Stabilizing Anionic Redox Chemistry in a Mn‐Based Layered Oxide Cathode Constructed by Li‐Deficient Pristine State

Abstract

Li-rich cathode materials are of significant interest for coupling anionic redox with cationic redox chemistry to achieve high-energy-density batteries. However, lattice oxygen loss and derived structure distortion would induce serious capacity loss and voltage decay, further hindering its practical application. Herein, a novel Li-rich cathode material, O3-type Li_0.6 [Li_0.2 Mn_0.8 ]O₂ , is developed with the pristine state displaying both a Li excess in the transition metal layer and a deficiency in the alkali metal layer. Benefiting from stable structure evolution and Li migration processes, not only can high reversible capacity (≈329 mAh g^-1 ) be harvested but also irreversible/reversible anionic/cationic redox reactions are comprehensively assigned via the combination of in/ex situ spectroscopies. Furthermore, irreversible lattice oxygen loss and structure distortion are effectively restrained, resulting in long-term cycle stability (capacity drop of 0.045% per cycle, 500 cycles). Altogether, tuning the Li state in the alkali metal layer presents a promising way for modification of high-capacity Li-rich cathode candidates.