Stabilizing Transition Metal Vacancy Induced Oxygen Redox by Co2+/Co3+ Redox and Sodium-Site Doping for Layered Cathode Materials

Anionic redox is an effective way to boost the energy density of layer-structured metal-oxide cathodes for rechargeable batteries. However, inherent rigid nature of the TMO6 (TM: transition metals) subunits in the layered materials makes it hardly tolerate the inner strains induced by lattice glide, especially at high voltage. Herein, P2-Na0.8Mg0.13[Mn0.6Co0.2Mg0.070.13]O-2 (: TM vacancy) is designed that contains vacancies in TM sites, and Mg ions in both TM and sodium sites. Vacancies make the rigid TMO6 octahedron become more asymmetric and flexible. Low valence Co2+/Co3+ redox couple stabilizes the electronic structure, especially at the charged state. Mg2+ in sodium sites can tune the interlayer spacing against O-O electrostatic repulsion. Time-resolved in situ X-ray diffraction confirms that irreversible structure evolution is effectively suppressed during deep desodiation benefiting from the specific configuration. X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations demonstrate that, deriving from the intrinsic vacancies, multiple local configurations of -O-, Na-O-, Mg-O- are superior in facilitating the oxygen redox for charge compensation than previously reported Na-O-Mg. The resulted material delivers promising cycle stability and rate capability, with a long voltage plateau at 4.2 V contributed by oxygen, and can be well maintained even at high rates. The strategy will inspire new ideas in designing highly stable cathode materials with reversible anionic redox for sodium-ion batteries.

Automated summary

Anionic redox can boost the energy density of metal-oxide cathodes, but TMO6 subunits are inherently rigid and may not tolerate inner strains induced by lattice glide. A designed material with vacancies in TM sites and Mg ions improves flexibility and stability, maintaining a long voltage plateau at 4.2 V during deep desodiation. The strategy paves the way for highly stable cathode materials with reversible anionic redox for sodium-ion batteries.