A High-Rate, Durable Cathode for Sodium-Ion Batteries: Sb-Doped O3-Type Ni/Mn-Based Layered Oxides.

O3-Type layered oxides are widely studied as cathodes for sodium-ion batteries (SIBs) due to their high theoretical capacities. However, their rate capability and durability are limited by tortuous Na diffusion channels and complicated phase evolution during Na extraction/insertion. Here we report our findings in unravelling the mechanism for dramatically enhancing the stability and rate capability of O3-NaNiMnSbO (NaNMS) by substitutional Sb doping, which can alter the coordination environment and chemical bonds of the transition metal (TM) ions in the structure, resulting in a more stable structure with wider Na transport channels. Furthermore, NaNMS nanoparticles are obtained by surface energy regulation during grain growth. The synergistic effect of Sb doping and nanostructuring greatly reduces the ionic migration energy barrier while increasing the reversibility of the structural evolution during repeated Na extraction/insertion. An optimized NaNMS-1 electrode delivers a reversible capacity of 212.3 mAh g at 0.2 C and 74.5 mAh g at 50 C with minimal capacity loss after 100 cycles at a low temperature of -20 °C. Such electrochemical performance is superior to most of the reported layered oxide cathodes used in rechargeable SIBs.