manual A ata aingieat E E semana wheat nant samuacsanennee 153 190
158. l solution without applying any electrical constraint to the system OCV period This includes A deaeration period with nitrogen or argon of the electrochemical cell with a mechanical stirring Anecessary period for a stationary state establishment with stirring In the case of fuel cells the membrane incubation with a gaseous flux on the electrodes without generating an electrochemical reaction 5 5 2 2 Electrochemical modifications These modifications require an electrochemical constraint by applying a potential or a current at the electrode surface The applied potential is commonly the starting potential of the electrochemical measurement Different reasons for applying the starting potential can be mentioned preconcentration accumulation of electroactive species on the electrode surface for example for metals while reducing on the electrode surface before an anodic stripping voltammetry detection Treatment of the electrode surface activation of electroactive functions or cleaning at a fixed potential or current value or in a dynamic mode with varying E or To avoid a great transient current or potential when the experiment will start In that case the working electrode will move from the equilibration potential to the starting potential that can be very different 5 5 3 EC Lab facilities for the pretreatment before an electrochemical measurement To perform preconditioning with EC Lab the u
159. lative error for each parameter Re Im 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 39 127 y EC Lab Software User s Manual P Diard P Landaud J M Le Canut B Le Gorrec and C Montella Electrochim Acta 39 1994 2585 3 4 4 Batteries menu This menu is only composed of process tools and these processes are described in the paragraph 3 5 3 4 5 Photovoltaic fuel cell menu The photovoltaic analysis provides characteristic values of a solar cell Photovoltaic analysis A s lection Trace lo ve Ene LP_PV mpr z lt b vs Ewe Pvs Ewe From point A ie To point ai 0 815 9e 3 T 41 19 m Total points 6300 PMAX 91 mW Results ler 41 181 m Eee 3145 ET 129 508 mia Prax 91 069 miw FF 70 3 Pin 750 Wn 5 28 500 cre Efficiency 18 3 Ewe V lt l gt mA MW d Eoc 3 145 V Mm Geode omy Seve Cae The resulting V characterization shows a typical vs E and P vs E curves Several parameters can be drawn from this curve with the Photovoltaic analysis tool Short Circuit Current ke which corresponds to the maximum current when E 0 V lec 41 mA in this example the Open Circuit Voltage E which is the
160. lculated upon moving a circle Mott Schottky Parameters Temperature 25 0 L Dielectric constant 10 A 000 err Surface Area Results File CNEC Lab ec lab 3 10 Range 0 020 16 0 260 7 Frequency 100 000 kHz Flatband potential 0 761 14 Donor density 2 fo2el2 cm Frequency 46 406 kHz Flatband potential 0 765 2 Donor density 0381 cm Frequency 10 000 kHz Flatband potential 0 748 Donor density 2 r el cm lt gt Copy Save Close Fig 161 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 124 EC Lab Software User s Manual 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 140 000 120 000 100 000 C 2 pF 2 co o o o a 40 000 20 000 04 0 3 0 2 4 1 a lt Ewe gt V Fig 162 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 Other available fit on impedance measurements are developed in the section 3 4 3 1 page 104 of this manual 3 4 3 4 4 Saving Fit and
161. ld be useful for the user to synchronize both channels 173 EC Lab Software User s Manual 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 ae HEF3 and CA1 AEF and Ground REF2 WE CE HE j L elecirocremizal cell Focus on the rear panel Analog Out Trigger Out 5 4 3 Temperature control Temperature control is possible with the auxiliary inputs outputs of a VMP3 with a voltage control Several thermostats have already been configured on the VMP3 such as Julabo series and Haake Phoenix series 174 EC Lab Software User s Manual External Devices RDE Configuration Channel Device Type Device Mare E v Thermostat v Haske Phoenix seres Analog OUT Analog IN 1 aoo Mo 100 Manual Control Analog IN 2 TC foo Convert EA to To M E U a ar one with lo ME T C max 0 v D E min 100 Fig 224 Haake Phoenix series thermostat control configuration with a VMP3 The user can configure other thermostats to only record temperatures Analog in or both control Analog Out and record Analog In temperature 5 4 4 Electrochemical Quartz Crystal Microbalance coupling The SEIKO EG amp G QCM 922 quartz crystal microbalance has been coupled with our potentiostat galvanostat to record both the frequency variation and the resistance varia
162. lection bar select Custom 121 EC Lab Software User s Manual File Selection Variables CME C Lab D atas amples POT_Fe_basique_1_2tit mpp a Fi freg Hz Rel10hm Imi Ohm El Ohm Phase deg Delta Re 214 Dieltal Im 21 Delta L1143 lt Delta Phase 14 lt QODOdOdaO HOUSOOUOOO HIMOUUUOOO Same selection for all files Hide Additional Variables Fig 158 Selector for the Zfit mpp file offering the possibility to display the relative errors These additional plots may be very useful in evaluating the acceptability of the equivalent circuit selected and the relevance of the measured data points 3 4 3 4 Mott Schottky fit Only the instruments equipped with the EIS measurement option have the capability of Mott Schottky fitting 3 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 1 2 kT L g Co O amp N e where Csc Is the capacitance of the space charge region e is the dielectric constant of the semiconductor Eq 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 semi 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 c
163. les such as Q and energy in this case 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 o Define the cycle as Auto loop increment every charge discharge alternance 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 3 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 automatically select all the variables of the native raw file An Export as text option as 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 o
164. m E Mechanism EEEE Setup Pero ez es es sep E 1 Reaction Reaction Reduction A zed E Reduction A zed E z i z 1 Eo nz Y Eo nz ko O00 em s ko oon cms Of o5 of 05 Species Species Ca initial fet Ea initial Da e5 Da Dg Beb Coleuate Copy Save Fig 130 CVSim window with a single Fig 131 CVSim window with several transfer transfers For each step the type of reaction and the species characteristics are set in two different frames 1 Reaction Reduction or oxidation has to 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 100 EC Lab Software User s Manual k is the heterogeneous rate constant ais the charge transfer coefficient in the forward direction 2 Species Cx is the concentration of the specie x As it is assumed that only one specie is initially in the solution concentration is only set in the first step of the mechanism Dx are the diffusion coefficients of the species x The experimental conditions are set in the Setup tab which is divided in five blocks Example Select e Electrode Mechanizm E l l ae al Geometry of the electrode can be linear semi E setup l infinite or spherical semi infinite Electrode The surface area of th
165. 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 If 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 www bio logic info potentiostat distributors html The highly qualifi
