Oscillation of Capacitance inside Nanopores

Porous carbons of high surface area are promising as cost-effective electrode materials for supercapacitors. Although great attention has been given to the anomalous increase of the capacitance as the pore size approaches the ionic dimensions, there remains a lack of full comprehension of the size dependence of the capacitance in nanopores. Here we predict from a classical density functional theory that the capacitance of an ionic-liquid electrolyte inside a nanopore oscillates with a decaying envelope as the pore size increases. The oscillatory behavior can be attributed to the interference of the overlapping electric double layers (EDLs); namely, the maxima in capacitance appear when superposition of the two EDLs is most constructive. The theoretical prediction agrees well with the experiment when the pore size is less than twice the ionic diameter. Confirmation of the entire oscillatory spectrum invites future experiments with a precise control of the pore size from micro- to mesoscales.