Investigation of carbon-coated silicon oxide phase changes during charge/discharge by oxygen and lithium K-Edge X-ray absorption fine structure spectroscopy

To understand the phase changes associated with the charge/discharge mechanism during cycling, we evaluated the electronic states of oxygen and lithium atoms in the high-capacity anode material SiO-C using O and Li K-edge X-ray absorption fine structure (XAFS) spectroscopy. Multiple peaks observed in the O K-edge spectrum in the 532-548 eV range were likely related to OSi bonds. During the initial charge, when SiO-C occludes Li, a new peak related to LiO bonds appeared at 534 eV. During the initial discharge, this peak was maintained at potentials below 0.7 V vs. Li/Li+, but decreased at higher potentials, suggesting the presence of a phase change point near 0.7 V vs. Li/Li+. This change was also supported by the Li K-edge spectrum. An examination of the phase change after charge/discharge cycling at negative electrode termination potentials of 0.66 and 1.1 V vs. Li/Li+ confirmed that the phase structure was stable when cycling at potentials below the phase change point, but unstable at higher potentials. Thus, stable charge/discharge cycling can be achieved by designing batteries with negative electrode termination potentials that are lower than the potential at which the phase change occurs.