First-principles modeling of structural and RedOx processes in high-voltage Mn-based cathodes for sodium-ion batteries

Abstract Sodium-ion batteries are increasingly regarded as a sustainable alternative to lithium-ion technology for large-scale energy storage, but their development remains limited by the lack of durable high-energy cathodes. Among the most promising candidates, P2–Mn-based layered oxides combine high theoretical capacity with structural versatility, yet their performance is constrained by two degradation pathways: (i) the irreversible participation of lattice oxygen in the redox process and (ii) voltage-driven solid-state phase transitions. This research article synthesizes our recent ab initio investigations aimed at disentangling the atomistic origins of these processes occurring in the high-voltage regime. We show that Mn deficiency activates oxygen redox but also promotes O 2 release, whereas Fe and Ru doping strengthen TM–O covalency, enabling reversible anionic redox. In parallel, we identify cooperative Jahn–Teller distortions and Na + /vacancy reorganization as the driving forces of high-voltage phase transitions and propose simple geometric descriptors as predictive tools for structural stability. Together, these insights help to establish quantum-based design guidelines for layered sodium cathodes: reinforce TM–O covalency, suppress oxygen evolution, and mitigate phase instabilities. By combining first-principles modeling with targeted compositional design, we pave the way toward the accelerated discovery of sustainable, cobalt-free, and high-energy cathodes for next-generation sodium-ion batteries.