World Journal of Chemical Education, 2021, Vol. 9, No.

1, 14-21
Available online at http://pubs.sciepub.com/wjce/9/1/3
Published by Science and Education Publishing
DOI:10.12691/wjce-9-1-3

Fundamentals and Applications of Electrochemical

Impedance Spectroscopy - A Didactic Perspective
Achim Habekost*

University of Education Ludwigsburg, Department of Chemistry, Ludwigsburg, Germany

*Corresponding author:
Received November 19, 2020; Revised December 20, 2020; Accepted December 27, 2020
Abstract Two experiments are presented to introduce students to the utility of electrochemical impedance
spectroscopy (EIS) in finding electrodes suitable for applications such as battery development. We used different
metal and carbon nanotube (CNT) screen-printed electrodes (SPEs) and compared EIS with cyclic voltammetry
(CV) curves. In addition, we prepared the SPEs with graphene powder to show the different behaviour of modified
and unmodified SPEs with CV and EIS.
Keywords: electrochemistry, electrochemical impedance spectroscopy
Cite This Article: Achim Habekost, “Fundamentals and Applications of Electrochemical Impedance
Spectroscopy - A Didactic Perspective.” World Journal of Chemical Education, vol. 9, no. 1 (2021): 14-21.
doi: 10.12691/wjce-9-1-3.

Ions in the solution diffuse in the alternating current

field. At high frequencies the diffusion is negligible
1. Introduction because the ions do not move very far. At lower
frequencies, however, the ions diffuse farther. This is
Along with other electrochemical measurements such described by the Warburg impedance.
as cyclic voltammetry (CV), square wave voltammetry The potential is described as
(SWV) or chronoamperometry (CA), electrochemical
impedance spectroscopy (EIS) plays an important role in E ( t ) = E0 exp ( jwt )
measuring the characteristics of electrode in electrolyte and the current response as
solutions.
If a potential is applied to an electrode-electrolyte =I ( t ) I 0 exp ( jwt − φ ). (1)
interface, a flow of charge and matter occurs. Without
going into details, in EIS the impedance (the resistance of φ: phase between potential and current; ω: radial
the AC circuit) of the electrochemical system is measured frequency = 2πν; ν: frequency, j: imaginary unit.
as a function of the applied frequency. The processes at The impedance, Z, is represented as the complex number
the electrode, immersed in the solution, can be described Z=
( w) E=
/ I Z 0 * exp ( jwt )
with different electrical compounds as resistors (solution (2)
resistor, Rs; charge transfer or polarization resistor, Rp), =Z 0 [cos ( wt ) + jsin( wt )] =Re ( Z ) + jIm ( Z ) .
capacitor (Helmholtz double layer in front of the electrode,
Cdl), and coil (inductance resulting from the current, which Re: real part and Im: imaginary part of the impedance.
induces an electromotive force that opposes a change in Therefore
current, L). One of the main purposes of EIS is to describe Re ( Z=
) Z=' Z 0 cos ( wt ) and Im ( Z=
) Z '' sin( wt ). (3)
an electrochemical system through a combination of these
passive electric compounds. In contrast to the ohmic The modulus of Z is
resistor, capacitors and coils have a frequency-dependent
( Z ')2 + ( Z '')
2
resistance, which is inversely proportional to the frequency =Z (4)
of the first and proportional to the frequency of the latter.
Table 1. Lists the standard electric elements

Electric element Impedance Description

Impedance of the solution
Rs ≠ f(ω)
Resistor (R) Impedance of the charge transfer
Rp ≠ f(ω) (polarization impedance)
Capacitor (Cdl) (jωC)-1 Double layer
Inductance (L) jωL Inductance effects
 World Journal of Chemical Education 15

Electric element Impedance Description

1 RT 1 1
ZW= (1-j)*σ with σ= (
+ )
ω 2 2
z F A 2D o cR
c
Warburg impedance (ZW) Warburg impedance coefficient, Diffusion
D: mean diffusion coefficient of oxidized and reduced species;
z: number of involved electrons; A: surface area, co und cR:
concentration of oxidized and reduced species
Non-ideal capacitor (irregular current
Constant phase element (CPE) (jωC)-α with 0.5≤α≤1.0
distribution, especially on rough surfaces)

In electrochemistry, a Randles circuit is one of the The exchange-current density, i0, is:
simplest electrical circuits to describe an electrochemical
io = F*k0*c (8)
system. It consists of an electrolyte resistance, RS, in
series with the parallel combination of the double-layer The double layer capacitance can be estimated from
capacitance, Cdl, and an impedance of a faradaic (i.e., Zmax of the semicircle (Figure 2).
electron-transfer) reaction, Rp. Sometimes a constant When calculating the Warburg impedance (Figure 1,
phase element CPE is used instead of an imperfect right), it is necessary to distinguish between two cases:
capacitor, which is in series to Rs or to Rp. The Warburg a) Low frequency case:
impedance (ZW) describes the diffusion. In real σ σ
electrochemical systems, EIS is more complicated and the Z=Rs+Rp+ – j( +2σ 2 Cdl)
Randles circuit may not give appropriate results; however, ω ω
in this article we restrict ourselves on simple, didactical =Z '− j Z ''= Re ( Z ) − j Im ( Z )
electrochemical systems.
Figure 1 shows the Randles circuit which is often used And therefore
at the beginning of fitting data. σ
Z''= +2σ 2 Cdl =Z'-(Rs+Rp-2σ 2 Cdl) (9)
ω
One can see that Z'' is scaled linearly with Z'.
The diffusion coefficient can be calculated from eq (10)
[2]

