物理化学学报 >> 2010, Vol. 26 >> Issue (10): 2633-2637.doi: 10.3866/PKU.WHXB20101015

电化学 上一篇    下一篇

水合肼对锂离子正极材料LiNi0.5Mn1.5O4 性能的影响

常照荣, 代冬梅, 李苞, 汤宏伟   

  1. 河南师范大学化学与环境科学学院,河南新乡453007
  • 收稿日期:2010-02-12 修回日期:2010-07-15 发布日期:2010-09-27
  • 通讯作者: 常照荣 E-mail:czr_56@163.com
  • 基金资助:

    国家自然科学基金(21071046)和河南省重点科技攻关项目(080102270013)资助

Effect of Hydrazine on the Performance of LiNi0.5Mn1.5O4Cathode Materials

CHANG Zhao-Rong, DAI Dong-Mei, LI Bao, TANG Hong-Wei   

  1. College of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453007, Henan Province, P. R. China
  • Received:2010-02-12 Revised:2010-07-15 Published:2010-09-27
  • Contact: CHANG Zhao-Rong E-mail:czr_56@163.com
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21071046) and Henan Key Scientific and Technological Project, China (080102270013).

摘要:

以NiSO4 和MnSO4 为原料, 在用共沉淀法经二次干燥制备锂离子电池正极材料LiNi0.5Mn1.5O4 的前驱体时, 加入水合肼进行还原处理. 实验结果发现: 经还原处理的前驱体制备正极材料LiNi0.5Mn1.5O4 的充放电比容量远远高于同样条件下不经水合肼还原处理的前驱体制备的正极材料的充放电比容量, 而且处理前驱体制备的正极材料在高倍率放电条件下电化学行为更好. 粉末X 射线衍射(XRD) 和扫描电镜(SEM) 测试结果表明, 用还原剂水合肼处理的前驱体合成的样品为单一的尖晶石结构, 晶粒呈规则的八面体形貌, 没有杂质相, 而未处理前驱体合成的样品则含有少量的杂质相. 这种杂质相是在前驱体的制备过程中由于Mn(OH)2 被O2 氧化而形成难溶Na0.55Mn2O4·1.5H2O 化合物, 最终转变为Na0.7MnO2.05.

 

关键词: 正极材料, LiNi0.5Mn1.5O4, 锂离子电池, 共沉淀法, 还原处理

Abstract:

Reduction pretreatment of the precursor of LiNi0.5Mn1.5O4 was carried out by adding hydrazine to a solution of NaOH during precursor synthesis. Accordingly, the effect of hydrazine on the performance of LiNi0.5Mn1.5O4 was studied by comparing the electrochemical properties of this sample with those of pristine samples (LiNi0.5Mn1.5O4 without hydrazine pretreatment). We synthesized LiNi0.5Mn1.5O4 by co-precipitation using a two-step drying method with NiSO4 and MnSO4 as raw materials. The results of electrochemical experiments show that the LiNi0.5Mn1.5O4 from the hydrazine pretreated precursor has a much higher special capacity than the pristine sample at the same charge/ discharge current density. Moreover, the former shows much better electrochemical performance at a high discharge current density. Results of powder X-ray diffraction (XRD) reveal that the LiNi0.5Mn1.5O4 from the hydrazine pretreated precursor shows a pure spinel phase (no impurity phase detected) while the pristine sample containsa minor impurity phase. Results of scanning electron microscopy (SEM) show that the crystal impurities have a layered structure and are mixed with octahedral crystals of LiNi0.5Mn1.5O4. We show that the impurity in the precursor is insoluble Na0.55Mn2O4·1.5H2O, which derives from the oxidation of Mn(OH)2 by O2 and a final transformation into Na0.7MnO2.05.

 

Key words: Cathode material, LiNi0.5Mn1.5O4, Lithium ion battery, Coprecipitation method, Reductiontreatment

MSC2000: 

  • O646