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An Equivalent Circuit of Carbon Electrode Supercapacitors

Usman S.Sani*, Ibrahim H.Shanono*
*Department of Electrical Engineering,
Bayero University, Kano, P.M.B. 3011, Nigeria.
Email: usmanssani@live.com, ihshanono.ele@buk.edu.ng



Abstract
Impedance spectroscopy test was performed on a commercial carbon electrode supercapacitor. Data
obtained was presented in form of a Nyquist plot which was then modeled into an equivalent circuit.
Six electro-chemical double layer supercapacitors were then fabricated. The fabricated
supercapacitors were modeled in the same manner. All the supercapacitors fitted the equivalent
model with errors in the form of chi square ranging from 1.081 10
-3
to 8.979 10
-3
, showing how the
equivalent circuit models an approximate behavior of a supercapacitor. Unlike in most cases where
by researchers show equivalent circuits of supercapacitors without accounting for the value of each
circuit element, the value of each circuit element is shown in this work.

Keywords:Equivalent circuit, Impedance spectroscopy, Tanhyperbole

Introduction
Supercapacitors are well known for their high energy and power densities, long
lifetime as well as great cycle number. Typical applications of supercapacitors include
memory backup to bridge short power interruptions, improving the current handling of a
battery as well as regenerative braking on vehicles. In the field of telecommunication it is
used to supply power during signal transmission because more power is needed during
transmission than during reception. Though supercapacitors perform well, there is a need for
improvement at higher frequencies. This is due to the fact that the supercapacitor no longer
behaves as a capacitor at high frequencies rather its behaviour changes closely to that of a
resistor. So also, resistances in supercapacitors have to be minimized to ensure maximum
power delivery [1]-[7].
An important aspect of study in a supercapacitor is its impedance which has an
imaginary part that is inversely proportional to its capacitance value. The impedance is
frequency dependant making the capacitance to be dependant on frequency too. The
impedance considered is thus a complex number consisting of a real part and a frequency
dependant imaginary part indicated by equation 1. The impedance of the supercapacitor is
determined by experimentation process known as the Impedance Spectroscopy Study from
which analysis is done to obtain the supercapacitors value and other parameters [7],[ 8].
(1)

II. Impedance spectroscopy
Impedance spectroscopy involves taking measurements of impedance for a device or
material over a certain frequency range. It is applied in the field of electrochemistry for
material characterization and new materials development, a process which requires
continuous measurements until the target goal is achieved. It involves conversion of the
signals involved from time domain to the frequency domain which are voltage and current. A
sinusoidal signal generated by a signal generator is applied to the system/device/material and
the resulting signal is recorded by a phase- sensitive recording device or by any other means.
The input control signal may either be a voltage signal or a current signal. If the applied
signal is a voltage source, the impedance spectroscopy is termed potentiostatic impedance
spectroscopy. Likewise for an applied current signal it is termed galvanostatic impedance


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spectroscopy. The impedance is determined by finding the ratio of the voltage to the current
and doesnt matter on which parameter amongst them is the input or the output. Thus any of
the impedance spectroscopy measurement techniques can be used [7]-[12].
The results obtained from measurements are used to draw a Nyquist plot, which is a
plot of the imaginary impedance (Z) versus the real impedance (Z) as a function of
frequency. Oscilloscopes have been used to obtain plots in a case where the input and output
signals are connected to the plates of an oscilloscope. The resulting plot is called a Lissajous
figure which takes the form of an ellipse. Further analysis is done based on which of the
signals is connected to the vertical plate and which is connected to the horizontal plate. This
method is called the Lissajous analysis. Bode plots are often used in some cases [7]-[12].
Nowadays, computers are used in measuring impedance by the application of Fast
Fourier Transform (FFT) in which the setup consists of an embedded measurement
instrument connected to a computer workstation which has software installed for data
presentation and analysis. The embedded measurement system contains analogue to digital
converters, instrumentation amplifiers and a data acquisition board which transfers data to the
work station computer as well as process any command issued via software in order to
control the experimental setup [7]-[12].

Methodology
Impedance spectroscopy was first carried out on a commercial supercapacitor using
VersaSTAT 3 and its accompanying V3-studio software. The purpose was to model it first
such that any other supercapacitor could be modeled based on results obtained. A GS113
capxxsupercapacitor was selected for the purpose. The supercapacitor is a thin prismatic
packaged supercapacitor suitable for application in portable devices such as mobile phone,
camera, digital music players, PCMCIA cards, notebook PCs, location tracking devices and
other automotive applications etc. Due to the type of packaging used capxxsupercapacitors
are well known for their low equivalent series resistance implying that they permit maximum
power delivery [13]. An equivalent circuit model was generated for the data obtained using
Zsimpwin software.


Figure 1: Picture of the Capxx prismatic supercapacitor.

The Nyquist plot from the impedance spectroscopy of the capxxsupercapacitor and
data obtained from equivalent circuit fitting is shown below:


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Figure 2: Impedance spectra of capxxsupercapacitor with fitted equivalent circuit data.


