Application note #9

Linear vs. non linear systems in impedance measurements

I- Introduction
Electrochemical Impedance Spectroscopy II- Test Box-3
(EIS) is an interesting tool devoted to the The experiments described on this paper were
study of linear systems. However, performed with a test box specifically designed
electrochemical systems are often non-linear. for the user to learn how to achieve impedance
Before explaining the different ways to deal measurements on linear and non-linear
with this issue, we will point out the main electrochemical systems.
differences between linear and non-linear
systems. These differences of behavior are
shown in Table 1. The impedance
measurement was performed using the
potentiostatic mode. The potential is defined
by:

E(t)  E WE  Va sin(2ft)

where EWE is the stationary potential for the

impedance measurement, Va is the potential
amplitude of the sine signal, f is the There are three different electrical circuits
frequency, and t is the time. inside the test box simulating real
electrochemical systems. With Test Box-3, it is
Table 1: Differences between linear and non-
possible to study general electrochemistry
linear systems. protocols like Cyclic Voltammetry or corrosion
protocols such as Linear Polarization and
Non-linear Generalized Corrosion.
Linear system
system
Steady-state Straight line III- Test circuit #1
I = f(EWE)
I vs. EWE curve I = f(EWE)
Fig. 1 shows the electrical circuit of the test
Impedance Invariant with Variant with circuit #1, the corresponding steady-state
vs. EWE EWE EWE: Z(EWE)
curve (I vs. EWE), and the Nyquist diagram of
Impedance Invariant with Invariant with the impedance measured at points a and b of
Va for all Va Va only for the steady-state curve. The impedance
vs. Va values low Va values
diagrams do not depend on the steady-state
potential EWE or on the amplitude Va. The
Three test circuits have been designed in Nyquist impedance diagram displays two semi-
order to highlight the differences in behavior circles. Only one impedance measurement is
between linear and non-linear systems. needed to characterize the equivalent test
circuit #1.
It can be a good exercise to determine the
different frequencies characterizing circuit test
#1 and compare them with the experimental

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values shown on the impedance diagram of
Fig. 1. -Im (Z) vs. Re(Z)
PEIS_circuit1.mpr # PEIS_circuit1_zfit.mpp

1.5

-Im(Z)/kOhm
1

0.5

0
CV_circuit1.m pr
<I> vs. Ew e
-0.5
2 4
0.1 Re(Z)/kOhm
b
0.08

0.06 Fig. 2: ZFit result on circuit #1 of Test Box-3.

<I>/mA

0.04
To verify these results with test circuit #1, you
0.02 can perform the following experiments:
a
0  1) Plot the steady-state I vs. EWE curve
-0.02 using cyclic voltammetry technique (in
0 0.2 0.4 EC-Lab® software, load the CV_circuit1.mps
Ewe/V vs. SCE
file, accept, and run the experiment).
-Im (Z) vs. Re(Z)  2) Select the PEIS technique. Apply a
PEIS_circuit1.mpr # PEIS_0-4V_circuit1.mpr
constant potential EWE = 0 V and perform an
23.4 Hz
impedance measurement from fi = 200 kHz to
2
ff = 1 Hz frequency with a low amplitude
1.5 Va = 10 mV (it is also possible to load the
-Im(Z)/kOhm

PEIS_circuit1.mps file).
1
12.7 kHz
 3) In the PEIS technique, apply a constant
0.5
potential EWE = 0.4 V and perform an
0 impedance measurement from fi = 200 kHz to
ff = 1 Hz frequency with a low amplitude
-0.5
2 4 Va = 10 mV (it is also possible to load the
Re(Z)/kOhm PEIS_0-4V_circuit1.mps file).

Fig. 1: Test circuit #1, I vs. EWE steady-state  In the PEIS technique, apply a constant
curve and Nyquist diagram for the impedance. potential EWE = 0.4 V and perform an
Impedance is measured at steady-state points impedance measurement from fi = 200 kHz to
a and b. The arrow indicates increasing ff = 1 Hz frequency with a high amplitude
frequencies. R0 = 501 , R1 = 1 k, Va = 100 mV (it is also possible to load the
R2 = 3.56 k, C1 = 10 nF, C2 = 2.3 µF.
PEIS_ampl100mV_circuit1.mps file).
Values of the various parameters of circuit #1  Overlay the three impedance measurement
are obtained using ZFit, available in EC-Lab® curves in the Nyquist plot mode.
and EC-Lab Express software. Result of the
fit is given Fig. 2. As test circuit #1 is a linear system, the three
impedance diagrams should be identical.

