High-ionicity fluorophosphate lattice via aliovalent substitution as advanced cathode materials in sodium-ion batteries

As a cathode for sodium-ion batteries(SIBs),Na3V2(PO4)2F3(NVPF)with 3D open framework is a promising candidate due to its high working voltage and large theoretical capacity.However,the severe capacity degradation and poor rate capability hinder its practical applications.The present study demonstrated the optimization of Na-storage performance of NVPF via delicate lattice modulation.Aliovalent substitution of V^(3^(+))at Na^(+)in NVPF induces the generation of electronic defects and expansion of Na^(+)-migration channels,resulting in the enhancement in electronic conductivity and acceleration of Na^(+)-migration kinetics.It is disclosed that the formed stronger Na O bonds with high ionicity than V O bonds lead to the significant increase in structural stability and ionicity in the Na^(+)-substituted NVPF(NVPF-Nax).The aforementioned effects of Na^(+)substitution achieve the unprecedented electrochemical performance in the optimized Na_(3.14)V1.93Na0.07(PO_(4))_(2)F_(3)(NVPF-Na_(0.07)).As a result,NVPF-Na0.07 delivers a high-rate capability(77.5 mAh g^(−1)at 20 C)and ultralong cycle life(only 0.027%capacity decay per cycle over 1000 cycles at 10 C).Sodium-ion full cells are designed using NVPF-Na0.07 as cathode and Se@reduced graphene oxide as anode.The full cells exhibit excellent wide-temperature electrochemical performance from−25 to 25C with an outstanding rate capability(96.3 mAh g^(−1)at 20 C).Furthermore,it delivered an excellent cycling performance over 300 cycles with a capacity retention exceeding 90%at 0.5 C under different temperatures.This study demonstrates a feasible strategy for the development of advanced cathode materials with excellent electrochemical properties to achieve high-efficiency energy storage.