Elucidating Curvature-Capacitance Relationships in Carbon-Based Supercapacitors.

Nanoscale surface curvatures, either convex or concave, strongly influence the charging behavior of supercapacitors. Rationalizing individual influences of electrode atoms to the capacitance is possible by interpreting distinct elements of the charge-charge covariance matrix derived from individual charge variations of the electrode atoms. An ionic liquid solvated in acetonitrile and confined between two electrodes, each consisting of three undulated graphene layers, serves as a demonstrator to illustrate pronounced and nontrivial features of the capacitance with respect to the electrode curvature. In addition, the applied voltage determines whether a convex or concave surface contributes to increased capacitance. While at lower voltages capacitance variations are in general correlated with ion number density variations in the double layer formed in the concave region of the electrode, for certain electrode designs a surprisingly strong contribution of the convex part to the differential capacitance is found both at higher and lower voltages.