A Na‐Free Surface Enables “Three‐In‐One” Enhancement of Structural, Interfacial and Air Stability for Sodium‐Ion Battery Cathodes

Abstract O3‐type layered oxides are regarded as one of the most promising cathode materials for sodium‐ion batteries. However, the multistep phase transitions, severe electrode/electrolyte parasitic reactions, and moisture sensitivity are challenging for their practical application because of the highly active Na ⁺ . Here, a Na‐free layer is built on the surface of NaNi _1/3 Mn _1/3 Fe _1/3 O ₂ (NMF111) via a leaching treatment and the subsequent surface reconstruction. Accordingly, both the structural degradation from bulk to surface and the overgrowth of the solid electrolyte interface (SEI) are greatly ameliorated, which results in the improved capacity retention of modified NMF111 from 58.3% to 89.6% after 400 cycles at 1 C. Besides, the Na‐free surface with rock‐salt structure prevents the H ⁺ /Na ⁺ exchange and then enables good reversibility and low polarization of the optimal NMF111 when exposed to wet air (50% RH) for 4 days. This work opens a new avenue for the comprehensive cyclability improvement of layered oxides via surface reconstruction.