Synergistic Zn/Al Co-Doping and Sodium Enrichment Enable Reversible Phase Transitions in High-Performance Layered...

Layered transition-metal oxides are among the most promising sodium-ion battery cathodes owing to their high specific capacities and structurally tunable frameworks. However, the prototypical P2-Na_0.67Ni_0.33Mn_0.67O₂ (NM) undergoes an irreversible P2 → O2 phase transition at high voltages, accompanied by severe lattice strain and capacity fade, which hinders practical deployment. Here, we propose a cooperative regulation strategy that couples Zn/Al co-doping with Na enrichment, and successfully synthesize P2-Na_0.80Ni_0.14Zn_0.14Mn_0.58Al_0.14O₂ (NMZA-N14). The optimized NMZA-N14 delivers an initial discharge capacity of 125 mAh g^-1 at 0.1C and demonstrates exceptional cycling and rate performance, retaining 98.6% of its capacity after 100 cycles at 0.2C and 93.6% after 200 cycles at 1C. Kinetic analyses indicate a higher Na⁺ diffusion coefficient and a lower charge-transfer resistance in NMZA-N14, evidencing substantially accelerated ion transport. In situ X-ray diffraction further reveals a reversible P2 → OP4 phase transition in the high-voltage regime with a unit-cell volume change of only ~2.27%, thereby avoiding the irreversible structural degradation observed in NM. This synergistic modulation markedly enhances structural stability and electrochemical kinetics, providing a viable pathway for the rational design of high-performance sodium-ion battery cathodes.