Application Area: Fundamental
Electrochemical Impedance Spectroscopy (EIS)
Part 4 – Equivalent Circuit Models
Keywords
Electrochemical impedance spectroscopy; frequency
response analysis; Nyquist and Bode presentations; data
fitting; equivalent circuit
Summary
The circuit elements described in the application note AN-
EIS-003 can be combined in series and parallel to build
equivalent circuit models, which can then be used to model
the various phenomena occurring at the interface. In this
note, the use of the circuit elements to build models is
described.
Model 1 – A resistor and capacitor in series Figure 1 - A typical Nyquist plot resulting from a resistor and
a capacitor in series
Model 2 – A resistor, a capacitor and an inductor in
series
Model 1 can be used, for example, to model a metal with an
undamaged high impedance coating. Here, the value of R
gives the resistance of the electrolyte, and the value of C
gives the coating capacitance. In Figure 1, the resulting
Nyquist plot is shown.
Model 2 can be used to model the response of a
supercapacitor. Here, the value of R gives the internal
resistance of the supercapacitor, and the value of C gives
the capacitance value of the supercapacitor, and L can be
attributed to the cables inductance. In Figure 2, the
resulting Nyquist plot is shown.
Application Area: Fundamental
Electrochemical Impedance Spectroscopy (EIS)
Part 4 – Equivalent Circuit Models
Figure 3 - A typical Nyquist plot resulting from the equivalent
Figure 2 - A typical Nyquist plot resulting from a resistor, a
circuit in Model 3. The blue dots represent the results with
capacitor and an inductor in series
the capacitor, the red dots, represent the results with a CPE
(n = 0.8).
Model 3 – A resistor and a capacitor in parallel. The
simplest example of a Randles circuit
Model 4 – Mixed kinetic and diffusion control
The Randles circuit is one of the simplest and most common
cell models. It includes a solution resistance (𝑅 ), a double
It can be used to describe electrode processes when both
layer capacitor C or a CPE and a generic element for the
kinetics and diffusion are non-negligible. Model 4 is a
Faradaic impedance, due to the electrochemical processes.
specific case of Randles circuit. It includes a solution
In the simplest case of the Randles circuit, the Faradaic
resistance (𝑅 ), a double layer capacitor C or a CPE, the
impedance is solely the charge-transfer resistance 𝑅 . It is
charge transfer resistance and the so called Warburg
used to model corrosion processes and is often the starting
element, 𝑍 , which contains information on the diffusion
point for other more complex models. In Figure 3 a typical
coefficient of the species. In Figure 4, a typical Nyquist plot
Nyquist plot resulting from the equivalent circuit of Model 3.
resulting from the equivalent circuit in Model 4.
The blue dots represent the Nyquist plot of the equivalent
circuit with the capacitor, the red dots, represent the Nyquist
plot of the equivalent circuit with a CPE (n = 0.8).
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Application Area: Fundamental
Electrochemical Impedance Spectroscopy (EIS)
Part 4 – Equivalent Circuit Models
Figure 4 - A typical Nyquist plot resulting from the equivalent Figure 5 - A typical Nyquist plot resulting from the equivalent
circuit in Model 4. circuit in Model 5.
Model 5 – Two Randles circuits in series Model 6 – Example of a complex circuit
Model 6 can be used, for example, to describe the
impedance of an organic coating on a metal substrate in
contact with an electrolyte. In Figure 6, a typical Nyquist plot
Model 5 can be used, for example, to model the response of
resulting from the equivalent circuit in Model 6.
batteries. Here, each R and C (or CPE) in parallel can
represent one electrode of the battery. In Figure 5, a typical
Nyquist plot resulting from the equivalent circuit in Model 5.
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Application Area: Fundamental
Electrochemical Impedance Spectroscopy (EIS)
Part 4 – Equivalent Circuit Models
Figure 6 - A typical Nyquist plot resulting from the equivalent
circuit in Model 6.
Non uniqueness of models
It is important to keep in mind that the equivalent circuit
modelling is a method that aims to match a theoretical
model of an electrochemical interface with an experimental
set of data. Proper assignment of the circuit elements can
only be performed when sufficient information on the
chemical and electrochemical phenomena taken place at
the interface is available.
Moreover, it is important to keep in mind that several
arrangements of circuit elements are possible for a given set
of data, and that some equivalent circuits are
mathematically identical.
Conclusions
This application notes shows how electrical elements can be
arranged, in order to build simple and complex equivalent
circuits for fitting EIS data. The resulting Nyquist plots for all
the circuits are shown as well.
Date
September 2019 AN-EIS-004
For more information
Additional information about this application note and the
associated NOVA software procedure is available from your
local Metrohm distributor. Additional instrument
specification information can be found at
http://www.metrohm.com/electrochemistry.
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