Chemical-state distributions in charged LiCoO2 cathode particles visualized by soft X-ray spectromicroscopy
Wen‐Xiong Zhang, Eiji Hosono, Daisuke Asakura, Hayato Yuzawa, Takuji Ohigashi, Masaki Kobayashi, Hisao Kiuchi, Yoshihisa Harada
Abstract
Abstract Lithium-ion deintercalation/intercalation during charge/discharge processes is one of the essential reactions that occur in the layered cathodes of lithium-ion batteries, and the performance of the cathode can be expressed as the sum of the reactions that occur in the local area of the individual cathode particles. In this study, the spatial distributions of the chemical states present in prototypical layered LiCoO 2 cathode particles were determined at different charging conditions using scanning transmission X-ray microscopy (STXM) with a spatial resolution of approximately 100 nm. The Co L 3 - and O K -edge X-ray absorption spectroscopy (XAS) spectra, extracted from the same area of the corresponding STXM images, at the initial state as well as after charging to 4.5 V demonstrate the spatial distribution of the chemical state changes depending on individual particles. In addition to the Co L 3 -edge XAS spectra, the O K -edge XAS spectra of the initial and charged LiCoO 2 particles are different, indicating that both the Co and O sites participate in charge compensation during the charging process possibly through the hybridization between the Co 3 d and O 2 p orbitals. Furthermore, the element maps of both the Co and O sites, derived from the STXM stack images, reveal the spatial distribution of the chemical states inside individual particles after charging to 4.5 V. The element mapping analysis suggests that inhomogeneous reactions occur on the active particles and confirm the existence of non-active particles. The results of this study demonstrate that an STXM-based spatially resolved electronic structural analysis method is useful for understanding the charging and discharging of battery materials.