Steady State I/E Recording

Fixed Sampling
Dynamic Scan

Zahner 01/2012

I/E

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I/E

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1. Recording Main Menu _______________________ 5

1.1 Edit Parameters _______________________________________________ 6
1.2 Control Potentiostat ____________________________________________ 6
1.3 Start Recording________________________________________________ 6
1.4 Display Diagram _______________________________________________ 6
1.5 File Operations ________________________________________________ 6
1.6 I/E - Analysis __________________________________________________ 6

2. Edit Parameters ____________________________ 7

2.1 Edge Potentials________________________________________________ 7
2.2 Scan Mode____________________________________________________ 8
2.2.1 Steady State Sampling ______________________________________ 8
2.2.2 Fixed Sampling ____________________________________________ 9
2.2.3 Dynamic Scan _____________________________________________ 9
2.3 General Parameters ___________________________________________ 10

3. Control Potentiostat _______________________ 11

4. Next Measurement ________________________ 12
5. Display Diagram __________________________ 13
5.1 Save Measurement ____________________________________________ 14
5.2 Create Data List ______________________________________________ 14
5.3 Export Drawing _______________________________________________ 15
5.4 Hardcopy ____________________________________________________ 15
5.5 Import Data List ______________________________________________ 15
5.6 Select Diagram _______________________________________________ 16
5.7 Enter Crosshair Mode _________________________________________ 16

6. File Operations ___________________________ 17

6.1 Open _______________________________________________________ 17
6.2 Save ________________________________________________________ 18

7. Steady State I/E Analysis ___________________ 19

8. Analysis Main Menu _______________________ 20

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9. File Operations ___________________________ 21

10. Select Measure Files ______________________ 21
11. Define Diagram Type______________________ 22
11.1 Selection of Diagram Type ____________________________________ 22
11.2 Setting of Display Limits ______________________________________ 23
11.3 Plot Diagram ________________________________________________ 23

12. Plot Diagram ____________________________ 24

12.1 Create Data List _____________________________________________ 24
12.2 Export Drawing ______________________________________________ 25
12.3 Hardcopy ___________________________________________________ 25
12.4 Select Diagram ______________________________________________ 25
12.5 Enter Crosshair Mode ________________________________________ 26

13. Tafels Slope ____________________________ 27

14. Butler-Volmer Analysis____________________ 29
15. Range Definition Mode ____________________ 31

I/E

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I/E Recording
I/E applies a defined potential curve to the sample and measures the current response. The results
are displayed as a I/E curve. With different scan modes and settings the following standard methods
can be easily done:

Chronoamperometry with Triangular Potential Sweep

Cyclic Triangular Wave Voltammetry
Linear Sweep Voltammetry
Stationary Electrode Voltammetry
Steady State Current/Voltage Curves
Tafel Scan

1. Recording Main Menu

I/E starts up with the graphical menu shown below. The installed submenus can be called up by
activation of the corresponding button.

The submenus can easily be recognized through their titles and symbols which are plotted within the
button. The main menu manages various submenus, which will be described briefly.

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1.1 Edit Parameters

setting of control parameters
edge potentials
scan rate
resolution
scan mode
tolerances
delay times
current limiting

1.2 Control Potentiostat

calls up submenu 'test sampling' of the impedance measurement
program EIS

1.3 Start Recording

starts next measurement

1.4 Display Diagram

displays last measurement

1.5 File Operations

disc i/o operations of I/E data (save and load measurement, select i/o device
and data path)

1.6 I/E - Analysis

calls I/E evaluation program

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2. Edit Parameters
The actual control parameters and the selected scan mode are indicated in the main menu within two
boxes.

2.1 Edge Potentials

Four edge potentials can be defined independent from each
other, wherever two successive potentials define a ramp. These
potentials can be changed by activating the corresponding
button and inputting the new value. The edge potentials can be
defined in two ways:
a) absolute potentials reference Eo=0V
b) relative potentials reference Eo=OC (open circuit potential)
The selected mode is indicated by a blue tick within the
checkbox. It can also be indicated during input by means of
appending the corresponding abbreviation (rel) or (abs) to the
actual value.
The relative mode function offers the possibility to investigate
different probes in a defined potential range relative to the open
circuit potential (ocp). The ocp is set to the actual value through
a change to the submenu 'test sampling' of the ZENNIUM
impedance measurement program. In addition, the potentiostat
has to be switched off. There is no ocp control during an I/E
recording.
Relative and absolute potential settings can be mixed for any
ramp. The setting of two successive edge potentials to the
same value reduces the number of ramps and the shape of the
control curve. It is possible to make a choice between bidirectional and mono-directional potential control.

