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Cpe Equivalent Capacitance Calculation

The document discusses the concept of constant phase elements (CPE) in electrochemical impedance spectroscopy, which model imperfect capacitive behavior. It provides equations for the impedance of CPE and compares it to ideal capacitors, explaining how the parameter alpha (α) affects the behavior of the element. Additionally, it outlines methods for calculating equivalent capacitance in circuits containing CPE, emphasizing the importance of frequency selection for accurate measurements.

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Sudipa Manna
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0% found this document useful (0 votes)
78 views7 pages

Cpe Equivalent Capacitance Calculation

The document discusses the concept of constant phase elements (CPE) in electrochemical impedance spectroscopy, which model imperfect capacitive behavior. It provides equations for the impedance of CPE and compares it to ideal capacitors, explaining how the parameter alpha (α) affects the behavior of the element. Additionally, it outlines methods for calculating equivalent capacitance in circuits containing CPE, emphasizing the importance of frequency selection for accurate measurements.

Uploaded by

Sudipa Manna
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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Constant phase

element

Calculating equivalent
capacitance

03/2021
Constant phase element

Constant phase element


In electrochemical impedance spectroscopy (EIS), constant phase elements (CPE)
are used to model imperfect capacitive behavior of electrical systems. The
impedance of a constant phase element (𝑍𝑍𝐶𝐶𝐶𝐶𝐶𝐶 ) is defined as
𝜋𝜋
1 1 − ( 2𝛼𝛼𝛼𝛼)
𝑍𝑍𝐶𝐶𝐶𝐶𝐶𝐶 = = 𝑒𝑒 (eq. 1)
(𝑖𝑖 𝜔𝜔)𝛼𝛼 𝑄𝑄 (𝜔𝜔)𝛼𝛼 𝑄𝑄

Here, 𝜔𝜔 is angular frequency and 𝜔𝜔 = 2𝜋𝜋𝜋𝜋. 𝑖𝑖 is imaginary number called iota. Also 𝑄𝑄
and 𝛼𝛼 are frequency-independent constants.

The impedance of an ideal capacitor (𝑍𝑍𝐶𝐶 ) is defined as

1
𝑍𝑍𝐶𝐶 = (eq. 2)
𝑖𝑖𝜔𝜔𝐶𝐶

Here, 𝐶𝐶 is the capacitance. In eq. 1, 𝛼𝛼 can have a value from 0 to 1. If 𝛼𝛼 = 1, then


eq. 1 becomes similar to eq. 2 and 𝑄𝑄 = 𝐶𝐶, hence with 𝛼𝛼 = 1 the constant phase
element behaves like an ideal capacitor. For 𝛼𝛼 = 0, the eq. 1 becomes frequency
independent. A frequency-independent impedance is the characteristic of a
resistor so with 𝛼𝛼 = 0, the constant phase element behaves like an ideal resistor.

Fig. 1 shows qualitative Bode plots of a constant phase element with different
values of 𝛼𝛼. For the CPE with 𝛼𝛼 = 0, the phase will be 0° (red lines in graphs) and
for the CPE with 𝛼𝛼 = 1, the phase will be - 90° (black lines in graphs). For CPE
(with 0 < 𝛼𝛼 < 1), the phase can be calculated via “- 90° * 𝜶𝜶” (derived at the end of
the application note). The phase of a CPE stays constant and does not change with
frequency, hence the electrical element is known as “constant phase element” (see
Fig. 1(b)).

a) b)
Fig. 1: Qualitative Bode plots (a) Impedance plots, and (b) phase plots of a constant phase element
with different values of 𝛼𝛼 .
Constant phase element

10n

Equivalent capacity / F
α
1n 1

100p
0,9
0,8
10p
(2π)-1 0,7
1p
0,6
0,5
1m 10m 100m 1 10 100 1k 10k 100k 1M
frequency
Fig. 2: Calculated equivalent capacitance of a CPE-element as a function of the frequency for
different exponents (𝛼𝛼).

For an ideal capacitor (or CPE with 𝛼𝛼 = 1), the impedance changes with frequency
but the capacitance stays constant (see Fig. 2). On the other hand, the equivalent
capacitance and the impedance of a CPE (with 0 < 𝛼𝛼 < 1) change with frequency
and 𝛼𝛼. The 𝑄𝑄 constant of the constant phase element has a unit of 𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹 ∗ 𝑠𝑠 𝛼𝛼 and
does not directly represent the equivalent capacitance of the constant phase
element. Hence when reporting equivalent capacitance of a CPE it is necessary to
also mention the frequency for which the equivalent capacitance is calculated. To
compare different constant phase elements, the impedances of the constant phase
elements are set equal to the impedance of an ideal capacitor (equating eq. 1 and
eq. 2).

