Study on the effect of vanadium source on the electrochemical performance of sodium vanadium phosphate cathode materials for sodium-ion batteries
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摘要: 以不同提钒工艺制备的中间产物多钒酸铵NH4V3O8（APV）和高纯五氧化二钒为钒源，Na2CO3、NH4H2PO4、柠檬酸分别作钠源、磷源、碳源，采用溶胶凝胶法合成了一系列Na3V2(PO4)3/C正极材料。通过XRD、SEM、电池测试系统和电化学工作站等详细研究了不同钒源对Na3V2(PO4)3/C正极材料的影响。结果显示：钠法提钒多钒酸铵为钒源制备的NaH-NVP正极材料呈现较好的循环性能和优异的高倍率性能，在5C和10C高倍率下分别表现出98 mAh/g和64 mAh/g的可逆容量。此项研究拓展了合成磷酸钒钠材料的钒源选择，对降低磷酸钒钠的制备成本具有积极意义。Abstract: A series of Na3V2(PO4)3/C anode materials were synthesized by sol-gel method, using the intermediate products ammonium polyvanadate (APV, NH4V3O8) prepared by different vanadium extraction processes and high-purity vanadium pentoxide as vanadium sources, and Na2CO3, NH4H2PO4, and citric acid as sodium, phosphorus, and carbon sources, respectively. The effects of different vanadium sources on Na3V2(PO4)3/C anode materials were investigated in detail through XRD, SEM, battery testing system and electrochemical workstation. The results show that the Na3V2(PO4)3/C (NaH-NVP) cathode materials prepared by ammonium polyvanadate from sodium method for vanadium extraction as the vanadium source present superior high-rate performance, i.e., reversible capacities of 98 mAh/g and 64 mAh/g at 5C and 10C, respectively. The research has expanded the selection of vanadium sources for synthesizing sodium vanadium phosphate materials, which has a positive significance in reducing the preparation cost of sodium vanadium phosphate.
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Key words:
- vanadium source /
- sol-gel method /
- sodium vanadium phosphate /
- cathode materials
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图 1 溶胶-凝胶法制备NVP正极材料的合成示意
Figure 1. Synthesis diagram of NVP cathode material prepared by sol-gel method
图 2 不同钒源制备的NVP正极材料的XRD衍射图谱
Figure 2. XRD patterns of NVP cathode materials prepared from different vanadium sources
图 3 不同钒源合成的NVP材料的表面形貌及区域放大
Figure 3. Surface morphology and regional magnification of NVP materials synthesized from different vanadium sources
(a)(d)NaH-NVP；(b)(e)GaH-NVP；(c)(f)GC-NVP
图 4 NaH-NVP、GaH-NVP和GC-NVP的充放电曲线和循环性曲线
(a)(b)(c)充放电曲线；(d)循环性曲线
Figure 4. Galvanostatic charge-discharge curves and cycling performance of NaH-NVP, GaH NVP and GC-NVP samples
图 5 NaH-NVP、GaH-NVP和GC-NVP材料的倍率性能
Figure 5. Rate performance of NaH-NVP, GaH-NVP and GC-NVP materials
图 6 NaH-NVP、GaH-NVP和GC-NVP样品的交流阻抗图谱和Warburg系数Zw图
(a)交流阻抗图谱；(b)Warburg系数Zw图
Figure 6. Electrochemical impedance spectroscopy and Warburg coefficients Zw of NaH-NVP, GaH NVP and GC-NVP samples
表 1 不同工艺钒源的成分表
Table 1. Compositions table of V2O5 from different processes
% V Ca Na Si Mn K Fe Cr 钙法APV 49.73 0.02 0.012 0.013 0.081 0.122 0.046 <0.01 钠法APV 50.16 0.248 0.082 <0.01 0.072 0.013 0.065 高纯V2O5 55.95 0.010 0.013 <0.01 <0.01 0.010 
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表 2 NaH-NVP、GaH-NVP和GC-NVP材料的循环性能和倍率性能
Table 2. Cycling and rate performances of NaH-NVP, GaH-NVP and GC-NVP materials
循环性能/(mAh·g−1) 倍率性能/(mAh·g−1) 1st 150th 0.2C 0.5C 1C 2C 5C 10C 回到0.2C NaH-NVP 117 111 117 110 110 109 98 64 111 GaH-NVP 112 107 118 107 106 104 80 108 GC-NVP 111 104 120 104 95 85 49 106
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