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, Na3V2(PO4)(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 (similar to 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 Na3V2-xZrx(PO4)(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-solutionreaction 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. (C) 2021 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by ELSEVIER B.V. and Science Press. All rights reserved.

Automated summary

The Zr-doped NVPF coated by N-doped carbon layer materials show improved electronic conductivity and structural stability. The optimized electrode of NVPF-Zr-0.02/NC exhibits high reversible capacities, superior rate capability, and excellent cycling performance, indicating great potential as a high-performance cathode material for sodium ion batteries.