R 2T2
D= (s is dependent on D). (10)
2A 2 z 4 F4 c2 σ 2
Figure 1. Randles circuit [R(RC)W]. Abbreviations: “[...]” means “in
series”, “(…)” means “parallel”. Indices are not shown. b) High frequency case:
In this case the Warburg impedance equals zero,
Calculating the equivalent circuit without the Warburg
because the ions do not diffuse. This results in the
impedance is complicated, and leads to [1,2,3,4]
equation
Rp ωCdlRp 2 2Rs+Rp 2 Rp
Z = R s+ +j (5) (Z' − ) +Z''=( )2 (11)
1+ω2 Cdl 2 Rp 2 1+ω2 Cdl 2 Rp 2 2 2
Rp This is a circular equation with the center at Z' = Rs +
Re(Z) = Z' = Rs+ Rp/2 and radius Rp/2.
1+ω2 Cdl 2 Rp 2
In a Nyquist diagram -Im(Z) = -Z'' is plotted against
and Re(Z) = Z' for different frequencies, from low frequencies
on the right side to high frequencies on the left side
ωCdlRp 2 (Figure 2). Figure 3 shows a three-dimensional plot. Note
Im(Z) = Z'' = .
1+ω2 Cdl 2 Rp 2 the shortcoming of the Nyquist plot that the frequency is
not displayed.
The faradaic current i0, caused by a charge-transfer The maximum of the semicircle is ω = 101 Hz. Therefore
through the electrode interface, is given by eq (6): with Rp = 649 Ω, Cdl = 1/(2π*101*649) = 2.4 µF, which is
RT a good estimation compared to the fitted value.
i0= (6) Another important presentation is the Bode plot. Here,
zFRp
both the modulus of the impedance, |Z|, and the phase
with z: number of electrons implied in the transfer; F: shift on the y-axis are plotted against log frequency on the
Faraday constant; T: temperature; Rp: charge transfer or x-axis. Current through capacitors is phase-shifted by 90
polarization resistor. degrees with respect to voltage. In contrast, current
The charge transfer resistance (Rp) correlates with the through inductors is phase-shifted by -90 degrees with
charge-transfer rate (k0) and the exchange-current density respect to voltage, while the current through a resistor
(i0): stays in phase with the voltage across the resistor.
Figure 4 shows the Bode plot of the above Randles circuit.
RT RT One can see that the Bode plot is an superposition of the
R p= = (7)
zF*i0 zF2 k0*c (RC) circuit and a Warburg impedance (Figure 4, bottom).
16 World Journal of Chemical Education

Figure 2. Nyquist diagram. Points: measuring points; solid line: fit with Randles circuit (Rs = 92 Ω, Rp = 649 Ω, Cdl = 2.2 µF, Yo(Warburg) = 3.02
mMho(s)1/2), see insert. Note: “Mho” is Ohm written backwards. Y0 is the admittance (reciprocal of the impedance) multiplied by sqr(ω)

Figure 3. Three-dimensional plot of Z'' against Z' and frequency

 World Journal of Chemical Education 17

Figure 4. Top: Bode plot for the same Randles circuit as in Figure 2. Middle: Simulation for RC. Bottom: Simulation for Warburg only
18 World Journal of Chemical Education

At low frequencies the capacitor blocks (high Graphene nanoplatelets, purity 91%, particle size up to
impedance), while at high frequencies the capacitor has 2µm: Plasma Chem GmbH PL-P-G750
low impedance. Instruments: CV and EIS were recorded with a
The phase is: DRP-STAT-I-400 potentiostat with EIS from Metrohm,
DropSens. DRP-STAT-I-400 is a dual-channel impedance
Z'' ωRp 2 Cdl instrument for multiplexed EIS measurements, controlled
Φ = arctan( ) = − arctan( ) (12)
Z' Rs+Rp+Rs(ωRpCdl)2 by DropView 8400 software. This allows specific EIS
features such as data presentation of Nyquist, Bode and
The Warburg impedance scales negative linearily with Lissajous plots, including information about time domain,
frequency: At low frequencies the Warburg impedance is frequency domain as well as EIS data treatment, including
high; at high frequences it is low. The phase is constant at fit and simulation, semicircle fit, and EIS analysis.
45 degrees. Procedure: A drop of the solution is placed on the SPE
with a pipette. The experiments were performed with different
SPEs: DS 1110 CNT with two CNT working electrodes
2. Experiments and CNT counter electrode, reference electrode: Ag (see
Figure 5, right) and Au-AT (working electrode and counter
Chemicals and procedure electrode: Au; reference electrode: Ag). The reference
K4[Fe(CN)6], 1 mmol/L in 0.1 M aqueous Na2SO4. potential of the silver electrode is a pseudo-potential.
electrode is a pseudo-potential.

