LiMn0.8Fe0.2PO4/C纳米复合材料的制备与电化学性能研究

doi:10.3724/SP.J.1077.2013.13142

无机材料学报 ›› 2013, Vol. 28 ›› Issue (11): 1248-1254.DOI: 10.3724/SP.J.1077.2013.13142

LiMn_0.8Fe_0.2PO₄/C纳米复合材料的制备与电化学性能研究

苏婧, 吴兴隆, 郭玉国

(中国科学院化学研究所分子纳米结构与纳米技术院重点实验室, 北京100190)

收稿日期:2013-03-08 修回日期:2013-04-24 出版日期:2013-11-20 网络出版日期:2013-10-18
作者简介:苏婧(1986-), 女, 博士研究生. E-mail:sujing@iccas.ac.cn
基金资助:
国家杰出青年科学基金(51225204); 国家重大科学研究计划项目(2012CB932900); 国家863计划 (2012AA110407); 新能源汽车产业动力电池创新项目((2012)1110号)

Preparation and Electrochemical Properties of LiMn_0.8Fe_0.2PO₄/C Nanocomposite

SU Jing, WU Xing-Long, GUO Yu-Guo

(CAS Key Laboratory of Molecular Nanostructure and Nanotechnology, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China)

Received:2013-03-08 Revised:2013-04-24 Published:2013-11-20 Online:2013-10-18
About author:SU Jing. E-mail:sujing@iccas.ac.cn
Supported by:
National Science Foundation for Distinguished Young Scholars of China (51225204); 973 Program (2012CB932900); 863 program (2012AA110407); Technical Innovation Project for New Energy Automotive Industry (2012(1110))

摘要/Abstract

摘要： 结合溶胶-凝胶和高温固相合成方法成功制备了橄榄石结构的LiMn_0.8Fe_0.2PO₄/C固溶体材料, X射线粉末衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)表征结果表明纳米尺度的LiMn_0.8Fe_0.2PO₄颗粒均匀分散于原位形成的碳导电网络中。将该纳米复合材料用作锂离子电池正极材料时, 充放电曲线中除了对应于Fe³⁺/Fe²⁺电对的较短平台(~3.5 V vs Li⁺/Li)外, 更高电压的长平台(~4.1 V vs Li⁺/Li)对应于LiMn_0.8Fe_0.2PO₄晶格中Mn随Li⁺脱出嵌入的氧化还原反应, 该高的电压平台可明显提高相应锂离子电池的能量密度。此外, 使用恒电流间歇滴定技术(GITT)和电化学阻抗谱(EIS)详细研究了LiMn_0.8Fe_0.2PO₄/C电极中锂的化学扩散行为, GITT和EIS所得的锂化学扩散系数D_Li分别为5×10^-15 ~ 1×10^-14 cm²/s和1.27×10^-13 ~ 2.11×10^-13 cm²/s。研究结果表明, DLi值随测试温度的升高而增加, 因此可以通过提高工作温度来改善该类材料的电化学性能。

关键词: LiMn_0.8Fe_0.2PO₄/C纳米复合材料, 恒电流间歇滴定技术, 电化学阻抗谱, 锂化学扩散系数, 锂离子电池

Abstract: Olivine-structured LiMn_0.8Fe_0.2PO₄/C solid solution was successfully prepared by a Sol-Gel approach combined with a high-temperature solid-state reaction, and characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM). The results revealed that LiMn_0.8Fe_0.2PO₄ nanoparticles were evenly dispersed in the in-situ formed carbon conductive network. When the nanocomposite served as a cathode material for lithium-ion batteries (LIBs), except a short plateau (~3.5 V vs Li⁺/Li) ascribed to Fe³⁺/Fe²⁺ couples in the charging/discharging profile, the long plateau at higher voltage (~4.1 V vs Li⁺/Li) is corresponding to the redox reaction of Mn during the Li+ extraction/insertion in the LiMn_0.8Fe_0.2PO₄ lattice, and this high voltage plateau can significantly enhance the energy density of relevant LIBs. In addition, the chemical diffusion behavior of lithium in the LiMn_0.8Fe_0.2PO₄/C electrode was investigated in detail using galvanostatic intermittent titration technique (GITT) and electrochemical impedance spectroscope (EIS), and the chemical diffusion coefficients of lithium, D_Li, obtained by GITT and EIS were 5×10^-15 -1×10^-14 cm²/s and 1.27×10^-13- 2.11×10^-13 cm²/s, respectively. The results indicate that the value of D_Li increases with elevated test temperature, and it can be inferred that the electrochemical properties of such materials can be improved by raising the working temperature.

Key words: LiMn_0.8Fe_0.2PO₄/C nanocomposite, galvanostatic intermittent titration technique, electrochemical impedance spectroscopy, chemical diffusion coefficient of lithium, lithium-ion battery

中图分类号:

TQ174

苏婧, 吴兴隆, 郭玉国. LiMn_0.8Fe_0.2PO₄/C纳米复合材料的制备与电化学性能研究[J]. 无机材料学报, 2013, 28(11): 1248-1254.

SU Jing, WU Xing-Long, GUO Yu-Guo. Preparation and Electrochemical Properties of LiMn_0.8Fe_0.2PO₄/C Nanocomposite[J]. Journal of Inorganic Materials, 2013, 28(11): 1248-1254.

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LiMn_0.8Fe_0.2PO₄/C纳米复合材料的制备与电化学性能研究

Preparation and Electrochemical Properties of LiMn_0.8Fe_0.2PO₄/C Nanocomposite

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