On the Interpretation of Measured Impedance Spectra of Insertion Cathodes for Lithium-Ion Batteries

In the literature, the interpretation of electrochemical impedance spectra measured on insertion cathode materials is far from being unique. In most cases, various arbitrarily selected equivalent circuits have been used for analysis of spectra whereby the criterion of merit has mainly been the quality of fit. Herein, we propose a different approach. We try to explain the main features such as the high and medium frequency arcs and the low frequency diffusional tail using convenient (simplified) equivalent circuits derived from a quite general description of impedance due to a particulate (porous) system. The proposed models have a clear physical background. The meaning of selected circuit parameters is experimentally verified using carefully modeled experiments on LiFePO(4) and LiCoO(2) materials. In particular, we discuss the effects of state of charge, external pressure, electrode mass (thickness), and electrolyte concentration on the measured and simulated equivalent circuits. In the last part, we discuss in certain depth the complications arising from poor electronic or ionic contacting (wiring) between different phases constituting electrodes. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3489353] All rights reserved.