硫掺杂Na3（VOPO4）2F正极材料的制备及储钠性能
收稿日期: 2023-04-26
网络出版日期: 2024-02-06
基金资助
国家自然科学基金项目(52002407);湖南省自然科学基金项目(2021JJ40730)
Preparation and sodium storage properties of sulfur-doped Na3（VOPO4）2F cathode materials
Received date: 2023-04-26
Online published: 2024-02-06
聚阴离子型Na3（VOPO4）2F材料具有结构稳定、安全性高及工作电压高等特性，其开放的三维框架结构可以为钠离子的快速迁移提供路径，是目前最具发展潜力的钠离子电池正极材料之一。然而，Na3（VOPO4）2F的本征电子导电性较差，导致倍率性能不理想。离子掺杂是一种提升材料导电性和电化学性能的有效策略。通过水热法成功制备了S2-掺杂的Na3（VOPO4）2S x F材料。XRD和电化学阻抗结果表明，S2-掺杂可以扩大离子扩散通道并降低电荷传输电阻；恒电流间歇滴定测试结果显示S2-掺杂可以加快离子迁移速率。因此，Na3（VOPO4）2S x F正极材料在钠离子半电池中表现出优异的电化学性能，在30C倍率下可逆比容量为66.8 mA·h/g，在10C倍率下循环500次后容量保持率可达96%。Na3（VOPO4）2S x F正极与硬碳负极组成的钠离子全电池可获得121.7 mA·h/g的高比容量，在1C倍率下循环60次后，其容量衰减可以忽略不计。
周煌 , 胡晓萍 , 任稳 , 曹鑫鑫 . 硫掺杂Na3（VOPO4）2F正极材料的制备及储钠性能[J]. 无机盐工业, 2024 , 56(2) : 30 -37 . DOI: 10.19964/j.issn.1006-4990.2023-0239
The polyanionic Na3（VOPO4）2F material has the characteristics of structural stability，high safety，and high operating voltage.Its open three-dimensional framework structure can provide a pathway for the rapid migration of sodium ions，making it one of the most promising cathode electrode materials for sodium ion batteries at present.However，the rate performance of Na3V2（PO4）2O2F is unsatisfactory because of its poor intrinsic electronic conductivity.Ion doping is an effective strategy for improving the conductivity and electrochemical performance of this material.S2--doped Na3（VOPO4）2S x F was successfully prepared by adding appropriate amounts of thioacetamide in the hydrothermal process.X-ray diffraction and electrochemical impedance spectroscopy results indicated that the doping of S2- could expand ion diffusion channels and reduce charge transfer resistance.The results of galvanostatic intermittent titration technique proved that S2- doping could accelerate ion migration rate.Thus，the Na3（VOPO4）2S x F delivered an excellent electrochemical performance in the sodium ion half-cell，showing a capacity of 66.8 mA·h/g at 30C and retaining 96% of its capacity after 500 cycles at 10C.A sodium ion full cell coupled with the Na3（VOPO4）2S x F cathode and hard carbon anode delivered a high capacity of 121.7 mA·h/g，and the capacity loss after 60 cycles at 1C could be ignored.
Key words： Na3（VOPO4）2F; ion-doping; cathode material; sodium ion batteries
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