无机材料学报 ›› 2015, Vol. 30 ›› Issue (7): 739-744.DOI: 10.15541/jim20150003

• • 上一篇    下一篇

Ni替代对锂离子电池材料LiMnTiO4性能的影响

张 栩, 王 禹, 李 悦, 杨 猛, 赵相玉, 马立群   

  1. (南京工业大学 材料科学与工程学院, 南京210009)
  • 收稿日期:2015-01-30 修回日期:2015-02-09 出版日期:2015-07-20 网络出版日期:2015-06-25
  • 作者简介:张 栩(1990 –), 女, 硕士研究生. E-mail: happyyizhan@163.com
  • 基金资助:
    国家自然科学基金(51404142);江苏省自然科学基金(BK20140936);教育部高等学校博士点基金(20133221110009);江苏高校优势学科建设工程(PAPD)

Effect of Nickle Substitution on the Performance of Lithium Ion Battery Material LiMnTiO4

ZHANG Xu, WANG Yu, LI Yue, YANG Meng, ZHAO Xiang-Yu, MA Li-Qun   

  1. (College of Materials Science and Engineering, Nanjing University of Technology, Nanjing 210009, China)
  • Received:2015-01-30 Revised:2015-02-09 Published:2015-07-20 Online:2015-06-25
  • About author:ZHANG Xu. E-mail: happyyizhan@163.com
  • Supported by:
    National Natural Science Foundation of China (51404142);Natural Science Foundation of Jiangsu Province (BK20140936);Specialized Research Fund for the Doctoral Program of Higher Education (20133221110009);Priority Academic Program Development of Jiangsu Higher Education Institution(PAPD)

摘要:

采用溶胶-凝胶法结合固相反应制备了具有立方尖晶石结构的LiMn1-xNixTiO4(x=0、0.1、0.2、0.3)锂离子电池正极材料。通过场发射扫描电镜(FESEM)观察材料的表面形貌, 所制备的材料均呈现出典型的烧结体特征; 用X射线衍射仪(XRD)分析材料的物相变化, Ni替代前后均产生杂相TiO2, 但没有产生与替代元素相关的杂相。通过循环伏安、恒电流充放电等测试研究样品的电化学性能。结果表明: LiMnTiO4有两对氧化还原峰, 分别对应Mn3+/Mn4+、Mn3+/Mn2+的转变, 而Ni替代后出现了额外的氧化还原对, 即Ni3+/Ni4+的转变。LiMn1-xNixTiO4(x=0.1、0.2、0.3)的电化学性能均优于LiMnTiO4, 尤其当Ni替代量为0.1时, LiMn0.9Ni0.1TiO4在30 mA/g电流密度下的首次放电容量为171.6 mAh/g, 48次循环后容量为162.8 mAh/g, 容量保持率为82.7%。对LiMn0.9Ni0.1TiO4进行非原位XRD测试发现, 材料一次循环后结构无明显变化, 不存在立方相与四方相之间的转变。

关键词: 锂离子电池, LiMnTiO4, Ni替代, 溶胶-凝胶法

Abstract:

Spinel LiMn1-xNixTiO4(x=0, 0.1, 0.2, 0.3) cathode materials were prepared by Sol-Gel method. The surface morphology and phase structure of LiMn1-xNixTiO4 (x=0, 0.1, 0.2, 0.3) were characterized by FESEM and XRD. FESEM analysis indicated all the samples consisted of irregular particles and XRD patterns showed that all the materials had impurity TiO2, but there were no impurities related to Ni element. Electrochemical studies of doped and undoped spinels were carried out by cyclic voltammetry (CV) and constant current charge-discharge. CV results showed that LiMnTiO4 had two couples of sharp redox peaks corresponding to Mn3+/Mn4+, Mn2+/Mn3+ redox reactions. However, after Ni substitution, there appeared the third redox coupled, which was related to the Ni3+/Ni4+ redox reaction. LiMn1-xNixTiO4 (x=0.1, 0.2, 0.3) exhibited improved electrochemical properties compared with LiMnTiO4. When the Ni substitution was 0.1, the first discharge capacity of LiMn0.9Ni0.1TiO4 was 171.6 mAh/g at current density of 30 mA/g, and after 48 charge-discharge cycles, the discharge capacity was 162.8 mAh/g, with the capacity retention of 82.7%. The Ex XRD pattern of LiMn0.9Ni0.1TiO4 showed that the material structure had no changes after the first cycle, and there was no transition between cubic phase and tetragonal phase.

Key words: lithium ion batteries, LiMnTiO4, Ni substitution, Sol-Gel

中图分类号: