Interfacial Engineering of P2-Type Ni/Mn-Based Layered Oxides by a Facile Water-Washing Method for Superior...

Owing to the strong basicity and reactivity, residual sodium compounds (RSCs) on the surface of Na-based layered oxides for sodium-ion batteries (SIBs) cause the deterioration of the electrochemical performance and processability of the oxide cathode materials. Herein, considering P2-type Na_0.66Ni_0.26Zn_0.07Mn_0.67O₂ as the model material, the water-washing treatment is proven to be a facile, economic, and highly efficient method to improve the electrochemical performance of P2-type Ni/Mn-based layered oxides. Experimental results show that RSCs on material surfaces can be effectively removed by water washing without causing severe damage to the bulk structure. Notably, water washing triggers the formation of an ultrathin (2-3 nm thick) Na-poor disordered interfacial layer on the surface of Na_0.66Ni_0.26Zn_0.07Mn_0.67O₂. This layer plays a passivating role in further enhancing the material's resistance to water and reduces the reactivity of the material surface with the electrolyte. These compositional and structural optimizations for P2-type Na_0.66Ni_0.26Zn_0.07Mn_0.67O₂ effectively suppress the release of gaseous CO₂, formation of thick cathode-electrolyte interphase films, and consumption of active Na⁺, enabling good Na⁺ transport kinetics during cycling. The water-washed Na_0.66Ni_0.26Zn_0.07Mn_0.67O₂ exhibits significantly improved cycling stability with a capacity retention of 89.1% at 100 mA g^-1 after 100 cycles and rate capability with a discharge capacity of 76.3 mA g^-1 at 2000 mA g^-1; these values are higher than those of the unwashed Na_0.66Ni_0.26Zn_0.07Mn_0.67O₂ (83.3%, 71.4 mA h g^-1). This work provides fundamental insights into the detrimental effect of RSCs on the electrochemical performance of layered oxides and highlights the importance of regulating interfacial compositions for developing high-performance layered-oxide cathode materials for SIBs.