The charging of electrical double layers inside a cylindrical pore has applications to supercapacitors, batteries, desalination and biosensors. The charging dynamics in the limit of thin double layers, i.e., when the double layer thickness is much smaller than the pore radius, is commonly described using an effective RC transmission line circuit. Here, we perform direct numerical simulations (DNS) of the Poisson-Nernst-Planck equations to study the double layer charging for the scenario of overlapping double layers, i.e., when the double layer thickness is comparable to the pore radius. We develop an analytical model that accurately predicts the results of DNS. Also, we construct a modified effective circuit for the overlapping double layer limit, and find that the modified circuit is identical to the RC transmission line but with different values and physical interpretation of the capacitive and resistive elements. In particular, the effective surface potential is reduced, the capacitor represents a volumetric current source, and the charging timescale is weakly dependent on the ratio of the pore radius and the double layer thickness.

}, issn = {1079-7114}, doi = {10.1103/PhysRevLett.125.076001}, author = {Gupta, Ankur and Zuk, Pawel J and Stone, Howard A} }