166. mpliance the electrodes connection experiment limits and the smooth option are used in specific experiments Depending of the instrument of the Bio Logic range used various Advanced Settings windows are available examples of these windows are given in the following figures To change the values click on the Modify button enter the new settings and click on the Accept bution to send the new settings to the instrument F cling with Potent Ei EC Lab V10 00 Channel 1 Turm to OCY between techniques lt lt Default ml Compliance Electrodes Connection de Advanced Modify on disconnected cells only Modify on disconnected cells only Cell Ewe from 10 Y g 10 Y o Characteristics Ecel 10 7 10 Y Parameters ae 7 WE Settings refl Less information i oy al TP l mo Ex ifEwe 000 Y o 0 E then Ece must be between 2 po ef se l 10 000 and 10 000 W 10 re Experiment Limits E E wema 00 Y L Ejye min 000 Y E 111 DOD m F JB Gol 000 m h E Analogic IM 1 max 000 Y E Analogic IN 2 max 000 for t gt wo m MI Miscellaneous E Test export E Filter 3 Edit C Smooth or 0 points E Create one data file per loop linked techniques only status Time Ewe I Butter Eoc Q Oo iy vMP3 AC Channel Bere g 948 Fig 39 Advanced settings window
167. 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 button lf one requires more accuracy it is 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 3 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 u
168. n one of these choices the following window appears for channels selection master CH3 CAZ Rer slave CH5 Refi Group Synchronize Stack Set inns m mode toni E slave CH5 Ret slave CHS 1 A E 4 ls W e Ss fio F slave CHS Refa F13 14 F F slave CHE Ref Select all Stack master df 3 Number of mesured elements in 4 i T p the stack slave CHE Ret slave CHE OF Cancel slave CHE Refa master CH3 CA1 Refs Ref Fig 55 Channel selection window for Stack measurements Thanks to the description on the right the user will have to select the master channel and the slaves The user must have in mind that each slave channel will measure the voltage of two elements as follow E1 Ref1 Ref2 E2 Ref2 Ref3 As an example with the picture above the master channel is ch3 and the unit has 5 channels to follow the slaves so the total amount of measured elements in the stack is 10 But the stack can be constituted with more 40 2 5 EC Lab Software User s Manual than 10 elements Only 10 elements will be measured in this configuration On the slave channels the current wires CA1 and CA2 are not used Note also that most of the techniques and applications can be used and linked in Stack mode When the user clicks on the Ok button the Techniques selection window is automatically displayed At this step the user can create the experiment with one or more techniques Batch mode The batch o
169. n the instrument is selected the corresponding number of available channels is displayed with additional choice for amplifiers and cables for SP 200 300 if required In this mode the user can create a setup and save it as a mps file 45 46 EC Lab Software User s Manual Virtual Potentiostat Instrument Channels Amplifier Cable z Virtual Potentiostat Instrument Channels Amplifier l 2 A amplifier 5 amplifier 10 A amplifier 20 A amplifier low current option 60 A amplifier 4 A amplifier 6 A amplifier 500 W load box 2 kW load box lt fJone lt fJone lt fJone lt fJone lt Mone lt Mone Cancel Fig 59 VMP3 Virtual mode EC Lab Software User s Manual 2 9 Configuration options Choose the Config Options menu to load the Option window 2 9 1 General options Options default General Waring Test export Colors References Tool bars menus Files Save data every F Add channel number to files names LOG files mpl automatic erasing on stop Create automatically saved files Directory CAMP Alles T emp auto B Prefix patrick 4 Create one folder per day Saved File director lt date gt lt index lt prefix mpr Hide processed on line files mpp Manage Reports Ll Stack temporary fles 7 mpr automatic erasing on stop Cancel Fig 60 Option window General tab Th
170. n transter reactions and adsorption processes It offers a rapid location of redox potential of the electroactive species CY consists of scanning linearly the potential of a stationary working electrode using a trangular potential wayvetorm During the potential sweep the potentiostat measures the current resulting from electrochemical reactions consecutive to the applied potential The cyclic voltammogram le a current response as a function of the applied potential Fig 27 CV technique picture and description on the experiment window 2 2 4 Parameter Settings When a technique is selected the default open window is the Setting Parameters window The user must type the experiment parameters into the boxes of the blocks Two ways are available to display a technique the detailed flow diagram Fig 28 and its table the detailed column diagram Fig 29 lt is possible to switch between the two displaying modes with the o button Setting parameters 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 Load settings Note Most of the techniques allows 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
171. naa wan tate gine in eeate we meus inatat weenie dtatewe ane eaaewgstts 143 A 105 Right click Ad CONTEN meee ee ener eee ee ee eee teas ee ee een eee eee 56 Graphic 100k Diaria ansias prada 10 FIS lala PON Siri dea 56 OOO e o 56 SUN SO o a 10 Right Click O An 54 AUTOS e a 54 A e stenadenstaaiceasteneds 53 188 EC Lab Software User s Manual A O A 13 MOUSE MODO Edu 54 PO tt a lee cb 54 Rotating elec rode Sheinn 172 173 AA PE y eee OE A nt ea eee aa 36 PPP 36 56 A A A FAE EEE E 45 SNSPA ZA e o ee ee ee eee 36 A AER E E TE eo en Oe ee 125 T gt gt pee nee nn ee ee eee eee eee 21 SI e e Ne 58 SU o o et 59 Add E o A E AQ eo ee ee eee eee 60 e e EE PUE EEE O 60 A A E E AO 60 A ct grec atatenat es itcuat catia tates anata ataaneanate ate mteeatsaaniiar Mateenennategace ae guee aeatemat ee seenates 60 S ale 6 aeeeeteme tee mre ted meat Reet ted e o e 60 A Se et ae ee Se he eo Lee ae ce a Leah a eR a hea baa Oa Seas ha eee 59 A 33 Sotware Updates 1 ateo acta 17 as 37 SOT anda Gear modelar a e a ae 129 nn nn eet ee ee eet eet eee ees 37 oleada 88 SU Le ols Ear OPA PO O E e A E a 135 Seal ra channel PA o o dlad erated a a a e easel 39 o eee ee 22 DRA 23 Repeal A Gaetan a eons teeta ener 23 A cee ere ee en eee eee ee eee eer eee eee 134 PEE 136 SA A teeta S 136 TOO niet obatinheus ait alanine arate muataue ara taiemietaie aietaiegmiat aie aietaleemietaeeem 33 i Sua cere Carte ere AARIA eae AELA A 62 Too
172. nce data Analy S S cexscc tect saci se5h o e secu a be eto eo een sen a Dd ated 104 Import SEPALO acc 155 A E 154 oo AA PA Pr err eee ar ey eee ate ere eee ce eee 106 A y A 18 A nese ease et repo en ere enous Ne eae eR re sa Be eae ears Neh er sus A E E peer anaa 89 o en e o reise ae ae es aan ae 32 MI pe cere Po PE II II II A E E TE 85 Misa o SA 87 A A o IE 158 custom ADDIICalO Misc ac e o e ba SE 158 KRANO O o cita 159 INSET TECHINGUC perserne enua NEENA ANENE 158 MOVE WO es cic isthe renia ET ET AT EET AET A 159 MOV O S 159 RIO MECA Me nd 158 Linked experiments settings ccccccsscccseeccecececcceeeccueeceueeceuecsueecueeseeessueesseessueessuseneeesaas 161 LOG MISTO uti diia 70 LOOP uretra ea diana diia d 61 153 Memory SIZO ada 45 e area ne era eee ee aoe ee a ese ee ee an ee ea 14 PP A 84 A A O csee eaet can 37 Mott Schottky A A E A E E E dseacdincctet 124 A a ore eer 123 EUAN Srl Fact acca cess NN 122 WIUMICH AMINE SCICCUON ari htared Sous eerie ones eae odes eee ee soled eae ole eas oid 37 MUtexponentlal SIN Flat id 93 A em o 31 INGWS Ol rasta 17 Option GO E O O ee la eee eel 50 E A reece ee Cn ET 47 ReTerencte ElOCIOG GS midis 50 TEXVE MOOK nti Gastanta carter Wontannedevten Gatita ul Dalai ui 49 o O 52 EC Lab Software User s Manual MW AUT AT 48 A ondsdcedand adi E ER 47 Parameter Settings WINDOW tissraisacas aria aii el 19 PAUSO a amines wees psestia E aaa test een en asa eerste
