Abstract

Manganese (Mn)-based positive electrode materials have attracted significant attention because of their low-risk resources, high valence ranges, and their ability to form polymorphs. Loose-crystalline rock-salt LiMnO2 (LCRS-LMO) synthesized via a mechanochemical method exhibited a capacity of ca. 190 mAh g−1 with a potential range of 5.0–2.0 V. The potential curve of LCRS-LMO after 11 charge/discharge cycles exhibited a characteristic 4 V signal, which is similar to the 4 V plateau observed in the transition from layered LiMnO2 or orthorhombic LiMnO2 to the spinel Li-Mn oxide. However, no diffraction peaks corresponding to a spinel-related structure were detected by X-ray diffraction (XRD) measurements of the bulk structure. Furthermore, in situ XRD revealed for the first time that the lattice size of LCRS-LMO approached that of the spinel-related oxide as the charge/discharge process progressed. The local structural changes of LCRS-LMO examined by in situ X-ray absorption fine structure measurements suggest that the local structure around the manganese ions tends to be aligned toward the spinel-related lattice.

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