Sustainable Anionic Redox by Inhibiting Li Cross-Layer Migration in Na-Based Layered Oxide Cathodes

The irrational utilization of an anionic electron often accompanies structural degradation with an irreversible cation migration process upon cycling in sodium-layered oxide cathodes. Moreover, the insufficient understanding of the anionic redox involved cation migration makes the design strategies of high energy density electrodes even less effective. Herein, a P3-Na 0.67 Li 0.2 Fe 0.2 Mn 0.6 O 2 (P3-NLFM) cathode is proposed with the in-plane disordered Li distribution after an in-depth remolding of the Li ribbon-ordered P3-Na 0.6 Li 0.2 Mn 0.8 O 2 (P3-NLM) layered oxide. The disordered Li sublattice in the transition metal slab of P3-NLFM leads to the dispersed | O 2p orbitals, the lowered charge transfer gap, and the suppressed phase transition at high voltages. Then the enhanced Mn–O interaction and electronic stability are disclosed by the crystal orbital Hamilton population (COHP) analysis at high voltage in P3-NLFM. Furthermore, ab initio molecular dynamics (AIMD) simulation suggests the order/disorder of the transition metal layer is highly correlated with the stability of the Li sublattice. The cross-layer migration and loss of Li in P3-NLM are suppressed in P3-NLFM to enable the high reversibility upon cycling. As a result, the P3-NLFM delivers a high capacity of 163 mAh g –1 without oxygen release and an enhanced capacity retention of 81.9% (vs 42.9% in P3-NLM) after 200 cycles, which constitutes a promising approach for sustainable oxygen redox in rechargeable batteries.