1 1
= (eq. 3)
𝑖𝑖𝜔𝜔𝐶𝐶 (𝑖𝑖𝜔𝜔)𝛼𝛼 𝑄𝑄

Considering on impedance modulus in eq. 3, one gets eq. 3a for the relation
between 𝑄𝑄 and 𝐶𝐶 . Complete derivation is provided at the end of the application
note.
1 1
= (eq. 3a)
𝜔𝜔𝐶𝐶 (𝜔𝜔)𝛼𝛼 𝑄𝑄

Taking log on both sides


− log(𝜔𝜔) − log(𝐶𝐶 ) = −𝛼𝛼 log(𝜔𝜔) − log(𝑄𝑄) (eq. 3b)
1
For frequency = 2𝜋𝜋 , the angular frequency 𝜔𝜔 = 1  log(𝜔𝜔) = 0, then

𝐶𝐶 = 𝑄𝑄
This shows that at a frequency of 1/(2𝜋𝜋), the equivalent capacitance of a single
constant phase element becomes equal to 𝑄𝑄 and does not depend on 𝛼𝛼. This
Constant phase element

frequency of 1/(2𝜋𝜋) is very low for practical use (further explanation later),
therefore to calculate the equivalent capacitance of the constant phase element at
a suitable frequency range the equation 3a can be modified to the following

(𝜔𝜔𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 )𝛼𝛼
𝐶𝐶 =
𝜔𝜔𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 𝑄𝑄 (eq. 4)

Here 𝜔𝜔𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 is the frequency where the equivalent capacitance of the constant
phase element is calculated. As a general rule, 𝜔𝜔𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 is usually taken from high
frequency range (e.g., 1 kHz).

Parallel R-CPE circuit

In practice, the constant phase element is used with other electrical elements in an
electrical circuit. In such cases, determining the equivalent capacitance is not very
straightforward. For calculating the equivalent capacitance of a constant phase
element in an electrical circuit, it is essential to choose a frequency range where
the constant phase element is dominant (measured impedance is primarily because
of the constant phase element, i.e., contributions of other elements to the overall
impedance can be neglected).

Fig. 3 shows a Bode plot of a parallel R-CPE. From Fig. 3 it is clear that at the
frequency of 1/(2𝜋𝜋), the phase angle is close to zero, indicating the dominance of
the resistor at this frequency. Only at frequency above 1 kHz, the phase angle is
close to - 81° (maximum phase angle for a CPE with 𝛼𝛼 = 0.9), illustrating the
dominance of the constant phase element at this frequency range. Therefore, the
equivalent capacitance of the constant phase element must be calculated at this
frequency range (using eq. 4), in particular, 𝜔𝜔𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 = 2𝜋𝜋𝜋𝜋 = 6.2 kHz as the
normalizing, angular frequency.

Fig. 3: Bode plot of a parallel R-CPE circuit. The CPE is dominant at frequencies above 1 kHz.
Constant phase element

Even at high-frequency range, the phase is not exactly - 81° (but - 80.1° at 1 kHz)
indicating a small contribution from the parallel resistance, so the calculated
equivalent capacitance contains some marginal error.

Hsu et al. derived a formula which provides equivalent capacitance of a constant


phase element in a parallel R-CPE circuit without having to consider the
appropriate frequency (𝑤𝑤𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 ). For this Hsu et. al. equated the impedance of the
complete R-CPE circuit with the Cole-Cole impedance expression for a circuit
containing parallel resistor and a capacitive-type element. The total impedance of
a parallel R-CPE (𝑍𝑍𝑅𝑅−𝐶𝐶𝐶𝐶𝐶𝐶 ) can be defined as

1 1
= + (𝑖𝑖𝜔𝜔)𝛼𝛼 𝑄𝑄
𝑍𝑍𝑅𝑅−𝐶𝐶𝐶𝐶𝐶𝐶 𝑅𝑅
𝑅𝑅
𝑍𝑍𝑅𝑅−𝐶𝐶𝐶𝐶𝐶𝐶 = (eq. 5)
1+(𝑖𝑖 𝜔𝜔)𝛼𝛼 𝑄𝑄𝑄𝑄

Cole-Cole expression for the impedance (𝑍𝑍𝐶𝐶𝐶𝐶 ) of a parallel Resistor-Capacitive type


element circuit is
𝑅𝑅
𝑍𝑍𝐶𝐶𝐶𝐶 = (eq. 6)
1+(𝑖𝑖𝜔𝜔𝜔𝜔)𝛼𝛼

Here, time constant 𝜆𝜆 = 𝐶𝐶𝐶𝐶, Equating eq. 5 and 6

(𝑖𝑖𝜔𝜔)𝛼𝛼 𝑄𝑄𝑄𝑄 = (𝑖𝑖𝜔𝜔𝜔𝜔𝜔𝜔)𝛼𝛼


1−𝛼𝛼 1
𝐶𝐶 = 𝑅𝑅( 𝛼𝛼
)
𝑄𝑄𝛼𝛼 (eq. 7)

