Post‐Substitution Modulated Robust Sodium Layered Oxides

Abstract Sodium layered oxides feature in high capacity and diverse composition, however, are plagued by various issues including limited kinetics and interfacial instability with residual alkali. Conventional substitution/doping and heterogeneous coating are promising to tackle the problems of bulk and surface, respectively, but normally insufficient to address both. Herein, a post‐substitution strategy is proposed to modify primary sodium‐layered‐oxide particles that can simultaneously deal with bulk and surficial issues. As a typical example, post Ti‐substitution for O3‐NaNi 1/3 Fe 1/3 Mn 1/3 O 2 is successfully performed by adjusting thermodynamic driving force, resulting in depth‐controllable Ti infusion from surface to bulk, as proved by energy dispersive spectroscopy maps collected at the cross‐section. Residual alkali species are efficiently diminished and benefited from the surface‐to‐bulk osmotic reaction, significantly improving Coulombic efficiency. Moreover, remarkable enhancements in reversible capacity (135 mAh g −1 at C/10), rate capability (74% retention at 5 C), and long‐term cycling stability (80% retention after 300 cycles at 2 C) are achieved by manipulating gradient‐like Ti distribution in a primary particle that brings with increased kinetics and strengthened interfacial stability, surpassing those given by rough heterotic coating and homogeneous Ti‐substitution. Such post‐substitution is expected to provide a universal strategy to modify primary layered‐oxide particles for developing advanced cathode materials of SIBs.