Iron–Manganese Dual-Doping Tailors the Electronic Structure of Na3V2(PO4)2F3 for High-Performance Sodium-Ion Batteries

Sodium superionic conductor (NASICON)-type materials are promising cathodes for sodium-ion batteries due to their stable multi-channel frameworks and exceptional ionic conductivity. Among them, Na₃V₂(PO₄)₂F₃ (NVPF) has attracted significant attention. However, the low electronic conductivity and phase impurities limit its sodium storage capability. Herein, we present a Fe and Mn dual-doped NVPF (FM-NVPF) cathode with improved phase purity, electronic conductivity, and electrochemical activities. Detailed ex-situ analyses and density functional theory calculations reveal that Fe and Mn dopants induce defect energy levels and modulate the electronic structure, resulting in a direct-to-indirect bandgap transition in NVPF, which in turn increases carrier concentration and lifetime, accelerates ionic/electronic transport, and improves structural stability. As a result, the FM-NVPF cathode delivers a high capacity of 126.6 mAh g⁻¹ at 0.1 C (1 C = 128 mAh g⁻¹) and outstanding high-rate capability of 67.6 mAh g⁻¹ at 50 C, corresponding to 1.2 min per charge. Furthermore, Na ion full cells assembled with the FM-NVPF cathodes and hard carbon anodes exhibit a high energy density of about 175 Wh kg^-1_{cathode+anode mass} and appealing cyclic stability. This work provides an efficient strategy for developing high-purity and high-performance NVPF cathode materials for advanced sodium-ion batteries.