Revealing the anionic redox chemistry in O3-type layered oxide cathode for sodium-ion batteries

Anion redox chemistry plays a crucial role in Na-deficient or Na-rich oxide cathodes for sodium-ion batteries (SIBs). But the oxygen redox chemistry has been rarely reported in O3-type (Na-full) layered oxides for SIBs. Herein, we reveal the anion redox chemistry in O3-type NaMn1/3Fe1/3Ni1/3O2 (MFN) cathode material, and propose an integrated strategy combining ZrO2 coating and Zr4+ doping to tune the anionic redox chemistry and crystal structures which improves the activity, reversibility, and stability of O2−. Oxygen redox reactions with high reversibility and cyclic stability mainly occur between 4.0 V and 4.3 V. The structure of Na-O-TM is regulated by Zr4+ doping, and the electronic state of O-2p occupies a higher energy level by the regulation of Na-O-TM structure. The electrons can migrate from O2- more easily and O2−/O− contribute more capacity. Zr4+ doping optimizes the lattice structure, enlarges the Na layer, and decreases TMO2 layer, which reduces the diffusion resistance of Na+ and increases the structural stability. ZrO2 layer effectively mitigates the corrosion of the electrolyte and ensures the integrity of the structure, which inhibits the formation of Na2CO3 on the surface and decreases CO2 release. This study not only reveals the anion redox chemistry in O3-type layered oxide cathode material but also is available for insights into regulating the redox activity, reversibility, and stability of oxygen.