With great superiorities in energy density,rate capability and structural stability,Na3V2(PO4)2F3 (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 fab-ricated 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)2F3/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.

Chuan Guo;Jianwei Yang;Zhiyuan Cui;Shuo Qi;Qianqian Peng;Weiwei Sun;Li-Ping Lv;Yi Xu;Yong Wang;Shuangqiang Chen

School of Environmental and Chemical Engineering,Shanghai University,Shanghai 200444,China

能源化学

[1]Chuan Guo;Jianwei Yang;Zhiyuan Cui;Shuo Qi;Qianqian Peng;Weiwei Sun;Li-Ping Lv;Yi Xu;Yong Wang;Shuangqiang Chen-.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)[J].能源化学,2022(02):514-523

xZrx

In,situ,structural,evolution,analysis,doped,Na3V2,PO4,2F3,coated,by,carbon,layer,high,performance,cathode,sodium,batteries,With,great,superiorities,energy,density,capability,stability,NVPF,attracted,much,attentions,battery,but,also,faces,challenges,its,poor,intrinsic,electronic,conductivity,controversial,sodiation,Herein,series,thickness,homogenously,materials,are,fab,ricated,gel,method,optimized,heteroatom,doping,amounts,improve,properties,enlarging,lattice,distance,enhancing,respectively,Specifically,among,samples,NC,electrode,delivers,reversible,capacities,mAh,excellent,cycling,monitored,ray,diffractometer,follows,step,wise,extraction,intercalation,multi,phase,changes,not,just,solid,solution,reaction,one,Full,cells,hard,demonstrate,capacity,out,put,voltage,good,This,work,favorable,accelerate,development,explore,possible,redox,mechanisms,SIBs

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