Orbital-modulation-induced charge redistribution enables high-rate and low-temperature O3-type sodium cathodes

The dynamic hysteresis of layered oxide cathodes intrinsically limits the performance of sodium-ion batteries under high-rate and low-temperature conditions. These limitations arise from unfavorable electronic configurations and valence band structures, including localized d-states, wide bandgaps, and weak orbital hybridization, all of which hinder electron transport and Na⁺ migration. Overcoming these bottlenecks requires a shift away from empirical modifications to the deliberate engineering of electronic structure and band alignment. In this work, we propose an electronic-structure engineering strategy based on orbital hybridization and charge redistribution. High-valence W⁶⁺ induces strong orbital hybridization with host 3d states, narrowing the bandgap and decreasing the charge-transfer barrier. Charge redistribution partially reduces adjacent Ni/Mn sites, increasing electronic conductivity and expanding Na⁺ diffusion channels. The modified cathode exhibits remarkable rate performance (96.2 mAh g⁻¹ at 20 C) and excellent low-temperature capacity (91.0 mAh g⁻¹ at −40 °C). This work establishes a mechanism-guided design approach that links orbital and electronic regulation to enhanced electrode kinetics, providing an attractive pathway for sodium-ion batteries under extreme conditions.