Abstract
We propose a new method for the kinetic treatment of self-discharge of intercalation electrodes based on a combination of cyclic voltammetry (CV) and chronopotentiometry under net zero current conditions. This was applied to composite graphite electrodes in 1 M dimethyl polycarbonate at four different temperatures from 25 to 80°C, and was quantitatively proved for small degrees of self-discharge. The degree of self-discharge and the self-discharge current, were shown to substantially increase with the increase in temperature. Self-discharge experiments, which continued for 50 h, were complemented by detailed impedance characterizations of the gradually discharged electrodes, which show an increase in the diameter of the high-frequency semicircles (HFS) with open-circuit time at different temperatures. A comparison between Arrhenius plots for the HFS, the chemical diffusion coefficient, and the self-discharge current may create a basis for a new method of “electrochemical temperature spectroscopy” for identification of the nature of the rate-determining step of self-discharge for different temperature ranges. Our results are discussed in light of studies by others of self-discharge phenomena and mechanisms (Li-graphite electrodes). © 2004 The Electrochemical Society. All rights reserved.
Published Version
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