I/E

E(1,2,3,4)=(0V,1V,-1V,1V)

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E(1,2,3,4)=(-1V,1V,1V,0V)
E2
E3

E2

E1

E4

E4

E3

E1

2.2 Scan Mode

The function 'scan mode' offers three operational modes. Different sets
of parameters define the control conditions. The following modes can
be selected:
steady state sampling
fixed sampling
dynamic scan

2.2.1 Steady State Sampling

The potential swings between the defined edge potentials. The potential
is changed in steps of E (resolution) in the scan direction
correspondingly. A step of potential usually perturbs the investigated
system and current oscillations may occur. In the 'steady state' mode
the induced current is continuously observed until certain steady state
conditions will hold. Current steady state is observed by four control
parameters:
absolute current tolerance
relative current tolerance

I n I n1
t
I I
I = n n1
t I n1
I =

minimum delay
maximum delay
The flowing current is measured after each step of the potential.
Current steady state is recognized if the current fluctuations will be at
least less than the absolute current tolerance or less than the relative
current tolerance. In case of steady state, however, potential variation
will pause for the minimum delay time relative to the last measurement.
Maximum delay time will have to be provided to bypass steady state
control if the system does not become stationary after a step of the
potential. The system will continue with the next step after the
maximum delay time has run out.
The following diagram describes steady state control graphically. The
current slope and the tolerances represent model functions. Each
diagram has been plotted in an arbitrary unit.

I/E
I rel

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minimum
delay time
not valid

I abs
valid

Irel = I n - I n-1
t

Iabs=

I n - I n-1
t . I n-1

I
Il

E
El + E
El
El - E
tl

tl
ts = t-tl
td

tl + ts

tl + td

I l : last current
El : last valid potential
E : resolution

: measuring time of last measurement

: time after steady state has been reached
: minimum delay time

2.2.2 Fixed Sampling

Fixed sampling' works without steady state control. The steps of the
potentials are printed out after the defined delay time has run out. Then
the next measurement will be carried out. 'Fixed sampling' results in
equidistant time resolution of the I/E data. The step width of the potential
is defined through resolution.
Eo 4Ed
Eo 3Ed
Eo 2Ed
Eo Ed
Eo
Eo Ed
Eo 2Ed
Eo 3Ed
Eo 4Ed

Ed = resolution

= measuring time

td = delay time
to 3 t d t o 2 t d t o t d

to

to td

to 2 td to 3 td to 4 td

2.2.3 Dynamic Scan

A dynamic scan works like a CV measurement but with a reduced slew
rate (10uV/s...10mV/s). The control parameters are slew rate and
resolution. The ramps are driven by the defined slew rate and the data
is registered in steps of the actual resolution of the potential. 'Dynamic
scan' does not work with the steady state control of the current.

I/E
Eo

2 Ed

- 10 Ed = resolution
= interval of integration

Eo Ed

E(t)=Es + slewrate*t

Eo
Eo Ed
Eo

= measuring time

ts = slewrate/resolution

2 Ed

to 2 ts

to ts

to

to ts

to 2 ts

2.3 General Parameters

Losses in potentials caused by, e.g., the electrolyte resistance or ohmic resistances
of the connecting lines can be compensated by positive feedback. A drop potential
is calculated by the actual cell current. This potential is added to the actual ramp
potential. Ohmic drop can be compensated up to a resistance of Rmax=1k.
'Resolution' defines the step width of the potential in the modes steady state and
fixed sampling. The dynamic mode resolution defines the step width of the
measured I/E data.
The anodic as well as the cathodic current range can be selected independently.
The exceeding of one of the limits would cause the actual ramp to be interrupted
and the corresponding end potential to be corrected. Finally, the next ramp will be
started with respect to the corrected edge potentials.
2

2
0

-2
2

2
0

4
2

2
2

-2

4
2

2
23

-2

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3. Control Potentiostat

This option starts the test-sampling menu of the EIS impedance measurement program. In this menu
different potentials may be applied to obtain information about the induced current. In addition, the
potentiostat can be set to the I/E starting potential. This offers the possibility to start the I/E scan
faster, otherwise the potentiostat automatically changes from the actual potential to the starting
potential by a ramp of dE/dt=4*slew rate.
Now the final condition of the potentiostat can be selected. If a I/E measurement is started with the
potentiostat switched on, the potentiostat will remain operational after the I/E measurement has been
finished. If the potentiostat has been switched off before starting a I/E measurement it will be switched
off at the end of the measurement.

