Reevaluation of Performance of Electric Double-layer Capacitors from Constant-current Charge/Discharge and Cyclic Voltammetry

Abstract

The electric characteristics of electric-double layer capacitors (EDLCs) are determined by their capacitance which is usually measured in the time domain from constant-current charging/discharging and cyclic voltammetry tests, and from the frequency domain using nonlinear least-squares fitting of spectral impedance. The time-voltage and current-voltage profiles from the first two techniques are commonly treated by assuming ideal R_sC behavior in spite of the nonlinear response of the device, which in turn provides inaccurate values for its characteristic metrics [corrected]. In this paper we revisit the calculation of capacitance, power and energy of EDLCs from the time domain constant-current step response and linear voltage waveform, under the assumption that the device behaves as an equivalent fractional-order circuit consisting of a resistance R_s in series with a constant phase element (CPE(Q, α), with Q being a pseudocapacitance and α a dispersion coefficient). In particular, we show with the derived (R_s, Q, α)-based expressions, that the corresponding nonlinear effects in voltage-time and current-voltage can be encompassed through nonlinear terms function of the coefficient α, which is not possible with the classical R_sC model. We validate our formulae with the experimental measurements of different EDLCs.