Fluoride Doping Na3Al2/3V4/3(PO4)3 Microspheres As Cathode Materials for Sodium‐Ion Batteries with Multielectron Redox

Abstract Sodium‐ion batteries (SIBs) are potential candidates for large energy storage usage because of the natural abundance and cheap sodium. Nevertheless, improving the energy density and cycling steadiness of SIB cathodes remains a challenge. In this work, F‐doping Na 3 Al 2/3 V 4/3 (PO 4 ) 3 (NAVP) microspheres (Na 3 Al 2/3 V 4/3 (PO 4 ) 2.9 F 0.3 (NAVPF)) are synthesized via spray drying and investigated as SIB cathodes. XRD and Rietveld refinement reveal expanded lattice parameters for NAVPF compared to the undoped sample, and the successful cation doping into the Na superionic conductor (NASICON) framework improves Na + diffusion channels. The NAVPF delivers an ultrahigh capacity of 148 mAh g −1 at 100 mA g −1 with 90.8% retention after 200 cycles, enabled by the activation of V 2+ /V 5+ multielectron reaction. Notably, NAVPF delivers an ultrahigh rate performance, with a discharge capacity of 83.6 mAh g −1 at 5000 mA g −1 . In situ XRD demonstrates solid‐solution reactions occurred during charge–discharge of NAVPF without two‐phase reactions, indicating enhanced structural stability after F‐doped. The full cell with NAVPF cathode and Na + preintercalated hard carbon anode shows a large discharge capacity of 100 mAh g −1 at 100 mA g −1 with 80.2% retention after 100 cycles. This anion doping strategy creates a promising SIB cathode candidate for future high‐energy‐density energy storage applications.