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4. Next Measurement

This function starts the next measurement. The measured E-I data is plotted online within a data
window. On the upper right of the recording window three 'digital' instruments indicate the numeric
values of the actual ones measured. A running measurement can be terminated with use of
<ESCAPE>.

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5. Display Diagram

The 'display diagram' function recalls the last spectrum measured. This spectrum is then displayed on
the screen. Data can be exported to other programs by means of the standard i/o routines.

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5.1 Save Measurement

Save the
recorded data + the measurement parameters + the comments to the hard disk and return to the I/E page.
Save the
recorded data + the measurement parameters + the comments to hard disk and pass them directly to the SIM
software for analysis. You will end up in the SIM page.
When clicking on either of the buttons a description box
opens where you may input your measurement parameters
and comments. Some lines will be filled automatically by the
software (e.g. potential, current and measuring time) others
are free for the user to fill. User parameters are not used by
the software for any calculation. They are for the users
information only.
Accept the inputs by clicking on the
button in the upper
right corner or reject the inputs by clicking on the
button.
Click on the
button to call the calculator.
In the following browser navigate to the desired path,
input a file name and
click on the
button to save the data or
click on the
button to cancel the saving.

5.2 Create Data List

Creates an ASCII list of the data:
and copies it to the Windows clipboard
or saves it as plain text-file
or copies it to ZEdit

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5.3 Export Drawing

Passes the actual graph as high quality vector

graphic to the Windows clipboard
saves graph as an EMF graphic file

Transfer the graph to the CAD graphic editor

section of Thales.
Edit the graph manually in the CAD section of
Thales for later clipboard or EMF export.

5.4 Hardcopy
Create a bitmap copy of the screen for export or printing:
Perform the selected output operation
Do a form feed
Select the output properties:
landscape = big format (DIN-A4) to printer
upright = small format (DIN-A5) to printer
to clipboard = sends screen to the Windows clipboard
save as file = saves the screen as a bitmap file

5.5 Import Data List

- inactive within I/E -

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5.6 Select Diagram

Show current data (y-axis) versus potential (x-axis)
Show potential (y-axis) versus current data (x-axis)
Compensate ohmic share from actual diagram

5.7 Enter Crosshair Mode

Move cursors through the curves with the

mouse. The course leads through the history
of the data source: moving from left to right
means moving from the first samples
recorded to later.
Use the cursor-left/right keys for fine steps.
You leave the crosshair mode by clicking the
middle mouse key.
If more than one data set is displayed, use
the cursor-up/down keys to change from one
curve to the next.

Click the right mouse button to open the option box:

Increase
stepwidth

cursor

key

Decrease
stepwidth

cursor

key

Set cursor to next / previous curve

Passes the data of the selected
measurement point to ZEdit
Not implemented, for future expansion

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6. File Operations

The 'display diagram' function will recall the last record. The measured data will be displayed on the
screen.

6.1 Open
This function allows you to load/save I/E data from/to the hard disk of
your PC. Click on the icon and decide in the submenu, whether you
want to open previously stored I/E data or save actual I/E data.

If there are no data in memory, this sub-menu is skipped.

After your decide to Open, a file browser will open displaying only I/E
data files (file extension .iss).

Select a path and a file and click on the LOAD button to load the file to
the Thales software. Click on the Display Spectrum icon on the IE
main page to display the data in a graphical form.

The next box shows the measurement parameters of the loaded data.
Click on it if you want to close it.
NOTE: Opening a file will switch off the potentiostat and configures
the potentiostat according to the loaded measurement-settings
automatically. Loading a measurement file is an easy way to
perform a new measurement with previously used settings.

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6.2 Save

If there are data in memory, usually after an IE data measurement, you

may want for Save them on hard disk for storage.