From eq. 7, the equivalent capacitance of a constant phase element in a parallel R-


CPE circuit can be determined. Here, as the effect of parallel resistor is also
considered so choosing an appropriate frequency range is not required. The
equivalent capacitance of the constant phase element (from eq. 7) corresponds to
the frequency where the imaginary impedance of the R-CPE circuit exhibits a
maximum.
Constant phase element

Appendix: Derivation

Modulus and phase calculation for a constant phase element

Starting with eq. 1,


𝜋𝜋
1 1 − ( 2𝛼𝛼𝛼𝛼)
𝑍𝑍𝐶𝐶𝐶𝐶𝐶𝐶 = = 𝑒𝑒
(𝑖𝑖𝜔𝜔)𝛼𝛼 𝑄𝑄 (𝜔𝜔)𝛼𝛼 𝑄𝑄

1 𝜋𝜋𝜋𝜋 𝜋𝜋𝜋𝜋
𝑍𝑍𝐶𝐶𝐶𝐶𝐶𝐶 = [cos � � − 𝑖𝑖 sin � �]
(𝜔𝜔)𝛼𝛼 𝑄𝑄 2 2

Here the real and imaginary parts are

1 𝜋𝜋𝜋𝜋
𝑍𝑍𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = {cos � �}
(𝜔𝜔)𝛼𝛼 𝑄𝑄 2

1 𝜋𝜋𝜋𝜋
𝑍𝑍𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 = − {sin � �}
(𝜔𝜔)𝛼𝛼 𝑄𝑄 2

Modulus:

𝑍𝑍 = �(𝑍𝑍𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 )2 + (𝑍𝑍𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 )2

Inserting values for real and imaginary part

1 𝜋𝜋𝜋𝜋 1 𝜋𝜋𝜋𝜋
𝑍𝑍 = �[ {cos � �}]2 + [− {sin � �}]2
(𝜔𝜔)𝛼𝛼 𝑄𝑄 2 (𝜔𝜔)𝛼𝛼 𝑄𝑄 2

1
Taking common,
(𝜔𝜔)𝛼𝛼 𝑄𝑄

1 𝜋𝜋𝜋𝜋 𝜋𝜋𝜋𝜋
𝑍𝑍 = �( )2 [{cos2 � �} + {sin2 � �}]
(𝜔𝜔)𝛼𝛼 𝑄𝑄 2 2

cos2(x) + sin2(x) = 1, so
1
𝑍𝑍 = �( )2
(𝜔𝜔)𝛼𝛼 𝑄𝑄

1
𝑍𝑍 =
(𝜔𝜔)𝛼𝛼 𝑄𝑄
Constant phase element

Phase
𝑍𝑍𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖
∅ = 2 tan−1 [ ]
�(𝑍𝑍𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 )2 + (𝑍𝑍𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 )2 + 𝑍𝑍𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟

Inserting values for real and imaginary part

1 𝜋𝜋𝜋𝜋
− {sin � �}
(𝜔𝜔) 𝑄𝑄
𝛼𝛼 2
∅ = 2 tan−1 [ ]
1 1 𝜋𝜋𝜋𝜋
+ {cos � �}
(𝜔𝜔)𝛼𝛼 𝑄𝑄 (𝜔𝜔)𝛼𝛼 𝑄𝑄 2
1
cancels out from numerator and denominator,
(𝜔𝜔)𝛼𝛼 𝑄𝑄
𝜋𝜋𝜋𝜋
−{sin �
�}
−1
∅ = 2 tan [ 2
𝜋𝜋𝜋𝜋 ]
1 + {cos � �}
2
Here, sin(x) = 2sin(x/2)cos(x/2) and 1+cos(x) = 2cos2(x/2)-1, so

𝜋𝜋𝜋𝜋 𝜋𝜋𝜋𝜋
∅ = 2 tan−1 [− tan � �] = −
4 2

∅ = −90° ∗ 𝛼𝛼

References
K.S. Cole, R.H. Cole; J. Chem. Phys. 9 (1941) 341–352

K.S. Cole, R.H. Cole; J. Chem. Phys. 10 (1942) 98-105

G. J. Brug, A. L. G. van den Eeden, M. Sluyters-Rehbach, J. H. Sluyters; Journal of


Electroanalytic Chemistry 176 (1984) 275-295

C.H. Hsu, F. Mansfeld; Corrosion 57/ No. 9 (2001) 747-748

M.R. Shoar Abouzari, F. Berkemeier, G. Schmitz, D. Wilmer; Solid State Ionics 180
(2009) 922–927

B. Hirschorn, M. Orazem, B. Tribollet, V. Vivier, I. Frateur, M. Musiani; El. Acta 55


(2010) 6218–6227

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