Stabilized Anionic Redox by Rational Structural Design from Surface to Bulk for Long‐Life Fast‐Charging Li‐Rich Oxide Cathodes

Abstract On account of high capacity and high voltage resulting from anionic redox, Li‐rich layered oxides (LLOs) have become the most promising cathode candidate for the next‐generation high‐energy‐density lithium‐ion batteries (LIBs). Unfortunately, the participation of oxygen anion in charge compensation causes lattice oxygen evolution and accompanying structural degradation, voltage decay, capacity attenuation, low initial columbic efficiency, poor kinetics, and other problems. To resolve these challenges, a rational structural design strategy from surface to bulk by a facile pretreatment method for LLOs is provided to stabilize oxygen redox. On the surface, an integrated structure is constructed to suppress oxygen release, electrolyte attack, and consequent transition metals dissolution, accelerate lithium ions transport on the cathode–electrolyte interface, and alleviate the undesired phase transformation. While in the bulk, B doping into Li and Mn layer tetrahedron is introduced to increase the formation energy of O vacancy and decrease the lithium ions immigration barrier energy, bringing about the high stability of surrounding lattice oxygen and outstanding ions transport ability. Benefiting from the specific structure, the designed material with the enhanced structural integrity and stabilized anionic redox performs an excellent electrochemical performance and fast‐charging property..