Charging dynamics of electrical double layers inside a cylindrical pore: predicting the effects of arbitrary pore size

Porous electrodes are found in energy storage devices such as supercapacitors and pseudocapacitors. However, the effect of electrode-pore-size distribution on their energy storage properties remains unclear. Here, we develop a model for the charging of electrical double layers inside a cylindrical pore for arbitrary pore size. We assume small applied potentials and perform a regular perturbation analysis to predict the evolution of electrical potential and ion concentrations in both the radial and axial directions. We validate our perturbation model with direct numerical simulations of the Poisson-Nernst-Planck equations, and obtain quantitative agreement between the two approaches for small and moderate potentials. Our analysis yields two main characteristic features of arbitrary pore size: (i) a monotonic decrease of the charging timescale with an increase in relative pore size (pore size relative to Debye length); (ii) large potential changes for overlapping double layers in a thin transition region, which we approximate mathematically by a jump discontinuity. We quantify the contributions of electromigration and charge diffusion fluxes, which provide mechanistic insights into the dependence of charging timescale and capacitance on pore size. We develop a modified transmission circuit model that captures the effect of arbitrary pore size and demonstrate that a time-dependent transition-region resistor needs to be included in the circuit. We also derive phenomenological expressions for average effective capacitance and charging timescale as a function of pore-size distribution. We show that the capacitance and charging timescale increase with smaller average pore sizes and with smaller polydispersity, resulting in a gain of energy density at a constant power density. Overall, our results advance the mechanistic understanding of electrical-double-layer charging.