Layered sodium transition-metal (TM) oxides generally suffer from severe capacity decay and poor rate performance during cycling, especially at a high state of charge (SoC). Herein, an insight into failure mechanisms within high-voltage layered cathodes is unveiled, while a two-in-one tactic of charge localization and coherent structures is devised to improve structural integrity and Na+ transport kinetics, elucidated by density functional theory calculations. Elevated Jahn-Teller [Mn3+O6] concentration on the particle surface during sodiation, coupled with intense interlayer repulsion and adverse oxygen instability, leads to irreversible damage to the near-surface structure, as demonstrated by X-ray absorption spectroscopy and in situ characterization techniques. It is further validated that the structural skeleton is substantially strengthened through the electronic structure modulation surrounding oxygen. Furthermore, optimized Na+ diffusion is effectively attainable via regulating intergrown structures, successfully achieved by the Zn2+ inducer. Greatly, good redox reversibility with an initial Coulombic efficiency of 92.6%, impressive rate capability (86.5 mAh g-1 with 70.4% retention at 10C), and enhanced cycling stability (71.6% retention after 300 cycles at 5C) are exhibited in the P2/O3 biphasic cathode. It is believed that a profound comprehension of layered oxides will herald fresh perspectives to develop high-voltage cathode materials for sodium-ion batteries.
Keywords: charge localization; coherent structures; failure mechanisms; layered oxide cathode; sodium-ion battery.