Electric Field-Dependence of Double Layer Capacitances by Current-Controlled Charge-Discharge Steps

Abstract

Voltage vs. time curves of double layer capacitances (DLCs) by current-controlled charge and discharge steps have been recognized to be composed of triangular waves. They are deviated slightly from triangles from the viewpoint of the time dependence or the constant phase element of the DLC. In order to evaluate the deviation, we measured DLCs of a platinum (Pt) electrode in KCl solution by current-control. Each time-voltage curve was convex rather a line, and was followed by the power law. Even if the time dependence was subtracted from each curve, the enhancement of the DLC was noticeable with an increase in the time well as the voltage. It can be attributed to the electric field effect, in which dipoles of solvents are oriented on an electrode so strongly that the DLC may be increased. The field dependence can be justified with the kinetic theory of interacting dipoles of solvents on an electrode through the observed linearity of the logarithmic DLC with the net voltage. This concept was applied to a commercially available super-capacitor to demonstrate a significant contribution of the field effect.