Transient dynamics of electric double-layer capacitors: Exact expressions within the Debye-Falkenhagen approximation

Abstract

We revisit a classical problem of theoretical electrochemistry: the response of an electric double layer capacitor (EDLC) subject to a small, suddenly applied external potential. We solve the Debye-Falkenhagen equation to obtain exact expressions for key EDLC quantities: the ionic charge density, the ionic current density, and the electric field. In contrast to earlier works, our results are not restricted to the long-time asymptotics of those quantities. The solutions take the form of infinite sums whose successive terms all decay exponentially with increasingly short relaxation times. Importantly, this set of relaxation times is the same among all aforementioned EDLC quantities; this property is demanded on physical grounds but not generally achieved within approximation schemes. The scaling of the largest relaxation timescale $\tau_{1}$, that determines the long-time decay, is in accordance with earlier results: depending on the Debye length, $\lambda_{D}$, and the electrode separation, $2L$, it amounts to $\tau_{1}\simeq\lambda_{D} L/D$ for $L\gg\lambda_{D}$, and $\tau_{1} \simeq 4 L^2/(\pi^2 D)$ for $L\ll\lambda_{D}$, respectively (with $D$ being the ionic diffusivity).