How Fluorine Introduction Solves the Spinel Transition, a Fundamental Problem of Mn-Based Positive Electrodes.

In pursuit of high-capacity Mn-based oxides as positive electrode materials for lithium-ion batteries, the changes in the charge-discharge curve due to the spinel transition still stand in the way of the cycling stability. We found in this study that Li 1.12 Mn 0.74 O 1.60 F 0.40 (LMOF05) positive electrodes with a loose-crystalline rock salt structure (LCRS), in which F is placed near Mn, show a stable and high capacity (300 mA h g -1 , 952 W h kg -1 ) with little change in the charge-discharge curve. We demonstrated by F K-edge soft X-ray absorption spectroscopy and X-ray diffraction (XRD) that a part of F in the LCRS positive electrode forms F-Mn bonds. Operando XRD/X-ray absorption fine structure measurements revealed the lattice size and Mn surrounding environment during charge/discharge of F-containing LCRS positive electrodes (LMOF05), LCRS-LiMnO 2 (LMO), and a spinel-like Li 1.1 Al 0.1 Mn 1.8 O 4 positive electrode (SPINEL). Micro- and macroscopic structural changes indicate how the introduction of F suppresses the local spinel transition in Mn-based positive electrodes. These findings should be an effective tool for applying Co-free positive electrode materials for lithium-ion batteries.