173. nced Settings Cell Characteristics y Channel Mew Experiment Ckrl HN gt Load Settings Ctrl L m Save Experiment Ctrl 5 gt Print Experiment Ctrl F Es Insert New Technique Ctrl I E Insert Technique From File Ctrl F e Remove Technique EA Remove All The Techniques Reset Settings To Default Fie Set Settings 4s Default grs A a Group Synchronize Channel 2 2 Remove Sequence Ctrl D Ef Reset Sequence Copy Sequence Ctrl C Ei Paste Sequence Ctrl V 2 Accept Ctrl M e Run Ctrl h E Display Current Settings Graph Description r Channel 2 Graph Ctrl G Fig 14 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 building to printing The third frame is for the modification of an experiment and creation of linked experiments The fourth one is devoted to sequences addition removing and the fifth one controls the run The last one is dedicated to the different view 2 2 2 The bar menu T Experiment Edit View Graph Analysis Tools Config Windows Help Fig 15 The bar menu of EC Lab software main window 14 EC Lab Software User s Manual The bar menu has been designed in such a way that it follows an increasing progression in the experiment from the experiment definition to the curves analysis Each menu is
174. nd 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 Rj conventional term defining the electrolytic resistance in a solid electrochemical system such as a battery R is defined as the ratio dE dl when the potentiostat switches from 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 E and the corresponding measured value for example Ewe Capacity per cycle processing function that calculates the capacity per cycle for the galvanostatic with potential limitation the chronocoulometr
175. nnel of the global view to select it You will get the following window EC Lab V10 00 Channel 1 no experiment EN Experiment Edit View Graph Analyse Tools Config Windows Help BORA E 2 a A 0 E 7 6 5 10 1 l2 la l4 15 1G Tum to OC between techniques ge Default Advanced Settings No experiment loaded on current channel Cell Turm into Modify mode menu Experiment Modify to unlock Characteristics the channel and define a new experiment set with Experiment ei Mew oor Experiment Load Settings itetus Time Ewe ee D o Range vMP3 Channel B Read mode 8 Fig 4 Opening window for experiment setting This window shows EC Lab Software User s Manual 2 2 1 1 Settings tool bar At the top e inthe blue title bar the software version with the active channel and the experiment selected e the main EC Lab bar menu Experiment Edit View Graph Analysis Help e the settings tool bar with short cut buttons Main Tool Bar BE E E e 0 E Ef amp Fig 5 Main tool bar The user can change the buttons displayed in the tool bar To do that the user can either click on Config options tool bar and select or deselect the desired buttons see part 2 9 6 page 52 for more details or right click with the mouse on the settings tool bar to display the icons selection The same option is available for the graphics tool bar Options default
176. noncononanonnnons 159 4 2 2 Application of linked experiments with ohmic drop compensation e 161 Advanced ear Sinai cia 163 5 1 Maximum current range limitation 2 4 A on the standard channel board 163 Silk OMS TSMUAMMM MAU ONS celta watacestoasaculna oaionsuoaratnnsaxannedioakagetananaten 163 5 1 2 Application to the GSM battery testing ccccooncncoccncncnoncnnononcncnnanonononcnnnnanennnnos 164 5 2 Optimization of the potential control resolution oooonccconccconcncnnncncnncnnonnnnonanonnnoss 166 9 2 1 Potential Gontrol range Span sida did 166 5 2 2 Setting of the Working Potential WINdOW ocooonccconcnccoccnconcncnnnnnnnncncnnannnoncnonnnos 167 5 3 Measurement versus Control current range coocccocccocncoconoconoconnconnnonanonnnonnronarinaninoss 168 5 3 1 The potenti Modena 168 5 39 27 The galvano Mor 168 5 3 3 Particularity of the 1 A current range in the galvano Mode cccceeeeeeeeeeeeeeees 169 5 3 4 Multiple current range selection in an experiment oocccoccconcccnccconcnconcnnncnconcnnnnnnnns 169 5 4 External device control and recording oocccocccoccococnconcnnnonocncnonanonnononnnnnnanonaronnnnnnns 170 5 41 General descripta a E e a 170 3 4 2 Rotating electrodes CONTO less anda delas E nee dell atos die pedal 172 5421 ORION OIG lesna a 173 54 3 Temperat re CONTO leissara aaa a E AN 174 5 4 4 Electrochemical Quartz Crystal Microbalance coupling
177. odes or of a set of selected files Multi Pitting Statistics CA Documents and Settingssebasten manips VMPIl sebiicorrosionbPPAMPP4_1_3 mpr LADocuments and Settingssebasten manips VMPIl sebiicorrosionPPAMPP4_1_ 4 mpr LA Documents and Settings sebasten manips VMPI sebiicorrosionMPPAMPP4_21_5 mpr C Documents and Settings sebasten manios VMPI sebiicorrosionMPPASMPP4 1 Empr CA Documents and Settings sebastientmanipe VMPI sebicorrosionMPPAMPP4 1S ompr Load Add Remove Statistics channel E init 4 1 396 1 061 1 418 1 445 E oc Mv Vas 1 045 1 399 1 433 Ep 4 0 529 0 567 0 530 0 533 E inite GE init E ocw SE uc Ep gt Ep We Print Settings Copy Print Close Fig 194 Multi pitting statistics window Note that the E value corresponds to the potential measured for lp 151 EC Lab Software User s Manual 3 5 2 Data File import export functions 3 5 2 1 ASCII 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 Tools Export as Text in the EC Lab menu bar This will load the window below C ME C Lab D atas Samples Fe bazique 1 mpr Format Options All Files Cycles loops selection Time i Same selection for all files Elapsed Time in Absolute Time mmetdd yyy bhermss 33 Export all Impedance Units All Fil EL Lab Text Format mpt ae Condu
178. opied 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 CV platinum 10 cycles_n mpp le ve Ewe cycle 1 lt gt A T 20 20 20 0 5 EwelV vs SCE Integral Selection Trace le vs Ewe From Point 58er a 0 836 7 Y Ae 0 161 4e 3 m To Pont b z a 0 166 Ae 2 215e 3 m Total pomts 135 Results Integral 3 531 14e 3 m Fig 115 Integral window Integral E Selection Trace From port mi Te To point ESE 0 076 49 a e 3 211 pA Total points 104 Results Integral 1 950 29 pA W Fig 116 Integral determination on a trace 89 EC Lab Software User s Manual 3 4 1 7 Fourier transform Fourier Transform Selecti This mathematical tool dit allows the user to calculate the tee eae discrete Fourier transform DFT which is a specific kind of mao ae Fourier Transform It transforms one function into another peo 47 which is called the frequency domain representation or ee 8 028 3 m simply the DFT of the original function But the DFT To point 80 requires a discrete input function and whose non zero A E values have a limited duration Yo Aiea mA Total points 37 The calculation is done following the formula u ead Parameters 1 ANA y XA T Deco X exp 2izft with Window Xel ee ee Xy X t x kdt Frequency range Auto Freg Min Hz When a data point zone is selecte
179. ot of a number abst absolute value rourndi round to the nearest integer trunci truncates a real number to an integer Calculator E Ind natural logarithm Mathematical expression laglo logarithm base 10 Variable sing sine of an angle in rad a cost cosine of an angle in rad kant tangent of an angle in rad arcsini inverse sine in rad arcoost inverse cosine in rad arctan inverse tangent in rad sinh hyperbolic sine of an angle in rad cosh hyperbolic sine of an angle in rad Earn hyperbolic tangent af an angle in rad arcsinht inverse hyperbolic sine in rad arccosh inverse hyperbolic cosine in rad arctanh inverse hyperbolic tangent in rad PI 3 141592 6535589 952385 degtorad conversion of degrees to radians radtodeg conversion of rad to degrees Fig 93 Axis processing window and available mathematical functions 76 EC Lab Software User s Manual 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 display He must select variables to be displayed on X axis and on Y1 and Y2 axes in the Representation window He can also define a processed display for each axis in the Advanced window Once definition o
