Coupling Redox Compensation and Interfacial Stabilization in Low-Ni O3-Type Sodium Layered Oxide Cathodes

Abstract Low-Ni O3-type sodium layered oxides are attractive cathodes for cost-robust sodium-ion batteries, yet high-voltage cycling is often limited by Fe-driven degradation, including cation migration/dissolution, irreversible slab gliding with large strain, particle cracking, and accelerated interfacial parasitic reactions. Here, we introduce a redox-interface codesign strategy using stoichiometric, charge-balanced Cu2+/Ti4+ cosubstitution while preserving full Na stoichiometry, transitioning from NaNi1/4Fe1/2Mn1/4O2 to NaNi1/4Fe1/5Mn1/4Cu3/20Ti3/20O2. With the cosubstitution, Cu and Ti suppress Fe migration and dissolution and facilitate sustained Fe oxidation at high voltage. Meanwhile, Cu is also shown to be redox-active, providing reversible cationic charge compensation that mitigates the capacity penalty typically associated with reducing Fe participation. Operando diffraction and spectroscopy collectively indicate a more reversible high-voltage structural evolution with suppressed Fe-related irreversibility. Particularly, spontaneous Ti enrichment at surface/grain-boundary regions stabilizes the cathode−electrolyte interface and promotes a more NaF-rich interphase signature. This work establishes a generalizable route to reconcile stability and capacity in low-Ni, Fe-containing O3 sodium layered oxide cathodes via compositionally encoded bulk-interfacial coupling.