Application Note A4.

Electrochemical impedance spectroscopy

Setting up a measurement
The EIS measurement is setup in IviumSoft
software. Depending on the requirements of the
measurement four different impedance methods
can be selected from the Method window as shown
in Figure 1.

Figure 1: Available impedance methods.

Figure 2: Constant E method parameters in Basic
mode.
The differences between these methods are:
• Constant E: this technique applies an AC
In the popup window the number of frequencies
voltage perturbation and measures the AC
that will be applied is automatically calculated from
current response
the input. The number of frequencies to be applied
• Constant I: similar to Constant E, but with an
per decade can be entered on the top right. After
AC current perturbation instead of a voltage
selecting Apply, a logarithmic spread of the
perturbation
frequencies will be automatically calculated and
• PotentialScan: potentiostatic frequency scans
listed in the table below. More frequencies mean
for a range of potentials
more data points, but also a longer measurement
• CurrentScan: galvanostatic frequency scans
time, especially at low frequencies.
for a range of currents

The first two methods are performed at a fixed

potential or current, whereas the last two methods
are particularly convenient to quickly get
information about the impedance of a system at a
different voltage or current. Once a specific
potential or current is of interest is identified a
more detailed measurement can be performed.

Constant E
Basic mode
By selecting Constant E the method parameters are
shown (see Figure 2). Note that these are the
method parameters available in Basic mode. If
desired a title of measurement can be given. E start
is the constant potential that is applied throughout
the EIS measurement. The frequency scan be
defined by clicking on the box, which opens up the
Edit frequencies popup window as shown in Figure
3.

Figure 3: Edit frequencies window.

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The start and end frequency can be entered in the
corresponding cells. Also, the amplitude of the
potential perturbation can be entered. Manual
override can be checked, which allows to manually
change the individual frequencies and amplitudes in
the table below. The latter can be used to create a
completely flexible frequency scan. Closing the
popup window will apply the frequency settings
during the EIS measurement.
Besides single sine the Edit frequencies window
offers more advanced sine wave perturbations.
These can be selected by the tabs at the top of the
window. Multi sine applies multiple sine wave
frequencies simultaneously and the corresponding
impedances are collected in a single measurement.
This is especially useful for measurements at lower
frequencies as this can decrease the measurement
time considerably and minimize artefacts caused by
time-variable impedances. With dual sine a sum of
2 frequencies is applied: 2x and 5x the base
frequency. Applying such a signal on a non-linear
cell will result in a mix of well-defined modulation
products.
The next method parameter in Figure 2 is selecting
a fixed current range. A dropdown selection is
available by checking the AutoCR box, which
overrides the fixed current range, i.e. the
instrument will automatically select the most
appropriate current range for the measured signal. Figure 4: Constant E method parameters in
It is highly recommended to select AutoCR as the Advanced mode.
potential perturbation during the EIS measurement
crosses zero, therefore the current will often The additional parameters are the Equilibration
change over multiple orders of magnitude. time, which is the time that the E start potential is
Selecting the checkbox of Pre ranging enables the applied prior to the EIS measurement. Noise can be
automatic current ranging to start before the convenient in cases that suffer from excessive
measurement so that the instrument will noise. However, it should be used with caution. It
automatically look for the best current range has three functions:
setting to start the measurement. • when activated, it will apply a stronger
The DualCR option may be checked for automatic filtering with the potentiostats
potentiostatic frequency scans that use AutoCR. It built in analog filters of the potentiostat.
will override the automatic current range selection • The acquisition period is the total period
and set the current range depending on a user that the sampled signal is measured
specified frequency: (averaged). A longer period will give better
• at frequencies > SwitchFreq, the AutoCR.Max noise reduction, but also a longer
range is selected. measurement time. The acquisition period
• at frequencies < SwitchFreq, the AutoCR.Min can be entered manually.
range is selected. • When drift correction is activated the
Note that this option is only active if the AutoCR results will be corrected for any DC drift
option is checked. during the EIS measurement.
When setting up a new method file the Filter and
Advanced mode Stability options are set to automatic. In this mode,
In Advanced mode more method parameters can be the system determines the most appropriate setting
set. A screenshot of the method window is depicted from the applied frequency. Overriding the
in Figure 4. automatic setting should be done with care,
because it may result in signal deformation. If
required it is possible to select the filter to 1 MHz,
100 kHz, 10 kHz, 1 kHz or 10 Hz.

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The stability setting determines the bandwidth of required to change them. If necessary, the default
the applied signals on the sample: automatic, settings can be reset by selecting the Set default at
highspeed, standard or high stability. The the bottom of the FRA settings window.
bandwidth determines the speed of the control loop
of the potentiostat. At higher speed, corrections are
applied faster, but the risk of the system becoming
instable increases. At lower speed the control loop
is slower, and this results in a more stable, but less
quickly responsive, system. In automatic mode, the
system determines the most appropriate setting Figure 5: FRA settings options.
from the applied frequency. Overriding the
automatic setting should be done with care,
because it may result in signal deformation and
instability.
With Connect to it is possible to select how the
electrochemical cell is connected. Cell-4EL and
Cell-2EL are used for 4 and 2 electrode
connections, respectively. Additionally, it is possible
to select one of the internal dummy cells, which
may be useful to test the method on a known
circuit prior to the actual measurement.
Apply wrt OCP can be a convenient way to define
the E start or E standby potential versus the open
cell potential (OCP).

Constant I
The method parameters of the Constant I
impedance technique are almost similar to the
Constant E technique. The main difference is that a
fixed current range needs to be selected (no
AutoCR).

PotentialScan
The implementation is analogue to the Constant E
variant, but it is repeated at a range of DC
potentials. The start and end potential can be
specified as well as the potential step. The results
can be stored as single files .idf, or all together as
dataset .ids.

CurrentScan
Galvanostatic impedance scans can be performed in
combination with a DC current scan, in much the
same way as the PotentialScan method. Select the
CurrentScan method, and set the DC scan
parameters: Istart, Istep and Iend. The frequency
scan will now be repeated at every dc-step value of
the ramp. The results can be stored as single files
.idf, or all together as dataset .ids.

FRA settings
The FRA settings are available by selecting
Options→Options from the top ribbon. In the popup
window select the corresponding tab. The settings
of the stabilization, Results optimization and the
acquisition period of the FRA measurement can be
adjusted manually, see Figure 5. The default values
are sufficient for most measurements; it will not be

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