The study of lithium insertion-deinsertion processes into composite graphite electrodes by in situ atomic force microscopy (AFM)

Li insertion-deinsertion into composite graphite electrodes, comprising synthetic graphite flakes (6 μm average size), polyvinylidene difluoride binder (PVdF), and copper current collectors, in commonly used alkyl carbonate solutions were studied by in situ atomic force microscopy (AFM). In this study, we were able to probe by in situ AFM the behavior of practical, composite graphite electrodes in ethylene carbonate-dimethyl carbonate (EC-DMC) solutions containing salts such as LiAsF₆ and LiPF₆ during entire lithiation-delithiation cycles. These in situ micro/nanomorphological studies could probe surface film formation on the graphite particles, as well as periodic volume changes in the graphite flakes during Li insertion-deinsertion cycles. These cyclic volume changes can explain the capacity fading of graphite electrodes upon prolonged cycling, in Li-ion batteries. While the overall morphology of these electrodes remains steady upon cycling in the appropriate solutions (in which the Li-C electrodes are efficiently passivated), there is a continuous problem in the extent of accommodation of the small volume changes in the graphite particles upon lithiation-delithiation, by the surface films. It is suggested that graphite electrodes fail during prolonged cycling due to small scale, continuous reactions of the active mass with solution species, which gradually increase their impedance and decrease the content of the lithium stored in the electrodes.