A description box opens where you may input your measurement

parameters and comments. Some lines will be filled automatically by the
software (e.g. potential, current and measuring time) others are free for
the user to fill and are not used for any calculation. The last three lines
are reserved for series recording information. In a series EIS run they
will be filled automatically. You may use these lines to define spectra for
series analysis even if they were created as single measurements.
Accept the inputs by clicking on the
button in the upper right corner
or reject the inputs by clicking on the
button. Click on the
button to
call the calculator.
In the following browser navigate to the desired path,
Input a file name and
Click on the
button to save the data.
Click on the
button to cancel the saving.

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7. Steady State I/E Analysis

This button calls up the I/E analysis software. The actual data will not be present there at the moment.
In order to be on the safe side a measurement has to be saved in the recording program which is to
be loaded first. Besides, it is evaluated by the analysis program.

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I/E Analysis
8. Analysis Main Menu
I/E analysis begins with the menu shown below. The offered functions and submenus are represented
by graphic primitives.

I/E

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9. File Operations
There are commonly known disc i/o functions to load measure data (see
I/E recording chapter 6) but with one restriction: The save option has
been blocked. The reason is that it is possible to use the I/E analysis to
manipulate the original data. If this data is saved, the original one will be
overwritten.

A file browser will open displaying only IE data files (file extension .iss).
You can also select more than one data file to open.

10. Select Measure Files

'select measure files' offers the possibility to select different sets of
measurement for evaluation. When this function is activated a file list
including all files which have already been loaded will be opened.

A blue background color indicate whether a file has been selected. To

select or deselect a data file simply click on the file name.

NOTE: Up to ten measurements can be loaded at the same time depending on the memory
space available. If a loading operation fails because of an overflow message, the analysis
program will have to be initialised with the 'INIT' function of the SIM program.

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11. Define Diagram Type

I/E measurements store data triplets of the format (E,I,t). The data can
be plotted in different graphical representations. During I/E recording
data is automatically plotted in the logI(E) mode. 'Define diagram' offers
selection of different display modes with linear and logarithmic scaling,
either manually or automatically.
An activated 'define diagram type' function offers the menu shown
below.

This submenu offers all definitions to create a plot of the data measured. The diagram can be affected
- by typing, logI vs E, I vs E, E vs I or E vs logI or
- by data ranges and display limits
The settings which are organized in a graphical control panel can be carried out by chosing the
corresponding option and by entering some parameters.

11.1 Selection of Diagram Type

The diagram type is selected by activating the corresponding button.

The activated mode is indicated by a green bar within this button and
the symbolized terminal will change its graphic.

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11.2 Setting of Display Limits

The display limits can be set in accordance with the selected diagram type. Each magnitude can be
scaled automatically (auto) or manually (user). In order to redefine the display limits one of the buttons
has to be selected

and the new values have to be input with help of the i/o box.

The values in brackets indicate the extreme values of the corresponding data track.

11.3 Plot Diagram

Redrawing the graphic without changing menus is effected by moving
the cursor to the symbolized terminal. The actual graphic is then
overlaid by the 'plot' button. The next diagram will be plotted after
confirmation with <ENTER> or mouse click.

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12. Plot Diagram

The diagram can be plotted after all settings have been made. Output is initiated by activating the
button 'plot diagram'. When the plotting procedure has been finished, five additional buttons will
appear on the right side of the screen and offer the options.

12.1 Create Data List

Creates an ASCII list of the data:
and copies it to the Windows clipboard
or saves it as plain text-file
or copies it to ZEdit

I/E

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12.2 Export Drawing

Passes the actual graph as high quality vector

graphic to the Windows clipboard
saves graph as an EMF graphic file

Transfer the graph to the CAD graphic editor

section of Thales.
Edit the graph manually in the CAD section of
Thales for later clipboard or EMF export.

12.3 Hardcopy
Create a bitmap copy of the screen for export or printing:
Perform the selected output operation
Do a form feed
Select the output properties:
landscape = big format (DIN-A4) to printer
upright = small format (DIN-A5) to printer
to clipboard = sends screen to the Windows clipboard
save as file = saves the screen as a bitmap file

12.4 Select Diagram

I/E measurements store data triplets of the format (E,I,t). This data can be
plotted in different graphical representations. During the recording, the data can
be plotted in the I(E) mode automatically. The 'select diagram' function allows to
select between the modes. Scaling can be done manually or automatically (see
I/E analysis chapter 11).

