Electrochemical and electronic properties of LiCoO2 cathode investigated by galvanostatic cycling and EIS

Abstract

The processes of extraction and insertion of lithium ions in LiCoO₂ cathode are investigated by galvanostatic cycling and electrochemical impedance spectroscopy (EIS) at different potentials during the first charge/discharge cycle and at different temperatures after 10 charge/discharge cycles. The spectra exhibit three semicircles and a slightly inclined line that appear successively as the frequency decreases. An appropriate equivalent circuit is proposed to fit the experimental EIS data. Based on detailed analysis of the change in kinetic parameters obtained from simulating the experimental EIS data as functions of potential and temperature, the high-frequency, the middle-frequency, and the low-frequency semicircles can be attributed to the migration of the lithium ions through the SEI film, the electronic properties of the material and the charge transfer step, respectively. The slightly inclined line arises from the solid state diffusion process. The electrical conductivity of the layered LiCoO₂ changes dramatically at early delithiation as a result of a polaron-to-metal transition. In an electrolyte solution of 1 mol L⁻¹LiPF₆–EC (ethylene carbonate) ∶ DMC (dimethyl carbonate), the activation energy of the ion jump (which is related to the migration of the lithium ions through the SEI film), the thermal activation energy of the electrical conductivity and the activation energy of the intercalation/deintercalation reaction are 37.7, 39.1 and 69.0 kJ mol⁻¹, respectively.