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IV- Test circuit #2 Fig. 4 shows the impedance change versus the
amplitude Va for a given Ewe value. We can
Test circuit #2 is made mainly of two semi-
clearly see that the semi-circle diameter
conductor diodes. This is a model for
decreases when Va values increase. The
exponential non-linearity. Test circuit #2
impedance does not depend on the amplitude
results from a circuit studied in [1].
of the excitation signal for low values of
The I vs. EWE steady-state curve is not a amplitude (Fig. 4). In that case, this system’s
straight line for test circuit #2. Therefore the behavior is similar to that of a linear system.
test circuit #2 is a non-linear circuit. The
Therefore, one impedance measurement is not
impedance of this circuit depends on the
sufficient to characterize a non-linear system.
steady-state value of the working electrode
potential EWE and on the amplitude Va. It can be a good exercise to try and find an
equivalent electrical circuit for test circuit #2.
The Nyquist diagram of the impedance
The user can also determine the electrical
measurement performed on test circuit #2 is
components’ values when its behavior can be
a semi-circle whose diameter changes along
compared to one of a linear system.
with the electrode potential EWE. (Fig. 3). The
impedance of a non-linear system is potential PEIS_0-15V_xxm V_circuit2.m pr
-Im(Z) vs. Re(Z)
dependant.
1.5
112.6 Hz
CV_circuit2.m pr
<I> vs. Ew e

1
-Im(Z)/kOhm

2
112.6 Hz

1.5 0.5
<I>/mA

112.6 Hz
1
0
b
0.5 0 1 2
Re(Z)/kOhm
m m .m pr
a RLF (kOhms) vs. log
0
0 0.1 0.2 0.3
Ewe/V vs. SCE 2.5
RLF (kOhms)

-Im (Z) vs. Re(Z) 2

PEIS_0-25V_circuit2.mpr # PEIS_0-2V_circuit2.mpr

1.5
200
806.3 Hz

150 1
-Im(Z)/Ohm

100 0.5 1 1.5 2

log(Va/mV)
50 5.780 kHz
Fig. 4: Nyquist impedance diagram measured
0 for different values of potential (EWE = 0.15 V)
and diagram displaying the in-phase impedance
0 200 400
(evaluated for a limiting value in low
Re(Z)/Ohm
frequencies) versus log(Va).
Fig. 3: Test circuit # 2, I vs. EWE steady-state
curve and Nyquist diagram for the impedance
which has been measured at points a and b. It is possible to verify these results with test
Arrows indicate increasing frequencies. circuit #2:

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 Plot the steady-state I vs. EWE curve using CV_circuit3.m pr

cyclic voltammetry technique (in EC-Lab®

<I> vs. Ew e

software, load the CV_circuit2.mps file, 1.5

b
accept, and run the experiment).
 Select PEIS technique. Apply a constant 1

<I>/mA
a
potential EWE = 0.2 V and perform an
impedance measurement from frequency
0.5
fi = 200 kHz to ff = 1 Hz with an amplitude
Va = 1 mV (it is also possible to load the
PEIS_0-2V_circuit2.mps file). 0
0 1 2
 In the PEIS technique, apply a constant Ewe/V vs. SCE
potential EWE = 0.25 V and perform an
impedance measurement from frequency PEIS_1-3V_circuit3.m pr
-Im(Z) vs. Re(Z)
fi = 200 kHz to ff = 1 Hz with an amplitude
Va = 1 mV (it is also possible to load the 0.12
166.5 Hz
PEIS_0-25V_circuit2.mps file). 0.1
-Im(Z)/kOhm
 In the PEIS technique, apply a constant 0.08
3.9 kHz
potential EWE = 0.15 V and perform several 0.06
impedance measurements from frequency
0.04
fi = 200 kHz to ff = 1 Hz with an amplitude
0.02
Va/mV= 2.5, 5, 10, 25, 50, 100 (it is also
possible to load the 0
-0.1 0
PEIS_0-15V_xxmV_circuit2.mps files for the
Re(Z)/kOhm
different values of Vpp).
PEIS_0-8V_circuit3.m pr
-Im(Z) vs. Re(Z)

