Activating Reversible Anionic Redox in Layered Oxide Cathodes for Highly Stable Sodium-Ion Batteries by Li/Nb Codoping

The exploitation of high-capacity, long-cycle cathode materials with reversible anionic redox activity and robust structural stability remains an essential challenge for sodium-ion batteries. Herein, we address these limitations through Na–O–A configuration modulation in P2–Na 0.67 [Ni x Li y Mn 1– x–y ]O 2, which fundamentally enables reversible anionic redox reactions and ensures structural stability. The obtained P2–Na 0.67 Ni 0.23 Mn 0.67 Li 0.08 Nb 0.02 O 2 cathodes deliver a remarkable reversible capacity of 158.4 mAh g –1 at 0.1C while maintaining extraordinary cycling stability with 98.2% capacity retention after 500 cycles at 5C (a minimal capacity fade of only 0.0036% per cycle). The introduction of the Na–O–Li/Nb configuration enables dual cationic and anionic redox reactions (ARR) to enhance capacity. Meanwhile, the high-valence Nb 5+ species not only suppresses oxygen release through robust Nb–O bonds, thereby improving the reversibility of ARR, but also reinforces the structural rigidity of the transition metal-layer framework. Ultimately, this modulation strategy provides a universal pathway for designing highly stable, high-energy cathodes for next-generation sodium-ion batteries.