由电解磷铁废渣制备的FePO4合成LiFePO4研究

doi:10.3724/SP.J.1077.2012.00475

摘要/Abstract

摘要：

在磷酸水溶液中, 以磷铁废渣为阳极、石墨为阴极, 恒流无膜电解后溶液由无色变为黄色, 用氨水调节pH值, 经过滤、洗涤、干燥, 得到淡黄色粉体, XRD和热分析结果表明该粉体组成为FePO₄·2H₂O. 在电解产物中加入LiOH·H₂O和葡萄糖, 用乙醇作溶剂充分研磨形成流变相前驱体, 在700℃氩气气氛中焙烧得到LiFePO₄/C复合物. 用动电位极化方法分析了磷铁的电解过程, 用XRD、SEM和循环伏安法(CV)研究了LiFePO₄/C复合物的结构、形貌及电化学性能. 测试结果表明LiFePO₄/C复合物没有磷铁原料的杂质峰, 氧化电位和还原电位分别在3.54和3.33 V, 说明经过阳极袋电解能够消除磷铁原料中的杂质元素影响及锂离子脱/嵌过程中极化较小.

关键词: 锂离子电池, LiFePO₄, Fe_1.5P, 电解, 循环伏安法

Abstract:

Fe_1.5P waste slag was galvanostatically electrolyzed without separator in a H₃PO₄ aqueous solution using graphite as the cathode, and the electrolyte color turned from achromatism to yellow after electrolysis. Light yellow powder was finally obtained by adjusting the value of pH using ammonia water, filtering, washing and drying in sequence. The results of XRD and TG-DTA showed that the as-electrolyzed product was FePO₄·2H₂O. The as-obtained FePO₄·2H₂O was mixed well with LiOH·H₂O and glucose to form a rheological phase precursor by using ethanol as a dispersing agent. LiFePO₄/C composite was synthesized successfully by calcining the above precursor at 700℃ in an Ar atmosphere. The electrolysis process was investigated via a potentiodynamic polarization method. The structure, morphology and electrochemical performance of the as-synthesized LiFePO₄/C composite were characterized by XRD, SEM and cyclic voltammetry, respectively. There was no impurity indexed peaks from Fe_1.5P raw material, and the oxidization potential and the reduction potential were at 3.54 V and 3.33 V, respectively. The good experimental results indicated that electrolysis of Fe_1.5P waste slag using an anode bag can eliminate the effect of impurities from raw material and the polarization between lithium ion intercalation and de-intercalation was low.

Key words: lithium-ion battery, LiFePO₄, Fe_1.5P, electrolysis, cyclic voltammetry

中图分类号:

TM911

刘严, 王贵欣, 闫康平, 李成佳. 由电解磷铁废渣制备的FePO₄合成LiFePO₄研究[J]. 无机材料学报, 2012, 27(5): 475-479.

LIU Yan, WANG Gui-Xin, YAN Kang-Ping, LI Cheng-Jia. Synthesis of LiFePO₄ Using FePO₄ Produced by Electrolyzing Fe_1.5P Waste Slag[J]. Journal of Inorganic Materials, 2012, 27(5): 475-479.

图/表 7

图1 磷铁原料的XRD图谱

Fig. 1 XRD pattern of the Fe-P raw material

图2 磷铁在磷酸水溶液中的动电位极化曲线

Fig. 2 Potentiodynamic polarization curves of the Fe1.5P in H3PO4 aqueous solution

图3 (a) 未焙烧, (b) 600℃空气中焙烧3 h电解产物的XRD图谱

Fig. 3 ? XRD patterns of the electrolytic products (a) uncalcined and (b) calcined at 600℃ in air for 3 h

图4 电解产物的TG-DTA 曲线

Fig. 4 TG-DTA curves of the electrolytic product

图5 由电解产物合成的LiFePO4/C的XRD图谱

Fig. 5 XRD pattern of the as-synthesized LiFePO4/C from the electrolytic product

图6 合成的LiFePO4/C复合材料的SEM 照片

Fig. 6 SEM image of the as-synthesized LiFePO4/C

图7 合成的LiFePO4/C的循环伏安曲线

Fig. 7 ββCyclic voltammogram of the as-synthesized LiFePO4/C

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由电解磷铁废渣制备的FePO₄合成LiFePO₄研究

Synthesis of LiFePO₄ Using FePO₄ Produced by Electrolyzing Fe_1.5P Waste Slag

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