An Advanced High‐Entropy Fluorophosphate Cathode for Sodium‐Ion Batteries with Increased Working Voltage and Energy Density

Abstract Impossible voltage plateau regulation for the cathode materials with fixed active elemental center is a pressing issue hindering the development of Na‐superionic‐conductor (NASICON)‐type Na₃V₂(PO₄)₂F₃ (NVPF) cathodes in sodium‐ion batteries (SIBs). Herein, a high‐entropy substitution strategy, to alter the detailed crystal structure of NVPF without changing the central active V atom, is pioneeringly utilized, achieving simultaneous electronic conductivity enhancement and diffusion barrier reduction for Na⁺, according to theoretical calculations. The as‐prepared carbon‐free high‐entropy Na₃V_1.9(Ca,Mg,Al,Cr,Mn)_0.1(PO₄)₂F₃ (HE‐NVPF) cathode can deliver higher mean voltage of 3.81 V and more advantageous energy density up to 445.5 Wh kg⁻¹, which is attributed by the diverse transition‐metal elemental substitution in high‐entropy crystalline. More importantly, high‐entropy introduction can help realize disordered rearrangement of Na⁺ at Na(2) active sites, thereby to refrain from unfavorable discharging behaviors at low‐voltage region, further lifting up the mean working voltage to realize a full Na‐ion storage at the high voltage plateau. Coupling with a hard carbon (HC) anode, HE‐NVPF//HC SIB full cells can deliver high specific energy density of 326.8 Wh kg⁻¹ at 5 C with the power density of 2178.9 W kg⁻¹. This route means the unlikely potential regulation in NASICON‐type crystal with unchangeable active center becomes possible, inspiring new ideas on elevating the mean working voltage for SIB cathodes.