180. ote that the fit results are automatically saved in case of multi cycles treatment References W H Press S A Teukolsky W T Vetterling 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 3 4 3 3 5 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 fy 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 ARO 2RC 119 EC Lab Software User s Manual 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 Im Z vs Re Z POT Fe basique 1 mpr POT Fe basique 1 zf t mpp Im 2 0 hm Re Z Ohm Fig 155 Fit results with an R1 R2 Q2 circuit Selection Results Equivalent circuit
181. pSim mpr Conductivity S cm 1 5 10 time s Fig 123 MultiExponential fit result 3 4 2 General Electrochemistry Menu 3 4 2 1 Peak Analysis A peak analysis 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 qu button in the graphic tool bar or select peak analysis in the right click analysis menu When this first part is done the peak analysis consists of two steps First the user must choose the baseline and second click on calculate to have the results 94 3 4 2 1 1 Baseline selection 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 polynomial baseline lf the user selects NO the analysis will be performed according to the abscissa axis If the user select LINEAR three different baselines can be set in manual mode with markers locked on the curve or regression mode with a linear regression made on the capacitive part of the curve before the peak or in a free mode two cursors defining a straight line unlocked to the curve If the user selects Polynomial a polynomial baseline is plotted and adjusted to the data points in the following way two data zones
182. 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 Aberrant 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 alicia for better fitting The data points must be selected with the selection mouse mode 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 62 EC Lab Software User s Manual lt gt mA 0 3 0 2 0 1 O 0 1 0 2 0 3 0 4 0 5 0 6 0 7 Fig 77 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 63 Comment
183. ph Advanced option offers seven different file formats for the graph copied enhanced metafile Bitmap SVG Post Script PCX GIF 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 He can also choose to print the log file and some comments added by the user in the comments tab All will be printed on the same paper page The printer setup is also available with the setup button A print preview is available to see the different parts of the page 71 EC Lab Software User s Manual Printer 1 SA HF Lasenlet 4100 Series PS Setup Preview LOG Comments lh Print Graph We Print Comments W Print LOG Fig 89 Print w
184. potential when the current is equal to zero ampere Eo 3 145 V the theoretical power Pr which is defined by the following relationship Pr ke X Eoc Pr 129 mW the maximum power Pmax 91 mW the fill factor FF which is the ratio of Puax and Pr FF 70 3 the efficiency can also be calculated If we assume that the solar power is equal to the means of the surfacic solar power 175 W m which is 499 mW for our photovoltaic cell surface area 28 5 cm The efficiency of the solar cell is 18 128 EC Lab Software User s Manual 3 4 6 Corrosion menu Several techniques such as Linear Polarization LP Constant Amplitude Sinusoidal microPolarization CASP and Variable Amplitude Sinusoidal microPolarization VASP measurements are used to characterize the corrosion behavior of metallic sample These measurements yield to determine the characteristic parameters such as e the corrosion potential Ecorr e the corrosion current horr e the Tafel constant for the anodic a metal oxidation and cathodic e oxidant reduction reactions and are defined as positive numbers Tafel constant can be given as b and b where ba In10 B and be In10 B The Corr Sim tool allows user to simulate data All Comicos these methods are based on the Stern and Geary P model Stern and Geary ref 1 proposed a model of a corroding system that involves two electrochemical Ecom Geum mm reactions an oxidation process and
185. ps or several cycles then one can display specific loops or cycles To access the cycle Loop selection the user has to add the cycle loop number to the data file In EC Lab Analysis menu select General Electrochemitry Process data After loading the data file select Cycle Number and Process The following window appears II Process Data LK Input File LAEC LabiDatas 5 amples CY platinum 10 cycles mpr Processed File CAEC LabiDatarSamplesi E platinum 10 cycles mpp Change Variables To select from the input file To be added mode cycle number osred E 0 Qo m h error 1 0 charge m h control changes O discharge m h counter inc F didim tz times control E mwer SEF All all Average E steps Allow Reprocessing Cycles definition C Export As Text Count half cycles Fig 75 Loops cycles process 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 activated on the graphic tool bar to select the cycle to display 61 EC Lab Software User s Manual le Show Cycle 4 b lt gt mA 0 2 02 0 4 0 6 Ewein Fig 76 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
186. r 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 in a multichannel mode to start different experiments on the selected channels 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 compensate the solution resistance Limits in the advanced settings window the experiment
187. r 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 description below A Count half cycle process is available to separate half cycles especially for discharge discharge measurements in battery testing Additionally a process is also available for QCM experiment and especially for the determination 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 13 143 EC Lab Software User s Manual 3 5 1 3 The derivative process Process Data Px Input File CAEC LabiDatas5 amples CY platinum 10 cycles mpr Processed File C EC Lab Data Samples C platinum 10 cpcles_ d mpp Variables To select from the input file To be added mode cycle number osred G Go m h error O charge m s h control changes O discharge ma h counter inc dl dbs mAs time s control Ewe 1 gt m All E Al Average lo steps Allow Reprocessing Cycles definition Export As Text Count half cycles Process Display Close Fig 184 Cyclic voltammetry processing window For techniques resulting in a current measurement when the potential is controlled
188. rantee 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 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 service this equipment EC Lab Software User s Manual Table of contents EQUIPBmentn stella Ma ta win ere aS ta win ere ent winter sue ANN O ee Intended use Of the equipMeNt oocccoccccncncccccoccnccncnnnnnnonnnonnnnnnnnnonnnonnnnonannnnnnonannnnnnnnnnns i ASTUCUONS TOUS Sia is ici a a General safety CONSIderatiONS cccooccccocnnccocnncnnnnonncnncnnnnonnnnnnnnnnnoncnonnnnnnnnnnnnnnnnnnnnnss iv LR so o A O 5 2 EC Lab software Sendai 7 2 1 Starting the Program iS Atado 7 2 2 Preparing and Running an Experiment with EC Lab software 9 221 EG MAN WIN do eee 9 22l E o DAR sa cersnt ees cs est lees ce es Sacre ead tao eras
