Mn2+掺杂对V2O5纳米材料结构与电化学性能的影响

doi:10.3724/SP.J.1077.2013.13137

无机材料学报 ›› 2013, Vol. 28 ›› Issue (11): 1200-1206.DOI: 10.3724/SP.J.1077.2013.13137

Mn²⁺掺杂对V₂O₅纳米材料结构与电化学性能的影响

李兆龙¹, 孙华君¹, 徐杰¹, 张晓艳¹, 黄胜男¹, 朱泉峣¹, 陈文¹, Galina S. Zakharova²

(1. 武汉理工大学材料复合新技术国家重点实验室, 武汉430070; 2. 俄罗斯科学院乌拉尔分院固态化学研究所, 叶卡捷琳堡620990, 俄罗斯)

收稿日期:2013-03-08 修回日期:2013-04-10 出版日期:2013-11-20 网络出版日期:2013-10-18
作者简介:李兆龙(1988-), 男, 博士研究生.
基金资助:
国家自然科学基金(51072152, 50872101); 国家自然科学基金国际合作项目(中-俄51011120252); 科技部国际合作项目(2013DFR50710); 湖北省自然科学基金重点项目(2010CDA015); 武汉市科学技术计划项目(201051730550); 中央高校基本科研业务费专项基金(125201010)

Effect of Mn²⁺ Doping on Structure and Electrochemical Properties of V₂O₅ as the Rechargeable Electrode Material

LI Zhao-Long¹, SUN Hua-Jun¹, XU Jie¹, ZHANG Xiao-Yan¹, HUANG Sheng-Nan¹, ZHU Quan-Yao¹, CHEN Wen¹, Galina S. Zakharova²

(1. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China; 2. Institute of Solid State Chemistry of the Ural Branch, Russian Academy of Science, Yekaterinburg 620990, Russia)

Received:2013-03-08 Revised:2013-04-10 Published:2013-11-20 Online:2013-10-18
About author:LI Zhao-Long.
Supported by:
National Natural Science Foundation of China (51072152, 50872101); Joint project of National Natural Science Foundation of China and Russian Foundation for Basic Research (NSFC-RFBR 51011120252); International Science & Technology Cooperation Program of China (2013DFR50710); Natural Science Foundation of Hubei Province (Key Program) (2010CDA015); Wuhan Scientific and Technological Project (201051730550); Fundamental Research Funds for the Central Universities (125201010)

摘要/Abstract

摘要： 以V₂O₅粉末、H₂O₂和Mn(CH₃COO)₂·4H₂O为原料, 采用水热法制备了纳米结构的锂离子电池阴极材料Mn_xV₂O₅。运用X射线衍射(XRD)、X射线光电子能谱分析(XPS)和扫描电镜(SEM)测试对制备的材料进行结构和形貌表征, 并利用充放电测试和交流阻抗测试研究了样品的电化学性能。结果表明: 随着锰掺杂量的增加, V₂O₅的正交晶型层状结构未发生改变, 其层间距逐渐扩大, 形貌由纳米短棒状向纳米带簇状变化。电化学测试表明: Mn²⁺掺杂提高了V₂O₅的电化学性能, 其首次充放电效率由70.8%提高到90%以上; Mn_0.01V₂O₅经过90次充放电循环后, 其容量仍为192.2 mAh/g。Mn²⁺掺杂对V₂O₅电极材料的离子电导率有影响, Mn_0.02V₂O₅离子电导率由未掺杂时的6.27×10^-4 S/cm提高到1.58×10^-3 S/cm。

关键词: Mn_xV₂O₅, 电极材料, 离子掺杂, 电化学性能

Abstract: Mn_xV₂O₅ (x=0~0.06) was prepared by hydrothermal method with H₂O₂ and V₂O₅ as precursors and Mn²⁺ added directly in the sol preparation process. Structures and morphologies of the materials were characterized by X-ray diffraction (XRD), X-ray Photoelectron Spectroscope (XPS) and scanning electron microscope (SEM). The results indicate that the V₂O₅ is well crystallized as an orthorhombic structure without any detectable impurity phase with the doping of Mn²⁺. The doping Mn²⁺ is situated between anionic sheets of VO₆ chain in the V₂O₅ and the morphology of V₂O₅ changes from nanorods to nanobelts cluster. The electrochemical behavior of the Mn_xV₂O₅ acted as cathode materials is studied by charge-discharge test and electrochemical impedance spectra (EIS) test through a three electrode system. The results indicate that the efficiency of the first charge-discharge of the material enhances to 90% with the Mn²⁺ doping. The discharge capacity of the Mn_0.01V₂O₅ is up to 192.2 mAh/g after 90 charge-discharge cycles at 0.2C rate. The doping Mn²⁺ performs efficiently in ionic conductivity of V₂O₅ electrode material, and the ionic conductivity of Mn_0.02V₂O₅ is enhanced from 6.27×10^-4 S/cm to 1.58×10^-3 S/cm.

Key words: Mn_xV₂O₅, electrode material, ion doping, electrochemical properties

中图分类号:

O657

李兆龙, 孙华君, 徐杰, 张晓艳, 黄胜男, 朱泉峣, 陈文, Galina S. Zakharova. Mn²⁺掺杂对V₂O₅纳米材料结构与电化学性能的影响[J]. 无机材料学报, 2013, 28(11): 1200-1206.

LI Zhao-Long, SUN Hua-Jun, XU Jie, ZHANG Xiao-Yan, HUANG Sheng-Nan, ZHU Quan-Yao, CHEN Wen, Galina S. Zakharova. Effect of Mn²⁺ Doping on Structure and Electrochemical Properties of V₂O₅ as the Rechargeable Electrode Material[J]. Journal of Inorganic Materials, 2013, 28(11): 1200-1206.

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Mn²⁺掺杂对V₂O₅纳米材料结构与电化学性能的影响

Effect of Mn²⁺ Doping on Structure and Electrochemical Properties of V₂O₅ as the Rechargeable Electrode Material

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