In-situ structural evolution analysis of Zr-doped Na3V2(PO4)2F3 coated by N-doped carbon layer as high-performance cathode for sodium-ion batteries

With great superiorities in energy density, rate capability and structural stability, Na 3 V 2 (PO 4 ) 2 F 3 (NVPF) has attracted much attentions as cathode of sodium ion battery (SIB), but it also faces challenges on its poor intrinsic electronic conductivity and the controversial de/sodiation mechanism. Herein, a series of Zr-doped NVPF coated by N-doped carbon layer (~5 nm in thickness, homogenously) materials are fabricated by a sol–gel method, and the optimized heteroatom-doping amounts of Zr and N doping improve intrinsic properties on enlarging lattice distance and enhancing electronic conductivity, respectively. Specifically, among all samples of Na 3 V 2− x Zr x (PO 4 ) 2 F 3 /NC (NVPF-Zr- x /NC, x  = 0, 0.01, 0.02, 0.05, and 0.1), the optimized electrode of NVPF-Zr-0.02/NC delivers high reversible capacities (119.2 mAh g −1 at 0.5 C), superior rate capability (98.1 mA h g −1 at 20 C) and excellent cycling performance. The structural evolution of NVPF-Zr-0.02/NC electrode, in-situ monitored by X-ray diffractometer, follows a step-wise Na-extraction/intercalation mechanism with reversible multi-phase changes, not just a solid-solution-reaction one. Full cells of NVPF-Zr-0.02/NC//hard carbon demonstrate high capacity (99.8 mA h g −1 at 0.5 C), high out-put voltage (3.5 V) and good cycling stability. This work is favorable to accelerate the development of high-performance cathode materials and explore possible redox reaction mechanisms of SIBs.