Boosting the Structural Reversibility of Layered Oxide Cathode for Realizing Long‐Term Cycle Life Through Electronic Structure Regulation

O3-type layered oxide cathode exhibits great application potential for practical sodium-ion batteries, due to its cost-effectiveness, abundant sodium and manganese resources, and high theoretical capacity. However, the irreversible phase transition, coupled with rapid capacity decay, which is primarily attributed to the Jahn-Teller effect of Mn³⁺, remains a significant bottleneck for commercial application. Additionally, the sluggish kinetics during the (de)sodiation process require urgent improvement. Herein, an electronic structure regulation strategy is proposed by low-valence Li/Cu co-substitution to address these issues. The roles of Li/Cu on the electronic structure, structural evolution, and electrochemical properties in the Na_0.96Ni_0.22Fe_0.2Mn_0.5Li_0.04Cu_0.04O₂ (NFMLC) cathode are comprehensively explored through systematic in situ/ex situ characterization techniques and theoretical calculations. The results reveal that this strategy effectively activates more Ni^2+/3+ and Fe^3+/4+ redox reactions above 2.5 V, while suppressing Mn^3+/4+ redox activity below 2.5 V, thereby achieving highly structural reversibility. Therefore, the NFMLC electrode displays excellent long-term cycling stability (81.5% capacity retention after 2000 cycles at 5 C), and significantly enhanced rate performance (from 45.5% to 80.4% under a ratio of 5 C to 0.5 C). This work provides a valuable perspective on the design of low-cost, long-life, and high-performance layered oxide cathodes for practical sodium-ion batteries.