Building Homogenous Li2TiO3 Coating Layer on Primary Particles to Stabilize Li‐Rich Mn‐Based Cathode Materials

Abstract Li‐rich Mn‐based oxides (LRMOs) are promising cathode materials for next‐generation lithium‐ion batteries (LIBs) with high specific energy (≈900 Wh kg −1 ) because of anionic redox contribution. However, LRMOs suffer from issues such as irreversible release of lattice oxygen, transition metal (TM) dissolution, and parasitic cathode–electrolyte reactions. Herein, a facile, scalable route to build homogenous and ultrathin Li 2 TiO 3 (LTO) coating layer on the primary particles of LRMO through molten salt (LiCl) assisted solid–liquid reaction between TiO 2 and Li 1.08 Mn 0.54 Co 0.13 Ni 0.13 O 2 is reported. The prepared LTO‐coated Li 1.08 Mn 0.54 Co 0.13 Ni 0.13 O 2 (LTO@LRMO) exhibits 99.7% capacity retention and 95.3% voltage retention over 125 cycles at 0.2 C, significantly outperforming uncoated LRMO. Combined characterizations of differential electrochemical mass spectrometry, in situ X‐ray diffraction, and ex situ X‐ray photoelectron spectroscopy evidence significantly suppressed oxygen release, phase transition, and interfacial reactions. Further analysis of cycled electrodes reveals that the LTO coating layer inhibits TM dissolution and prevents the lithium anode from TM crossover effect. This study expands the primary particle coating strategy to upgrade LRMO cathode materials for advanced LIBs.