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 Na₃ V₂ (PO₄ )₂ F₃ (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 Na₃ V_1.9 (Ca,Mg,Al,Cr,Mn)_0.1 (PO₄ )₂ F₃ (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.