189. re x x is the average To point 113 ai 111 43 PSD with DFT It is also possible to calculate the standard Ue Me se rs deviation from the Power Spectral Density PSD indeed talromts 111 according to the Parseval theorem it is possible to link variance Parameters o and Power Spectral Density of the x variable P f Select ls of P f df Ewe trend removal 0 Mones Note that P f X2 f where X f is the Fourier transform of x t trend removal None PSD with MEM The Maximum Entropy Method MEM is an Mad estimation of the PSD suggested by information theory Calculation of the PSD can be done with the following relationship whedon MEM order P f Atoy Results XX p Ewe average 2 448e 3 W 2 OPE AN average 0 473 5e b A k 1 O Ewe O03de 3 V Gl 0 402 be 6 4 An F065 Ohm Fig 181 Electrochemical Noise Analysis window 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 A description of the analysis windows that can
190. right click menu and on the settings window right click menu 92 3 1 1 EC Lab Software User s Manual EC Lab software Graphic Display The 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 now perform an electrochemical experiment and follow the plot on the current graphic window and fit or analyze curves resulting 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 or more graphs depending on the number of graphs When an experiment is run the graphic window is automatically opened with selection of the corresponding result file s Default graphic parameters have been chosen for example plot vs E for the CV technique The user can replace the default graphic parameters by his 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 plot versus time and one for the impedance spectroscopy plot versus frequency For synchronous multi channel protocol all the corresponding files are displayed in the same way as linked techniques The graphic window right clic
191. rrent 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 Click on Save to file to save the surface in the raw data file 68 EC Lab Software User s Manual The user can show or hide the graph legend He can Graph properties define the position the Sencar font name style and size the background color and 2 the transparency of this Custom Graph Style background The legend Traces 4 Legend includes the file name Axes Position Top v Note When several traces Units Font Name Arial v are plotted on a graph the fist Serd VPS Usor san ealoet The ace Options Background Iwe Ml trace by clicking on the corresponding legend A title can be added to the ve Title graph to describe the JE Tee S O experiment The text must Font Name Arial be be typed in the box The Font Style Bold ahs sl user can choose the title s Font Color MM Red OOOO format font font style size and color Sie To improve contrast and Back Color legibility for a presentation for example the user can change the color of the graph background Transparency J Fig 85 Graph window Graph properties Predefined Graph Style This window allows the T user to select the curren
192. ructure 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 practice 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 141 EC Lab Software User s Manual 3 5 1 Data 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 General Process data window Capacity and energy per cycle and sequence Summary per protocol and cycle Constant power protocol summary 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 3 5 1 1 Process window Select Analysi
193. s Batteries Process Data to load the processing window Process Data Input Files DAEC LabiDatarSamplez4PITT 2300604 1 mor Technique Potentodwnario Cycling with Galvanostatic Acceleration Processed File O EC Lab DataSamples PITT 2300604 1_ QsnE mpp Load Add Bemove Clear Variables To select from the input file To be added mode el mA osred 0 0 0 4m ha error Wie control changes cycle number Ns changes O charge m h counter irc G discharges m h time s 42 Energy h control Energy chargeswh E mey Energy dischangesw h E dor EE Fj Fi An FJA Process E Allow Reprocessing Cycles definition auto IP Esport s Text Compact Count half cycles DONE Display Close Fig 183 PCGA Process window 142 EC Lab Software User s Manual This window is separated in 3 parts in the first part Input File on the top of the window the user will add the raw data files to process Click on the Load button to load a raw data file in our example a PCGA file The second part Variables is dedicated to the variable selection generated the processed 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 l gt Q Qj or in the computer as processed variab
194. s available with the SP 200 and SP 300 Electrodes Connection Modify on disconnected cells only WE to ground ground 31 T WE WE 52 Fee ae Fig 46 WE to ground connection for SP200 300 This configuration is very useful for hydrogen permeation measurements where one working electrode is grounded and connected with two different couple of counter electrode and reference electrode 2 2 6 3 Experiment limits Most of protocols already have potential current or charge limits for example Galvanostatic Cycling with Potential Limitation GCPL limit Ewe to Ey and AQ to AQu that are used to make decision in general the next step during the experiment run The experiment limits are of another kind They have been designed to enter higher limits than the limits set into the protocols to protect cells against damages Once an experiment limit is reached the experiment is paused Then the user can correct the settings and continue the run with the Resume 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 for t gt 100 ms Then the limit will be reached if Ewe is greater than 5 V during 100 ms Once selected an experiment limit is active during the whole experiment run 32 EC Lab Software User s Manual Warning the experiment limits cannot be modified during the experiment run and must be set before 2 2 6 4 Miscellane
195. s with C the equivalent circuit will be R1 C1 2 For elements 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 elements 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 separate the different elements If the syntax is not correct an error message will be displayed 112 EC Lab Software User s Manual A circuit definition error syntax error A R1i 01MR2 C3 A3 is already included into the circuit list 6 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 7 For the selected file ZPOT Fe basique mpr find the correct circuit Randles Circuit R1 Q2 R2 W2 8 Click on Calculate to show the corresponding curve on the graphic window Ek Set Frequencies T from F 500 000 o f fran with i O points Equivalent circuit A1 02 A244 2 v Edit g parameter Ohm F s a1 Ohmi Ohrn s 142 hl ene Fig 148 ZSim Circuit Edition window 1 050 9 To adjust this curve to the experimental one the user must adjust values for each parameter as described in the window below and click on Calcul
196. 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 convenience Selecting all cycles for the fit and randomisation on only the first cycle will lead to an automatic fit When the Minimization is launched a new graph is added at the bottom right hand 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 118 EC Lab Software User s Manual BEEF moo a Selection Results lina Equivalent circuit TestBox3 3 SPEIS mpr TestBox3_3_SPEISS_zfitmpp cycle 11 Ril C2 R2 C3 A3 wa param sel 219n value 1 741 Ohm 0 375 4 0 461 Be 6 F 14 19e 9 101 8 Ohm 1 867 8 256 6 F 0 115e 6 2rd Ohm 1 588 2 000 Re Zp Ohm Calculate Cu Documents and Settings sebastien benorft Desktop TestBox3_3_SPEIS zfitparam mpp ROM va Ewer CAF vz lt Eywe Fit Sle sel Method Randomize Simplex v Stop randomize on h 0000 iterations weight 1 w t B i 13 32 Iterations 10000 Simples Cycle 21 R3 0 hm Fig 154 Successive fits on cycles with randomization on the first cycle We can see the potential evolution of the resistance R3 and the capacitance C2 The parameters of the equivalent circuit components are stored for each cycle in the Filename_Zfitparam mpp file N
