Mitigating the Formation of Tetrahedral Zn in Layered Oxides Enables Reversible Lattice Oxygen Redox Triggering by the Na–O–Zn Configuration

Na-ion layered oxides with Na-O-A' local configurations (A' represents nonredox active cations such as Li⁺, Na⁺, Mg²⁺, Zn²⁺) are attractive cathode choices for energy-dense Na-ion batteries owing to the accumulation of cationic and anionic redox activities. However, the migration of A' would degrade the stability of the Na-O-A' configuration, bringing about drastic capacity decay and local structural distortions upon cycling. Herein, we uncover the close interplay between irreversible Zn migration and the inactivation of lattice oxygen redox (LOR) for layered oxides based on Na-O-Zn configuration by ²³Na solid-state NMR and Zn K-edge EXAFS techniques. We further design a Na_2/3Zn_0.18Ti_0.10Mn_0.72O₂ cathode in which irreversible Zn migration is effectively prevented, and the LOR reversibility is significantly enhanced. Theoretical insights demonstrate that the migrated Zn²⁺ is more inclined to occupy the tetrahedral site rather than the prismatic site and can be effectively minimized by incorporation of Ti⁴⁺ into the transition-metal layer. Our findings substantiate that the Na-O-Zn configuration can be utilized as an appropriate structure to achieve stable LOR by the cautious manipulating of intralayer cation arrangements.