Effect of low-temperature conditions on passive layer growth on Li intercalation materials - In situ impedance study

Electrochemical impedance spectroscopy has been applied to investigate the formation of insulating layers at the sur faces of microscopic particles of mesocarbon microbeads (MCMB), graphite, and hard carbon during the first Li-intercalation into these materials at ambient temperature as well as at -20 degrees C. Investigations were carried out in a three-electrode sandwich cell, designed for impedance measurements in the frequency range 64 kHz to 5 mHz. The impedance spectra, obtained in the potential range 1.5 and 0.02 V during the first charge, were analyzed by complex nonlinear least square fits. A new model, taking into account the porous structure of the intercalation material, electrochemical processes at the interface, as well as spherical diffusion of Li ions toward the centers of the particles, has been used for this analysis. The first intercalation at -20 degrees C results in formation of an insulating layer, which is about 90 times thinner than in the room-temperature case, as concluded from an analysis of experimental results. The irreversible capacity loss, which is 1.3 times larger at -20 degrees C than at room temperature, is ascribed to the formation of a porous precipitate of electrolyte decomposition products on the particle surface. Additional Li intercalation at room temperature results in an irreversible capacity loss of 26% from the initial value, and formation of a composite layer, including low-temperature and room-temperature deposited components.