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12.5 Enter Crosshair Mode

Move cursors through the curves with the

mouse. The course leads through the history
of the data source: moving from left to right
means moving from the first samples
recorded to later.
Use the cursor-left/right keys for fine steps.
You leave the crosshair mode by clicking the
middle mouse key.
If more than one data set is displayed, use
the cursor-up/down keys to change from one
curve to the next.

Click the right mouse button to open the option box:

Set cursor to next / previous curve
Increase
stepwidth

cursor

Decrease
stepwidth

cursor

key
key

Passes the data of the selected

measurement point to ZEdit
Not implemented, for future expansion

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13. Tafels Slope

The Tafel plot (logI vs E) is a useful tool to determine kinetic parameters through I/E measurements. In
general, there is an anodic and a cathodic branch:

log I anod

(1 ) nF
2.3RT

log I cath

nF

The linear segments can be extrapolated to = E-E0 = 0 and will intercept at logI0. When being close
to = 0, the plots will deviate from the linear behaviour because of influences of the back reactions. At
high values of diffusion processes and ohmic behaviour may well dominate the current slope.
The Tafel evaluation defines the 'linear' segments. Two-line segments are calculated by linear
regression. Eventually, the point of interception is calculated.
After Tafels's slope has been called up, four markers have to be set. The program automatically
prompts the following when the Tafel's slope is entered for the first time.

Define the anodic and the cathodic branch, each of them is limited by two markers. Move the markers
by using the mouse or the cursor keys. There is no strict order of input as the markers are sorted by
the program in accordance with rising potential. The range markers can be changed for further
calculations within different range(s) after the evaluation. The range(s) can be changed during any
graphical output on the screen with the crosshair.

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A marker is changed by moving it to its last position and by activating the motion with <ENTER>. Now
the marker has to be moved to the new position and this position is fixed by pressing <ENTER> one
more time. The step width can be changed by the <HELP> function which calls up the mouse help
routine. The linear segments can be defined monofold or multifold, see section I/E analysis chapter
15.
Finally, the lines of regression and the point of intersection is plotted. The corresponding parameters
are printed in the data window to the right of the window of the graphic.

The regression is calculated by the familiar chi-square test

N

2 = [ yi (a + bxi )]2 = min

i =1

and results in
N

b=

(x
i =1

x )( yi y )

( xi x )

a = y bx

(x =

1
N

xi ;
i =1

y=

1
N

y)
i =1

i =1

The coefficient of correlation is

N

rxy =

( x x )( y y )
i =1

( xi x ) 2
i =1

(y
i =1

y)2

The slopes are denoted in units of mV/dec. Current and potential indicate the point of intersection.

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14. Butler-Volmer Analysis

I/E data is fitted by the Butler-Volmer equation

I ( ) = I 0 (e zf e (1 ) zf )
Free parameters are:

E0
I0

= E E0

reduced potential

f =

F
RT

zero count potential

current at zcp
coefficient of symmetry
effective charge number

The fitting procedure is a least squares algorithm and minimizes the chi-square sum
N

2 = ( I meas I theo ) 2
i =1

The Butler-Volmer fit allows to enter starting values of the running parameters. Default values are
calculated by means of the I/E scan.

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Eventually, the fit is displayed and the standard i/o routines offer output as a hardcopy, as a data list or
a CAD file.

Fitting can be effected in the monofold or multifold mode. The fitting limits can be changed and
another fit can be started by the crosshair routine.

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15. Range Definition Mode

When an I/E curve is measured with edge potentials E relative to the ocp, as shown below, the
results of the descending branch will differ from those of the ascending branch.

E/V

Relativpotentiale
E(1,2,3,4)= (-1V,1V,-1V,-1V)

a2

b1

a1

b2

a1

ocp
-1

logI/A

E2

E1

a2
b2 b1

E3
E4

Potential E/V
I/E analysis presents two modes of 'range definition', either the monofold or the multifold one. In the
multifold mode all measure points within the limits are selected for evaluation, whereas the monofold
mode offers the possibility to select only one branch for calculations.

Fitting can be done in the monofold as well as in the multifold mode. The fitting limits can be changed
and another fit can be started by the crosshair routines.