V- Test circuit #3
166.5 Hz
Test circuit #3 mainly consists of two
0.1
transistors. It is a model for metal passivation
-Im(Z)/kOhm

3.9 kHz
which has been extracted from [2]. This
circuit has also been studied in [1, 3, 4]. 0.05

The shape of the impedance diagram evolves

0
along with the electrode potential EWE as it
can be observed in Fig. 5. Let us consider the
steady-state I vs. EWE curve showing a peak 0 0.1 0.2 0.3
Re(Z)/kOhm
(as in the case of metal passivation). For low
frequencies, the in-phase impedance is Fig. 5: Test circuit # 3 (Z3), I vs. EWE steady-state
negative. Therefore, a part of the impedance curve and Nyquist diagram for the impedance
diagram is on the left side of the complex which has been measured at points a and b. The
plot, i.e. Re(Z(w)) < 0. arrow indicates increasing frequencies.

It is possible to verify these results with test

circuit #3 by performing the following
experiments:
 Plot the steady-state I vs. EWE curve using
cyclic voltammetry technique (in EC-Lab®
software, load the CV_circuit3.mps file, accept,
and run the experiment).

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Web: www.bio-logic.info
 To plot diagram a on Fig. 5: select the Exercise answers:
PEIS technique and apply a constant
potential EWE = 0.8 V and perform an - circuit test #1: the characteristic frequency,
impedance measurement from frequency i.e. the frequency at the top of the semi-circle
fi = 200 kHz to ff = 1 Hz with an amplitude of an RC circuit, is given by
Va = 10 mV (it is also possible to load the
PEIS_0-8V_circuit3.mps file). 1
fc 
 To plot the b diagram: in the PEIS 2RC
technique apply a constant potential The two characteristic frequencies for circuit
EWE = 1.3 V and perform an impedance test #1 are:
measurement from frequency fi = 200 kHz to 1
ff = 1 Hz with an amplitude Va = 10 mV (it is f c1   16 kHz
2  10 3  10 8
also possible to load the
1
PEIS_1-3V_circuit3.mps file). f c2   20 Hz
2  3.57  10 3  2.2  10  6
These values are close to the frequency values
VI- Conclusion given at the top of the semi-circles present on
Linear systems are simpler to study. Only one Fig. 1.
impedance measurement is sufficient to - Circuit test #2: the impedance diagram
characterize their behavior. represents a semi-circle. The equivalent
On the other hand, it becomes quite electrical circuit can be assimilated to an RC
complicated when dealing with non-linear circuit. It is possible to determine the circuit
systems. Several impedance measurements resistance values on the Im(Z) vs. Re(Z) plot.
are necessary to characterize their behavior. They correspond to the in-phase impedance
In order to study a non-linear system with for the lowest frequencies (-Im(Z) ≈ 0). R value
impedance measurement by assimilating its varies with Ewe.
behavior with a linear system behavior, it is For point a of the steady-state curve, we find:
necessary to use a low modulation amplitude, Ra = 420 Ω
Va.
and for point b: Rb = 70 Ω.

References:
With the resistance values determined above,
the user can determine the capacitance using
[1] Diard, J.-P., Le Gorrec, B., and Montella, C. the following equation:
Deviation from the polarization resistance due to
non-linearity. I Theoretical formulation.
J. Electroanal. Chem. 432 (1997), 27-39. 1
C
[2] Mahadevan, K., and Gopala, Y., Electronic 2π f c R
Engineering, (1973), 20.
where fc is the frequency at the top of the semi-
[3] Diard, J.-P., and Le Gorrec, B, Use of a new circle. The results should be similar for Ra and
generator with negative impedance for studying Rb. We find C~490 nF.
the anodic behavior of zinc in an alkaline medium
J. Electroanal. Chem. 103 (1979), 363-374.
[4] Diard, J.-P., Landaud, P., Le Gorrec, B., and
Montella, C. Recent Res. Devel. Electroanal.
Chem., 2003, ch. Impedance measurement near
a saddle-node bifurcation due to ohmic drop, pp.
1-23.

Bio-Logic Science Instruments, 1 rue de l'Europe, F-38640 Claix - tel: +33 476 98 68 31 – Fax: +33 476 98 69 09 5
Web: www.bio-logic.info