197. se Fig 119 Fourier Transform window lt I gt vs time cv noise cycle6 filter mop cv noise_cycle6 mpr 1 04 1 02 MA ly TN ir hi ly E viel 20 98 Wise i A L f AA 0 96 Aia UNT TIPA Mitra 0 92 98 98 5 time s Fig 120 Filter result Red curve is the raw data file and blue curve is the filtered curve 92 3 4 1 9 Multiexponential Sim Fit It is possible to model data with multiexponential behavior up to order 6 with EC Lab software This tool is particularly interesting for conductivity measurements A simulation tool Multi Exponential Sim and a fitting tool Multi Exponential Fit are available in the Math menu Multi Exponential Sim This tool allows user to plot a curve from a multi exponential equation First of all order of the multiexponential equation is selected up to 6 Several units for x 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 window it is possible to add noise if the box Add noise is ticked Click on the Calculate button to obtain simulated curve Multi Exponential Fit As previously the user can select the order of the exponential up to 6 In the table a line is created for each parameter Clicking on Calculate the calculation without randomization or fit of the parameters will be done If the result is not acceptable it is possible to reac
198. se this data process click on process in the graphic window or choose Batteries Constant 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 CPWRAGONE mpr time s Pra Enerqu s h 0 Qoj m A Ewe initial l m initial Ewe final l final 1185 7890 8 0006 2 6122 760 15 4 063 9 16247 3 001 3 2 665 8 2602 6217 3 9986 3 425 7 1 007 2 3 646 1 296 6 3 001 8 1 332 3526 4155 200271 3 642 6 1 OF 3 2935 477 93 3 007 4 EE 06 4686 4659 1 000 7 3 454 4 11136 3 171 223 45 3 002 1 333 35 5565 7811 0 497 89 3 820 9 1 135 5 3 097 6 58 968 3 001 4 165 58 6457 3199 0 250 27 3 862 8 1 149 4 3 056 1 18 914 3 001 7 283 376 Yrl46683 0 124 41 3 893 7 1 155 6 3 036 7 17 24 3 002 2 41 44 DONE Process Copy Cloze Fig 189 CPW process window 148 EC Lab Software User s Manual 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 a graphic software in order to have a Ragone plot see figure below 10 Power W 0 i i L L i i i L i L L 2 2 5 3 3 5 4 Energy W h Fig 190 Ragone plot for a Li ion
199. se to Eco it is possible to simplify the Stern and Geary equation such as E Ln TR Bo Pe In 10 PP This equation is commonly presented with E as function of I o Re p LB B InlO When expressed this way it is easy to see that E E for O The slope of this equation is termed the polarization resistance because it has the unit of a resistance and is commonly abbreviated Rp PP Dor Ba P In10 Polarization resistance R DE 132 For the Rp Fit the user has to select the data points and the fit with the R fit button as described before Then click on Calculate The software will automatically find a potential value E on the curve for 0 Two circle markers are set in a 25mV potential range around E This range and fa and Be values used for the fit are defined in the Parameters frame The Rp Fit calculates the polarization resistance R and the open circuit potential Eco by a linear regression around E 25 mV on I vs E plot All the data points in the potential range are used for the linear regression Rp is given by the inverse of the linear fit slope and Ecorr by the potential value calculated from the linear equation for 0 The correlation coefficient shows the accuracy of the linear regression It is also possible to determine leor by adjusting the Tafel coefficients Ba and Be previously determined by the Tafel Fit The results can be copied to the clipboard to be pa
200. ser must use one of the following protocols OCV Chronoamperometry Chronopotentiometry Modular Potentio MP or Modular Galvano MG for a detailed description see the corresponding section in the techniques and applications manual Particularly modular potentio and modular galvano are very useful protocols for preconditioning before the experiment Thus the modular potentio mode allows the user to apply a defined potential for a given time potentiostatic mode and record other variables The modular galvano mode allows the user to apply a particular current for a given time galvanostatic mode and record other variables The potentio or galvano dynamic modes allow the user to apply a potential or a current ramp respectively 177 6 2 6 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 File 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 t
201. sted in the print window comment zone or in a text file They can also be saved in a text file Selection Trace le vs Ewe From Point 40 a 0 350 9 Y e 0 427 Te 3 m To Point E 0 298 4 Y Y 0 395 1e 3 m Total ports 22 Parameters 120 0 mv 120 0 m 25 0 m 63 155 8 Ohm 324 5052 m Correlation 0 998 3 corr 0 413 057 pA Fig 172 R Fit window DEK lt i gt vz Ewe LF iron corrosion bis impr Fig 173 Linear polarization curve of an iron electrode in H2SQ 0 1 M EC Lab Software User s Manual 133 EC Lab Software User s Manual Note The user can adjust the R Fit He must grab and move markers The fit result is automatically updated It is not necessary to click on Do fit again One could use the Linear fit to get the same results but the R fit is more convenient for the R calculation 3 4 6 3 Tafel Fit The Stern and Geary equation predicts that for E gt Ego the anodic reaction predominates and that for E lt Esor the cathodic reaction predominates EE I T 4 10 Pa for E gt Eso E E pr I z 1 10 forE lt Eon So in a log versus E representation one should see two linear parts for E gt Eco and E lt Ecorr for E gt Ecorr corr log z 2 log a for E lt Ecorr corr E E log x log 3 4 6 3 1 Tafel Fit window The Tafel Fit window allows the user to find the anodic and cathodic Taf
202. sults of the analysis are displayed in the Results frame Several values for the wave are displayed E42 and the limit anodic and cathodic currents 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 Fig 128 wave results tab I ma Ewe V Fig 129 Wave analysis on a curve resulting from a RDE experiment 99 EC Lab Software User s Manual E12 is the half wave potential obtained by the intersection of the curve with the median between both linear regressions ha is defined by the current value for E E on the top linear regression for the oxidation reaction 3 4 2 3 CV sim CV Sim is a tool designed for the simulation of cyclic voltammetry curves It is a useful tool to elucidate the mechanism of an electrochemical reaction To perform the simulation it is assumed that e Only one species Red or Ox is initially in the solution e The Initial current is equal to zero So the voltage sweep will start from the open circuit voltage First to perform the simulation the user has to define the number of electron transfer steps that are involved in the mechanisms 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 Example Select Example Select Mechanis
203. t Custom Graph Style polarity conventions to Traces Current polarity convention display data files Ayes 2 Positive oxidation standard IUPAC convention Oo The standard current Units O Positive reduction inverted convention convention from Graph IUPAC with a positive Monitor i ae value for the oxidation onitor format ae current Hote common para e 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 Fig 86 Options window 69 EC Lab Software User s Manual 3 2 6 The LOG History file The log file summarizes all parameters used for an experiment with the possible modifications on line Log displays the history of the experiment from its beginning cyclage 25 A 2 01 mpr LOG File cpclage 25 4 2 01 mpr w BF points 4 742 bytes Galvanostatic Cycling with Potential Limitation Run on channel 1 5M 2996 User CE vs WE compliance from 10 Y to 10 Y Electrode connection CE to ground Ewe ctrl range min 0 00 Y max 6 00 Y Acquisition started on O4 23 2009 08 40 30 Saved on File cyclage 5 4 2 D01l mpr Directory C Documents and Settings magqali maccarioa sDesktop mar Host 192 109 209 146 Device SP 150 56 0050 Address 192 109 209 222 EC Lah for windows v9 92 software Internet server vO 90 firmware Command interpretor v9 90 firmware Electrod
