Anionic‐Based Layered Oxide Cathodes with High Electrochemical Performance through Dual‐Site Substitutions for Sodium‐Ion Batteries

Mn-rich layered oxide cathodes with anionic redox promise high energy density for sodium-ion batteries (SIBs) due to ultra-high capacity derived from both Mn and O redox couples. Nevertheless, instability of the reactions that lead to poor electrochemical stability hinders the cathodes from practical applications. Here, the Al and Zn dual-site substitution strategy is proposed to enhance electrochemical performance. The designed cathode, Na_0.73Zn_0.03Li_0.25Mn_0.76Al_0.01O₂ (AlZn), delivers a high discharge capacity of 242 mAh g^-1 with an impressive rate capability (162 mAh g^-1 at 1000 mA g^-1) and excellent capacity retention (89.69% over 150 cycles). In addition, full-cell SIB based on AlZn coupled with hard carbon exhibits a high energy density of 317 Wh kg^-1 (based on both cathode and anode mass) and a reasonable capacity retention of 80.8% after 250 cycles. Revealed by advanced investigations, the synergy of robust Al-O in TM layers and O-Zn-O pillars in Na layers helps alleviate severe inactive spinel/rock-salt phase transformation and intragranular cracks in the AlZn cathode. This consequently leads to greatly enhanced electrochemical performance over the pristine cathode. This work provides insight into improving electrochemical properties of anionic-redox-based layered oxides by Al/Zn co-substitutions toward high-energy SIBs.