纳米FePO4的合成及其正极材料LiFePO4/C的电化学性能研究

doi:10.3724/SP.J.1077.2012.00422

摘要/Abstract

摘要：

以Fe³⁺为铁源, 采用控制结晶技术合成了纳米FePO₄·xH₂O, 将FePO₄·xH₂O于500℃热处理4?h后得到纳米FePO₄前驱体, 然后通过碳热还原在不同温度下煅烧合成橄榄石结构的纳米LiFePO₄/C样品. 采用差热/热重、X射线衍射、扫描电镜、比表面测试、电化学性能测试等分析测试方法对纳米FePO₄·xH₂O、FePO₄前驱体及不同煅烧温度下制得的纳米LiFePO₄/C样品进行表征.研究结果表明, 700℃烧结10?h合成LiFePO₄/C样品的粒径在40~100?nm左右, 比表面积为79.8 m²/g; 700℃煅烧合成样品在电压2.5~4.2?V, 倍率为0.1C、1C、5C、10C、15C时的放电比容量分别达到156.5、134.9、105.8、90.3和80.9 mAh/g, 具有较好的倍率性能; 样品还表现出较好的容量保持率.

关键词: 控制结晶, LiFePO₄/C, 纳米, 锂离子电池

Abstract:

Nano FePO₄·xH₂O powders were synthesized by controlled crystallization method, using Fe(Ⅲ) compound as the iron source. The nano FePO₄·xH₂O powders were pretreated at 500℃ for 4?h in air to obtain nano FePO₄ precursor. Then the olivine nano LiFePO₄/C composites were obtained through carbonthermal reduction process at different temperatures. The structure, morphology, physicochemical properties and electrochemical properties of the nano FePO₄·xH₂O powder, FePO₄ precursor and LiFePO₄/C composites synthesized at different temperatures were characterized in detail by thermogravimetric/differential scanning calorimeter (TG/DSC), X-ray diffraction (XRD), scanning?electron?microscope (SEM), Brunauer-Emmett-Teller (BET) surface area measurement and electrochemical measurement. The results show that the nano LiFePO₄/C composite calcined at 700℃ for 10?h has fine particle sizes of about 40-100?nm .The BET test shows that the as-prepared nano LiFePO₄/C composite has great specific surface area of 79.8 m²/g. The nano LiFePO₄/C composite cathode material can deliver an initial discharge capacity of 156.5, 134.9, 105.8, 90.3 and 80.9 mAh/g in the voltage range of 2.5-4.2?V, at rate of 0.1C, 1C, 5C, 10C and 15C respectively, which exhibits good rate performance. The nano LiFePO₄/C composite also demonstrates excellent cyclic performance.

Key words: controlled crystallization method, LiFePO₄/C, nano, lithium ion battery

中图分类号:

TM912

武玉玲, 蒲薇华, 任建国, 姜长印, 万春荣. 纳米FePO₄的合成及其正极材料LiFePO₄/C的电化学性能研究[J]. 无机材料学报, 2012, 27(4): 422-426.

WU Yu-Ling, PU Wei-Hua, REN Jian-Guo, JIANG Chang-Yin, WAN Chun-Rong. Synthesis of Nano FePO₄ and Electrochemical Characterization of Composite Cathode Material LiFePO₄/C[J]. Journal of Inorganic Materials, 2012, 27(4): 422-426.

图/表 6

图1 FePO4·xH2O的TG/DSC曲线

Fig. 1 TG/DSC curves of FePO4·xH2O

图2 纳米FePO4·xH2O及不同温度煅烧的纳米LiFePO4/C粉体的XRD图谱

Fig. 2 XRD patterns of nano FePO4·xH2O and LiFePO4/C composites calcined at different temperatures

图3 FePO4前驱体及不同温度煅烧所得LiFePO4/C粉体的SEM照片

Fig. 3 SEM images of nano-FePO4 precursor and LiFePO4/C composites calcined at different temperatures

图4 表1 不同温度下煅烧合成纳米LiFePO4/C样品在不同倍率下的放电比容量

Fig. 4 Cycle performance of the nano LiFePO4/C composites at different rates

Table 1 Specific discharge capacity of nano LiFePO4/C composites at different rates

Sample	Discharge capacity / (mAh·g^-1)
Sample	0.1C	1C	5C	10C	15C
S600	154.5	110.9	85.7	69.2	57.3
S700	156.5	134.9	105.8	90.3	80.9
S800	161.8	128.1	98.0	74.7	41.3

图5 S700样品在不同充放电倍率下的充放电曲线

Fig. 5 Charge-discharge curves of S700 sample at different rates

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纳米FePO₄的合成及其正极材料LiFePO₄/C的电化学性能研究

Synthesis of Nano FePO₄ and Electrochemical Characterization of Composite Cathode Material LiFePO₄/C

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