204. t Diagram lmle ve Rel Fig 138 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 imaginary negative part Im Z lt Q 3 4 3 1 4 Capacitor C Description Capacitor Li Impedance 21 Cent WNoguist Diagram lmle7 vs Rel Fig 139 Capacitor element description The capacitor impedance is also frequency dependent The Nyquist plot of such an element corresponds to a vertical straight line in the imaginary positive part Im Z gt 0 The faradic impedance decreases when the frequency increases 106 EC Lab Software User s Manual 3 4 3 1 5 Constant phase element Q Description Constant Phase Element CFE FE Impedance 1 ijan MNyquist Diagram lmle7 vs Ref Fig 140 Constant Phase Element description The CPE impedance is also frequency dependent The Nyquist plot of such an element corresponds to a straight line in the imaginary positive part Im Z gt 0 with a az 2 angle with the real axis The faradic impedance of the CPE decreases when the frequency increases 3 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
205. the points of the resulting curve File 1 File 2 The spacing can be defined in a linear or logarithmic spacing in spacing e aconstant time step Over omo Y 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 Fig 113 Linear interpolation window lt l gt vs Ewe z CV_1nA_10Vs_solution mpr cycle 2 z CV_1inA_10Vs background mpr cycle 2 z CV_inA_10Vs solution z_CV_1inA_10Vs background mpp lt I gt nA 0 0 2 0 4 Ewe V vs SCE Fig 114 Use of the Subtract Files tool on the blue and red curves Obtained curve is given in green 88 3 4 1 6 Integral EC Lab Software User s Manual Much like the Linear Fit method one can calculate the integral value of a selected trace between two makers On the graphic display select the Integral with the Integral button i in the analysis menu or the mouse right click and the data points where the fit will be performed The Integral analysis window is displayed Click on Calculate Two markers delimit the integrated trace The markers can be moved to adjust the fit selected zone The fit is updated automatically The integral is calculated according to X axis A pinkish area is displayed on the integrated zone The units of the integral fit result depend on the plotted data points For a cyclic voltammetry the units will be A V The results can be c
206. ting 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 R 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 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 background 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 Taf
207. tion The configuration for the EQCM coupling is described in the figure below External Devices RDE Configuration Channel Device Type Device Name 1 v acm iv E Analog OUT Manual Control TC fog l Analog IN 2 AR range TROhm Fig 225 SEIKO EG amp G QCM 922 configuration window 175 EC Lab Software User s Manual 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 173 2 000 4 000 6 000 Frequency Hz 8 O00 y SLL O0 3318 5159H 10 000 H 12000 H time s Fig 226 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 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 5 5 Preconditioning methods before an electrochemical experiment An electrochemical experiment generally contains several stages that can be combined in the following order 1 experiment installation 2 equilibrium state establishment or preconditioning and 3 electrochemical measurement The first and third stage can follow each other without the second one However the user often needs to do preconditioning stages before the electroch
208. try SW 4 Impedance Spectroscopy Pulsed Techniques Graph Representations Black Impedance oy T ame Black Impedance odd El we t Moott S chottky Advanced Advanced Bode Admittance r Hepresentations MNuquist Admittance Black Admittance i El Phase error Style Line style we eve E Ece vs t Techniquets association Ewe Ece ve t Selected techniques Bode Al Graphic style association l cy cycle ve time CA freg ve time Ewel we freq lve freq E wel I ve freg Remove Fig 94 Graph Style and technique selection 11 EC Lab Software User s Manual 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 Representations window will be displayed in this window select the Advanced tab and the four already predefined Graph Styles will be displayed Fig 95 To define your own Graph Style click on the button the window Graph Properties will be displayed as shown Fig 96 Graph Representations ve t 78 Ewe vs t Ewe vs l
209. ts galvanostat Electrochemical Noise Analysis this tool is dedicated to analysis corrosion data and to determine 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 charge 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 180 EC Lab Software User s Manual 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 Filter this filte
210. uced to 8 6 V instead of 10 V whatever is the chosen current range see figure below HA 15 10 8 6 5 0 5 0 610 15 Ese Fig 217 Current versus Potential available domain in the galvano mode 5 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 150 and 500 mA for SP 300 But 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 The average current for either measurement or control must not bypass 400 mA 800 mA for SP 150 and 500 mA for SP 300 This is especially used for GSM battery testing Please refer to the part 5 1 page 163 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 5 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 w
211. ulated in the instrument record external signals pH T P using auxiliary inputs 1 Analog In1 and 2 Analog In2 access the external device configuration window using the link in blue EC Lab Software User s Manual 2 2 5 2 Cell characteristic window in column format Cell Description Advanced Settings Electrode maternal Au Pd Cell Initial state _ Characteristics Electrolyte NaCl 0 2 Parameters C Settings aitsi ecc 1 0 Battery gt gt Electrode surface area 0 001 one dl Characteristic mass 0 001 go Equivalent eight 0 000 greq Density 0 000 gor Reference electrode SCE Saturated Calomel Electrode Offset potential vs Normal Hydrogen Electrode 0 241 Record Ece a Ewe E ce E J J PAN WE Analog IN 1 Analog IN 4 ref Record external devices on Analog INH CE Files Fig 36 Cell characteristic window in column format 2 2 5 3 Battery Cell Characteristics window Two other buttons are available in this window Battery and Files The battery cell characteristics are automatically displayed when a battery testing setting file is loaded The corresponding window is as follows 20 EC Lab Software User s Manual T dvance J Cell Description Record settings Electrode material iCal Ecen Cell Initial state Eme ces A lector Ana Parameterz ee Saa Analog IN 14 Settings Comments solid state synthesis Analog IM 24 i Record external de
212. urve 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 122 EC Lab Software User s Manual double layer capacitance 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 is a series combination of a resistor and a Capacitance the space charge capacitance The capacitance is calculated from the imaginary component of the impedance Im Z using the relationship sa eT This model is adequate if the frequency is high enough on the order of kHz 3 4 3 4 2 The Mott Schottky plot The Mott Schottky plot presents 1 C versus Eye or 1 C versus Eye for each frequency with C 1 calculated from the previous relationship Im Z 2 7 f E Frequencies 100 000 kHz 68 125 kHz 46 406 kHz v 31 622 kHz Wh 31 547 kHz en this plot is selected the window on the left is sac displayed to select the frequencies The user can select 6816 kHz several or all frequencies Click on Ok to display the
