Comparison Between the Electrochemical Behavior of Disordered Carbons and Graphite Electrodes in Connection with Their Structure

Abstract

This work relates to a rigorous study of the surface chemistry (Fourier transform infrared, X-ray photoelectron spectroscopy), crystal structure (X-ray diffraction), galvanostatic, cyclic voltammetric, and impedance behavior of lithiated carbon electrodes in commonly used liquid electrolyte solutions. Two different types of disordered carbons and graphite, as a reference system, were explored in a single study. All three types of carbons develop a similar surface chemistry in alkyl carbonate solutions, which are dominated by reduction of solvent molecules and anions from the electrolyte. The differences in the crystal structure of these carbons lead to pronounced differences in the mechanisms of Li insertion into them. Whereas Li-ion intercalation into graphite is a staged process, Li-ion insertion into the disordered carbons occurs in the form of adsorption on both sides of the elementary graphene flakes and on their edges. The electroanalytical behavior of the disordered carbons was found to correlate well with their unique structure described in terms of the butterfly model. Both types of the disordered carbons reveal exceptionally good cyclability in coin-type cells (vs. Li counter electrodes), with only moderate capacity fading. Highly resolved plots of the chemical diffusion coefficient of Li-ions, D vs. potential E, for the disordered carbon electrodes were obtained. Surprisingly, a maximum in D appears on these plots at intermediate levels of Li-ion insertion corresponding to ca. 0.4-0.5 V (vs. Li/Li+).Li/Li+). We propose that these maxima may originate from a combination of two effects, (i) repulsive interactions between the inserted species, and (ii) pronounced heterogeneity of Li insertion sites in terms of carbon-Li interactions and Li-ion mobility. © 2001 The Electrochemical Society. All rights reserved.