Anionic Redox and Electrochemical Kinetics of the Na2Mn3O7 Cathode Material for Sodium-Ion Batteries

Manganese-based layered oxides have gained wide attention as cathode materials for sodium-ion batteries due to their cost-effectiveness and nontoxicity. Among them, Na2Mn3O7, which shows promising electrochemical properties as a host material for sodium ions, has been extensively investigated recently. However, the charge compensation mechanisms during battery operation are still ambiguous. Herein, we investigate the electronic structure of Na2Mn3O7 using X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering techniques. Mn L-II,L-III-edge XAS spectra show that manganese ions do not undergo any oxidation reaction during the first charge process, suggesting that sodium removal is instead charge compensated by oxygen-ion redox reactions. This, in turn, has an impact on the cycling performances delivered by the material, especially the capacity retention over cycles and also the electrochemical kinetics of sodium ions in Na2Mn3O7.