Microscopic Insights into the Electrochemical Behavior of Nonaqueous Electrolytes in Electric Double-Layer Capacitors.

Electric double-layer capacitors (EDLCs) are electrical devices that store energy by adsorption of ionic species at the inner surface of porous electrodes. Compared with aqueous electrolytes, ionic liquid and organic electrolytes have the advantage of larger potential windows, making them attractive for the next generation of EDLCs with superior energy and power densities. The performance of both ionic liquid and organic electrolyte EDLCs hinges on the judicious selection of the electrode pore size and the electrolyte composition, which requires a comprehension of the charging behavior from a microscopic view. In this Perspective, we discuss predictions from the classical density functional theory (CDFT) on the dependence of the capacitance on the pore size for ionic liquid and organic electrolyte EDLCs. CDFT is applicable to electrodes with the pore size ranging from that below the ionic dimensionality to mesoscopic scales, thus unique for investigating the electrochemical behavior of the confined electrolytes for EDLC applications.