Equivalent circuit and continuum modeling of the impedance of electrolyte-filled pores

Abstract

Batteries, supercapacitors, and several other electrochemical devices charge by accumulating ions in the pores of electrolyte-immersed porous electrodes. The charging of such devices has long been interpreted using equivalent circuits and the partial differential equations these give rise to. Here, we discuss the validity of the transmission line (TL) circuit and equation for modeling a single electrolyte-filled pore in contact with a reservoir of resistance $R_{r}$. The textbook derivation of the pore-reservoir impedance $R_r+Z_p$ from the TL equation does not correctly account for ionic current conservation at the pore-reservoir interface. However, correcting this shortcoming leads to the same impedance. We also show that the pore impedance $Z_p$ can be derived directly from the TL circuit, bypassing the TL equation completely. The TL circuit assumes equipotential lines in an electrolyte-filled pore to be straight, which is not the case near the pore entrance and end. To determine the importance of these regions, we numerically simulated the charging of pores of different lengths $\ell_p$ and radii $\varrho_p$ through the Poisson-Nernst-Planck equations. We find that pores with aspect ratios beyond $\ell_p/\varrho_p\gtrapprox5$ have impedances in good agreement with $Z_p$.