CPE Analysis from cyclic voltammetry and electrochemical impedance spectroscopy
Abstract
The electric properties of an electrode can be evaluated by the determination of the capacitance of the
interface. However, the literature reports a large panel of experimental protocols for capacitance
determination, which involve either cyclic voltammetry (CV) or electrochemical impedance
spectroscopy (EIS). On the one hand, CV is a routine electrochemical technique widely used for the
determination of electric properties of super capacitors or energy storage devices. The capacitive
charge is determined through the variation of the scan rate in a non-faradaic current domain and is
often used to estimate the performances of these electrodes. On the other hand, EIS is used for the
determination of interfacial processes and also provides precise information on the double layer
capacitance and the oxide capacitance in the case of more complex systems. However, substantial
discrepancies in the assumptions are made between both techniques as in CV, the system is usually
considered as ideal (and the current-scan rate relationship is assumed to remain linear at all
frequencies), whereas in EIS, the system is usually considered as non-ideal and a CPE element is
introduced. Although both techniques are used to provide similar information on the capacitive
characteristics of electrochemical interfaces, a clear correlation between the results obtained with each
technique is not straightforward. In fact, recent work from Allagui et al. [1]revealed that the time-voltage
relationship cannot be used when the system is considered as ideal.
In this work, electrochemical impedance spectroscopy and cyclic voltammetry were performed on well-
known systems showing capacitive behaviours on a wide frequency domain and over a wide potential
range: a blocking electrode (Au) and an electrode with a thin oxide film (Al). The capacitive charge was
determined using cyclic voltammetry from the analysis of the conventional current to scan rate linear
relationship and EIS measurement. In CV measurements, the calculated capacitance predominantly
stems from the double layer capacitance for the considered scan rate ranges (low frequency range).
Additionally, it was shown that the value of the determined capacitance is scan-rate dependent. Such
experimental results highlight the arbitrary character of the scan rate ranges used in the literature as
they usually remain in low frequency range. In fact, careful selection of scan rate is critical and should
be adapted to the electrode considered, particularly for systems involving a thin oxide film as the Cdlor
the Coxresponse depends on the frequency range. Similarly, the EIS response shows that the
capacitance determination cannot be performed without a large error when a non-ideal behaviour is
experimentally obtained. From a physical point of view, such outcome in this frequency domain is the
results of observations made in the selected time domain [2].
References
[1] A. Allagui, T.J. Freeborn, A.S. Elwakil, B.J. Maundy, Reevaluation of Performance of Electric
Double-layer Capacitors from Constant-current Charge/Discharge and Cyclic Voltammetry, Sci Rep, 6
(2016) 38568.
[2] O. Gharbi, M.T.T. Tran, B. Tribollet, M. Turmine, V. Vivier, Revisiting cyclic voltammetry and
electrochemical impedance spectroscopy analysis for capacitance measurements, Electrochim. Acta,
343 (2020) 136109.
Symposium Selection:
F02 - Advances in Application and Theory of Electrochemical Impedance Spectroscopy