Figure 5. Left: DS Au-AT (AT means: high temperature curing ink). Right: DS 1110 CNT with two CNT working electrodes

Electrochemical cells are normally non-linear. This In addition, the electrodes were modified by rubbing
means that doubling the potential does not necessarily graphene on them with a Q Tip.
double the current. In EIS, only small excitation potentials We compared CV and EIS spectra. Both were fitted:
(amplitude) in the range of few 10 mV are used. Therefore, CV with DigiElch (professional)®, and the EIS spectra
the cell response is (pseudo-)linear. This means that a after defining Randles circuits.
sinusoidal potential results in a sinusoidal, phase-shifted a) Metallic working electrodes with and without graphene
current. Figure 6 shows the CV of the K4[Fe(CN)6] solution
As mentioned above, different working materials were with Au-AT (solid line) and Au-AT decorated with
investigated, including metallic and non-metallic materials. graphene (dotted line).

400
300
200
100
current / µA

0
-100
-200
-300
-400
-0.2 -0.1 0 0.1 0.2 0.3 0.4 0.5 0.6

potential / V

Figure 6. CV of K4[Fe(CN)6] with Au-AT (solid line) and with Au-AT / graphene (dotted line).
 World Journal of Chemical Education 19

A comparison of the (fitting) curves shows that the electron transfer is faster when the gold electrode is decorated with
graphene (k'0 = 0.0033 cm/s vs k'0 = 0.007 cm/s).

Figure 7. Left: Au-AT without graphene. Fitting parameters: E0 = 0.14 V; k'0 = 0.0033 cm/s. Right: Au-AT with graphene. Fitting parameters: E0 = 0.17
V; k'0 = 0.007 cm/s. (k0 (eq. (8) and k'0 have different dimensions)

Figure 8 shows the EIS spectra.

Figure 8. EIS spectra of K4[Fe(CN)6] with Au-AT (pink dots) and with Au-AT / graphene (blue dots). Lines: fitted curves. Insert: Randles circuits

Curve fitting shows that the charge-transfer resistance current peaks move slightly together. Fitting with
differs significantly from 62.3 Ω (Au-AT) to 13.1 Ω DigiElch Professional® confirms this: the rate constant
(Au-AT / graphene). Therefore, the charge-transfer rate with graphene is higher (k'0 = 0.0046 cm/s vs k'0 =
(k0 or k'0) is faster with Au-AT / graphene. Theoretical 0.0033 cm/s).
considerations must explain these results, but this goes Figure 10 shows the corresponding Nyquist and
beyond the scope of this paper. Bode plots. The Nyquist plot differs between CNT
a) CNT working electrodes with and without graphene with and without graphene, but the Bode plot, where
Figure 9 shows the CVs of K4[Fe(CN)6] with CNT both the modulus of the impedance |Z| is plotted against
with (dotted line) and without graphene (solid line). the frequency, is more meaningful. At each frequency,
It can clearly be seen that the current peaks rise when |Z| is smaller for CNT with graphene than without
the CNT is decorated with graphene. In addition, the graphene.
20 World Journal of Chemical Education

Figure 9. Top: CV of K4[Fe(CN)6] with CNT-WE without (solid line) and with graphene (dotted line). Bottom: CV and fitted curves. Left: CNT with
graphene; k'0 = 0.0046 cm/s. Right: CNT without graphene; k'0 = 0.0033 cm/s
 World Journal of Chemical Education 21

Figure 10. Top: EIS of K4[Fe(CN)6] with CNT-WE with graphene (blue points) and without graphene (red points). Top: Nyquist diagram. Bottom:
Bode plot.

3. Conclusion (Frankfurt, Germany), and the University of Education

Ludwigsburg (Germany) for financial support.
EIS is a very powerful technique to measure
electrochemical behavior and model the results using
Randles circuits. The EIS can be easily measured with References
inexpensive disposable screen-printed electrodes that can
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be easily modified and compared with CV. Our explorative impedance spectroscopy, Electrochim. Acta (2006), 51, 1376-
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spectroelectrochemistry provide a way to understand spectroscopy: an overview of biological applications, J. Anal.
Methods (2013), 5, 1098-1115.
electrode processes in a didactic sense.
[3] D. Ende, K-M. Mangold, Impedanzspektroskopie, Chemie in
unserer Zeit (1993), 27, 134-140.
[4] Andrzej Lasla, Electrochemical Impedance Spectroscopy and its
Notes Applications, Springer, New York, 2014.

The author declares no competing financial interest.

Acknowledgments
The author would like to thank the Vector Foundation
(Stuttgart, Germany), the Fonds der Chemischen Industrie

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