Towards a Universal Design Principle for Low-Hysteresis High-Valent Redox in Battery Cathodes: Synergizing Cationic Ordered Vacancies with Tunable Metal-Ligand Hybridization

Sodium-ion batteries (SIBs) have the potential to meet growing demand for energy storage due to their low costs stemming from natural resource abundances, but their cathode energy density must be improved to be comparable to lithium-ion battery (LIBs) cathodes. One strategy to improve performance is accessing high voltage capacity through high-valent redox reactions. Such reactions usually cause instability in cathode materials, but Na2Mn3O7 (NMO) has demonstrated excellent performance in the high-valent regime with high reversibility due to its unique lattice structure with ordered Mn vacancies. This work seeks to expand the universality of ordered-vacancy as a design principle and increase the material candidates with such exceptional electrochemical behavior. Our approach involves synergizing cationic ordered vacancies with tunable metal-ligand hybridization through partial metal substitution. Particularly, we successfully incorporated Fe3+ for Mn4+ in NMO to make Na2.5Mn2.5Fe0.5O7 and achieved improved high-valent redox behavior. Fe substitution leads to larger specific capacities compared to pristine NMO (171 to 159 mAh/g first cycle discharge) and enhanced cycle stability (97 to 60 mAh/g after 50 cycles) in the voltage range 1.5-4.3 V vs. Na/Na+ as well as superior rate performance. This study lays the foundation for developing new cathode materials with stable high-valent redox through substitution of redox active transition metals by employing cationic ordered vacancy and partial transition metal substitution as design principles in tandem.