213. ve Ewe delta vs Estep Loglll vs Ewe Ewe ve Loglll L vs Ap vs t Bode Impedance Bode Impedance odd Nyguist Impedance Nyquist Impedance oc Black Impedance Black Impedance odd vs t Mott Schottky font Representation Advanced Graphic style association None Techniquel Line style Line Markers style select Y prop style Monochromatic style Fig 95 Graph Style selection EC Lab Software User s Manual Graph properties Predefined Graph Style Leste Mga Traces Traces Mame ges de 2 Units J 4 Graph F Options E Style Plat Undersampling Line Options Hide OLY Paints points Mote common parameters for all points graphic windows Draw only lines over Undersample traces over 1000C Graph style name Hame Style example Fig 96 Graph Properties window in the Graph Style creation 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 example is defined in such a way that the curve 1 is defined as red solid lines and fushia triangles marker and the curve 2 is defined as blue solid lines and blue sky diag cross marker Fig 97 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
214. vices on Analog INH Files Mags of active material 7000 000 mg ats 11 O00 WE Molecular weight of active material at x 0 90 930 g mol El E Atomic weight of intercalated ton 6 940 g mol d Acquisition started at xo 0 900 Number of e transfered per intercalated ions 1 ue for Ax AQ 1916 926 m h Electrode surface area 0 001 cot oF Characteristic mass 0 001 Reference electrode unspecified ha n Offset potential vs Normal Hydrogen Electrode 0 000 Y Fig 37 Cell characteristics window for a battery experiment This window offers the following possibilities to the user e add information about the electrochemical cell material initial state electrolyte and comments e This window has been designed for battery electrode materials acting as intercalation electrode which is the case of several primary and secondary batteries It allows you to enter the physical characteristics corresponding to the active material of the working electrode This makes on line monitoring of the redox processes possible in term of normalized units molar amounts of intercalation The mass m of active material in the cell has to be set with a given intercalation rate for example Xf 1 for LiCoO The molecular weight of the active material does not include the intercalated ion for which the atomic weight is set in a separate box For the example of LiCoOs above the molecular weight of CoO is 90 93 g mol an
215. w Traces Axes Units Graph Options Creation of a new graph style is possible with the button This new graph style will be recorded automatically 66 EC Lab Software User s Manual Graph properties e Predefined Graph Style i 2 Custom Graph Style Traces Manis avis E Units sa Iseae 32046138001 Scientific Notation ees C Invert Axis Options 2471 Proportional Shift axes Options Fig 82 Axes window All the Axes properties can be changed in this tab Select the axis you want to modify in the index tabs It is possible to change the title of the axis but also to adjust the axis range to the users convenience The user can also change the notation to scientific mode or invert the axis positive values on the left and negative 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 option part the user can choose to display his data with the X and Y axes proportional generally used for Nyquist representation and to differentiate from the rest of the grid the axis origin color style or line size The font 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 uy and move the axis 67 Graph
216. w h Cycling rate discharge O discharge mm h I control rnd Process Display Fig 187 Capacity and energy per cycle and sequence processing window The result of the calculation is a compacted processed file that contains several columns depending on the selected variables The values can be processed as densities using the electrode surface area or the characteristic mass 3 5 1 6 Summary per protocol and cycle This process allows the user to analyze CV CA CP GCPL GCPL2 GCPL3 and PCGA linked experiments in calculating Qanodic Qeathodic ANA Xmin ANd Xmax X being lanodic lcathodic for each cycle and linked experiment loop Select this tool in the General electrochemistry analysis Summary per protocol and cycle Experiments File List CAEC LabiDataSamplesv18650_G TT_030604_1 mpr Load Add CNEC Lab Data S amples CY Fe basigue 1 mpr loop feyele fespt Qan m h fUcatm h jlan m mn flantm mas Jlcafm mn lcatm mas Ean end Ecay end fl O GCPL1263 492 1270018 130 000 130 000 130 000 130 000 4 295 2 923 0 001 0 001 0 000 0 159 0 007 0 224 0 001 0 001 0 000 0 209 0 000 0 221 0 001 0 001 0 000 0 208 0 000 0 225 0 000 0 000 0 000 0 188 0 001 0 088 j Fig 188 Summary per protocol window 147 EC Lab Software User s Manual Then select the raw data files that correspond to two experiments with the Load Add Remove and Undo buttons In the example above 18650_GITT_030604
217. y chronoamperometry the cyclic voltammetry 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 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 179 EC Lab Software User s Manual 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 decreases a lot between the counter and the reference electrode CE to ground connection also called
218. y default Nevertheless it is not always possible to make a reduction after an oxidation so then chose the 3 points method 150 EC Lab Software User s Manual Note one can perform more than the 4 points and 3 points method with the Polarization Resistance technique but the process here accepts only these two lf 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 Chose the R unit Q cm or Q and click on Compute to calculate the next values ES b Ci e a R a and R Panodic Peathodic Panodic L A P cathodic La pE L Paveraged 2 L L E 3 points method Lon with r lt and r 4r 3r hi l 1 1 4 points method with e i being the potential and the average ii 4i i current without excluded points on the potential step AE e2 i2 on 2AE e3 i3 on AE or 3AE according to the selected method and es is 2AE Note if there are several loops n gt 0 then the i values are averaged on the different loops before the calculus 3 5 1 9 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 potentials Eoc and pitting potentials E of a set of electr
219. ysis of EC Lab is available with the new generated files 3 5 2 4 FC Lab data files importation 3 6 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 Reports A report file can be associated with each EC Lab data file to add all kinds of additional information The data file and the report file have the same name but with different extensions mpr for the data file and rep for the report file Note that the report file must be in the same directory as the corresponding data file in order to be recognized For instance Data file c vmp files XXxXX mpr Report file c vmp files XXxXX rep Reports are called from the Graphic Display window Right click with the mouse on the graphic window and select Report to call the report associated with the current data file If the report does not exist a message box appears to let the user create a new report EC Lab 19 00 2 Mo report associated with the File C EC LabiDatalSamplesiCy Fe basique_ 1 nm mpp Do ou want Eo create one Fig 198 Message window Here is an example of a report The user can define the project material and results 155 EC Lab Software User s Manual Report C EC LabWata Samples CV

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