Influence of Synthesis Parameters on the Short-Range Structure and Electrochemical Performances of Li₂MnO₂F

In the last years, disordered rocksalt structure (DRS) materials were proposed as a positive electrode for lithium-ion batteries. In particular, the fluorinated DRS materials were proposed to be more stable upon cycling than pure oxide counterparts. These materials are mainly obtained by mechanosynthesis in order to incorporate a significant number of F ions and maintain a disordered structure. Since the local structural arrangement is crucial for battery application, we aim to monitor its evolution upon the synthesis of Li₂MnO₂F from two sets of precursors: Mn₂O₃, Li₂O, and LiF or LiMnO₂ and LiF. The synthesis progress was thus followed, by ⁷Li and ¹⁹F MAS NMR coupled to XRD to probe the structure at different scales. This allowed us to identify an optimal milling time to reach the final compounds. We show that they exhibit similar morphology (by SEM), medium- and short-range orders (by XRD, ⁷Li and ¹⁹F NMR, EXAFS), and average Mn oxidation degree (by XANES). The electrochemical performances of the two compounds are almost similar, with high specific capacities of 319 mAh·g^-1 ("from LiMnO₂") and 304 mAh·g^-1 ("from Mn₂O₃") for the first charge to 4.8 V vs Li⁺/Li, proving their interest as post-NMC candidates as positive electrode materials.