Figure 2 above showed a legend composed of Z, Msd and Z, Calc. Z, Msd is the
measured impedance spectra, while Z, Calc is the data for the fitted equivalent circuit. It will
be noticed that the data was almost the same indicating how matched the measured data is to
the fitted equivalent circuit data.
The fitted circuit model resulted by matching the data obtained by measurements
against all the circuit models available in the software and selecting the best among them.
The software Zsimpwin by iteration process computes the global minimum chi square ( )
for a selected circuit and shows the optimal circuit parameters using the Down-hill Simplex
Method [14]. Since is the sum of squared errors divided by the variance [15], the circuit
that gave the least chi square was selected as the appropriate model. A kind of circuit coding
system was used to indicate a circuit by symbols rather than by figures. In such codes,
elements in series are represented by a concatenation of their symbol letters. Parallel
components are bracketed and concatenated with other series or parallel elements. In the case
where the first element or first set of elements in series are in parallel with the remaining
circuit components, the whole expression is put into bracket. Table I below shows the list of
circuit elements used for equivalent circuit fitting.

Table 1: Circuit elements used for modelling impedance spectroscopy data.
Description Symbol Parameter
Resistance R R
Capacitance C C
Inductance L L
Warburg W Yo
Constant phase Element Q Yo,
Tanhyperbole T Yo, B
Cothyperbole O Yo, B
Gerischer G Yo, B



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. The equivalent circuit model for the capxxsupercapacitor and its code is shown
below:

Figure 3: Equivalent circuit model of capxxsupercapacitor.

Circuit code: R(CR)(CR)T

For easy identification, each of the circuit components was given a number designation.
Numbers 0 to 5 were used as shown below:

R(CR)(CR)T
0 12 34 5

Table 2 shows each parameter, its designated number and value.

Table 2: Equivalent circuit parameters of the capxxsupercapacitor












Six carbon electrode supercapacitors were fabricated, each of which was given a letter
designation from A to F. Impedance spectroscopy test was performed on each supercapacitor
and the results were fitted unto the equivalent circuit that matched the capxxsupercapacitor.
The results are shown below:
Number designation Component Parameter Value
0 R() Solution resistance. 0.0660
1 C(F) Double layer capacitance. 0.0165
2 R() Solution resistance. 0.0053
3 C(F) Double layer capacitance. 2.3600
4 R() Solution resistance. 0.0936
5 T Yo(S) Admittance. 3.4180
B(s) Time constant. 0.3128


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Figure 4: Impedance spectra of supercapacitor A with fitted equivalent circuit data.


Figure 5: Impedance spectra of supercapacitor B with fitted equivalent circuit data.


Figure 6: Impedance spectra of supercapacitor C with fitted equivalent circuit data.



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Figure 7: Impedance spectra of supercapacitor D with fitted equivalent circuit data.


Figure 8: Impedance spectra of supercapacitor E with fitted equivalent circuit data.




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Figure 9: Impedance spectra of supercapacitor F with fitted equivalent circuit data.

The equivalent circuit parameters of each supercapacitor are shown in the table below:

Table 3: Values of equivalent circuit parameters of the fabricated supercapacitors













The chi-square ( ) value obtained from the equivalent circuit fitting of each
supercapacitor is shown below:

Table 4:Chi square values obtained from the equivalent circuit fitting of each
supercapacitor
Supercapacitor capxx A B C D E F
Chi-square X 10
-3


2.339

3.705

3.880

2.833

8.979

1.210

1.081

N0.

Component

Supercapacitor
A B C D E F
0 R() 0.5447 0.3843 0.5279 0.4263 0.4193 2.2790
1 C(F) 54.050 9.9480 12.210 3.8640 46.48 0.5668
2 R() 2.4900 5.8410 1.9370 7.3530 0.3327 2.8740
3 C(F) 0.0754 1496.0 113.90 604.60 4226 233.3
4 R() 1.1300 0.4664 0.3640 0.1747 0.0751 0.4387
5 T Yo(S) 0.1063 1.4270 0.6464 0.4104 0.5225 0.2372
B(s) 54.710 2.4580 2.9530 3.3700 1.5140 1.1880


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Discussion of Results
From the equivalent circuit fitting it was seen that the supercapacitor could be
represented with a resistance in series with 2 time constants and a Tanhyperbole (T) element.
The presence of the T element indicates that finite diffusion takes place in the supercapacitor.
This is a sort of an impurity in an electrochemical double layer supercapacitor. But the level
of diffusion is not much because a T element describes a process with a limited number of
electro-active species. The moment they are finished, they cant be replenished.
Resistors with designation numbers 0, 2 and 4 are solution resistances together with
contact resistance and separator resistance. By mentioning the term solution resistance, the
electrolyte resistance and charge transfer resistance are being referred to. This is because the
fitting was done using software and one cant differentiate the contributions of each
resistance. Meanwhile a totality of there effects is shown by the resistors. The same also
applies to the double layer capacitors.

Conclusions
Impedance spectroscopy tests were carried out on seven supercapacitors, the result of
which was used in determining an equivalent circuit that models the behavior of a
supercapacitor. Results showed that a supercapacitor can be represented by an equivalent
circuit consisting of a resistor in series with two time constants and a Tanhyperbole.

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