Li3Fe2(PO4)3/C正极材料的电化学性能及其反应机理研究

doi:10.13208/j.electrochem.141045

电化学（中英文） ›› 2015, Vol. 21 ›› Issue (2): 123-129. doi: 10.13208/j.electrochem.141045

• 化学电源及其材料近期研究专辑（客座编辑：复旦大学夏永姚教授） • 上一篇下一篇

Li₃Fe₂(PO₄)₃/C正极材料的电化学性能及其反应机理研究

谢勇¹，钟贵明²，龚正良^1*，杨勇^1,2*

1. 厦门大学能源学院，福建厦门 361005；2. 固体表面物理化学国家重点实验室，厦门大学化学化工学院，福建厦门 361005

收稿日期:2014-11-03 修回日期:2014-12-19 出版日期:2015-04-28 发布日期:2014-12-25
通讯作者: 龚正良，杨勇 E-mail:zlgong@xmu.edu.cn; yyang@xmu.edu.cn
基金资助:
国家重点基础研究发展计划（No. 2011CB935903）、国家自然科学基金项目（No. 21233004，No. 21303147）和福建省自然科学基金项目（No. 2014J05019）资助

Electrochemical Performance and Reaction Mechanism of Li₃Fe₂(PO₄)₃/C Cathode Material

XIE Yong¹, ZHONG Gui-ming², GONG Zheng-liang^1*, YANG Yong^1,2*

1. College of Energy, Xiamen University, Xiamen 361005, Fujian, China; 2. State Key Lab of Physical Chemistry of Solid Surfaces, and College of Chemistry & Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China

Received:2014-11-03 Revised:2014-12-19 Published:2015-04-28 Online:2014-12-25
Contact: GONG Zheng-liang, YANG Yong E-mail:zlgong@xmu.edu.cn; yyang@xmu.edu.cn

摘要/Abstract

摘要： 采用溶胶凝胶及高能球磨制得Li₃Fe₂(PO₄)₃/C材料，利用多种物理及其电化学技术观察材料形貌，表征材料结构及电化学性能，用电化学原位XAFS等初步研究Li₃Fe₂(PO₄)₃/C超理论容量电化学反应机理. 结果显示，Li₃Fe₂(PO₄)₃/C的结构为单斜晶系，空间群P21/n. 2.0 ~ 4.0 V电位区间，10 mAh·g^-1电流密度，Li₃Fe₂(PO₄)₃/C电极的首周期放电比容量为129 mAh·g^-1，达到其理论容量. 若电位区间拓宽至2.0 ~ 4.95 V，其首周期放电比容量高达165 mAh·g^-1，超出理论的“额外”容量30%. 电化学原位XAFS测试未观察到明显的Fe³⁺/Fe⁴⁺氧化还原对参与电化学反应，初步推测“额外”容量可能来自于该复合材料的高浓度表面缺陷.

关键词: 锂离子电池, Li₃Fe₂(PO₄)₃/C, 电化学性能, 电化学原位XAFS

Abstract: The cathode material of carbon coated Li₃Fe₂(PO₄)₃(Li₃Fe₂(PO₄)₃/C) is successfully prepared by sol-gel method and ball-milling carbon coating technique. The cathode material is characterized by XRD, SEM, TEM, and in-situ XAFS techniques. XRD results indicate that the as prepared Li₃Fe₂(PO₄)₃ is of high purity and single phase, and has monoclinic structure with space group of P21/n. Electrochemical measurements show that the carbon-coated material is able to deliver a high initial discharge specific capacity of 128.6 mAh·g^-1 in the voltage range 2.0 ~ 4.0 V at 10 mA·g^-1. While in the voltage range 2.0 ~ 4.95 V, its initial discharge specific capacities can reach 165 mAh·g^-1, which is 1.3 times higher than the theoretical capacity. In-situ XAFS study show that no obvious evidence of Fe³⁺/Fe⁴⁺ redox couple is involved in the electrochemical reaction, indicating that the capacities which beyond the theoretical capacity may come from the high concentration of surface defects introduced by ball milling process.

Key words: lithium battery, Li₃Fe₂(PO₄)₃/C, electrochemical performance, in-situ XAFS technique

中图分类号:

O646

谢勇，钟贵明，龚正良*，杨勇*. Li₃Fe₂(PO₄)₃/C正极材料的电化学性能及其反应机理研究[J]. 电化学（中英文）, 2015, 21(2): 123-129.

XIE Yong, ZHONG Gui-ming, GONG Zheng-liang*, YANG Yong*. Electrochemical Performance and Reaction Mechanism of Li₃Fe₂(PO₄)₃/C Cathode Material[J]. Journal of Electrochemistry, 2015, 21(2): 123-129.

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https://electrochem.xmu.edu.cn/CN/Y2015/V21/I2/123

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Li₃Fe₂(PO₄)₃/C正极材料的电化学性能及其反应机理研究

Electrochemical Performance and Reaction Mechanism of Li₃Fe₂(PO₄)₃/C Cathode Material

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