应用化学 ›› 2010, Vol. 27 ›› Issue (02): 220-226.DOI: 10.3724/SP.J.1095.2010.90106

• 研究论文 • 上一篇    下一篇

单斜层状结构锂离子电池正极材料LiYxMn1-xO2的合成及电化学性能

粟智*,刘丛,徐茂文   

  1. (新疆师范大学生命科学与化学学院 乌鲁木齐 830054)
  • 收稿日期:2009-02-18 修回日期:2009-06-11 出版日期:2010-02-10 发布日期:2010-02-10
  • 通讯作者: 粟智
  • 基金资助:
    新疆师范大学博士博士后科研资助基金项目(XJNU0807)

Synthesis and Electrochemical Properties of Monoclinic Layered Structure LiYxMn1-xO2 as Cathode Materials for Lithium-ion Batteries

SU Zhi*, LIU Cong, XU Mao-Wen   

  1. (College of Life and Chemistry Science,Xinjiang Normal University,Urumqi 830054)
  • Received:2009-02-18 Revised:2009-06-11 Published:2010-02-10 Online:2010-02-10

摘要:

以Na2CO3 、(CH3CO2)2Mn•4H2O、Y2O3和CH3COOLi•2H2O为原料,采用高温固相法经过2次灼烧和水热离子交换法得到一系列钇掺杂的LiMn1-xYxO2 (x=0.01,0.02,0.03,0.05) 化合物。通过XRD、XPS、循环伏安及恒电流充放电测试,研究了钇掺杂离子对合成正极材料结构及电化学性能的影响。X射线衍射测试结果表明,所得产物均具有单斜层状结构。循环伏安及恒电流充放电测试结果表明,合适的钇掺杂可以起到扩展锂离子脱嵌通道和稳定骨架结构的作用, 钇离子的引入可以部分取代原有的三价锰离子, 由于钇离子的离子半径较三价锰离子大, 因此稀土掺杂锰酸锂材料的晶胞参数比未掺杂材料大, 在一定程度上扩充了锂离子迁移的三维通道, 更有利于锂离子的嵌入与脱嵌,提高单斜层状LiMnO2 材料的电化学循环可逆性及循环稳定性。通过对所得化合物进行了钇掺杂量及电化学性能的研究,得到性能比较优良的LiY0.021Mn0.979O2化合物,其首次放电比容量为125.7 mA·h/g,100次循环以后,放电比容量达212.1 mA·h/g,远高于未掺杂材料的放电容量138 mA·h/g。交流阻抗测试结果表明, Y3+的掺入能降低材料的电化学反应阻抗和提高材料中Li+的扩散能力。

关键词: 单斜LiMnO2, 锂离子电池, 正极材料, 钇掺杂, 电化学性能

Abstract:

A series of yttrium(III) ion doped layered lithium manganese oxides LiYxMn1-xO2 ( y = 0. 01, 0. 02, 0.03 and 0.05) compounds were synthesized with Na2CO3,(CH3COO)2Mn.2H2O ,CH3COOLi?2H2O and Y2O3 as the starting materials by two step high temperautre solid state reaction and hydrothermal ion exchange method. The Y3+-doping effect on structure and the electrochemical performances of the samples were investigated by XRD, XPS ,cyclic voltammetry and charge-discharge tests. The XRD results show that the samples exhibit the same phase as pure monoclinic sturcture compounds . Electrochemical performances indicate that the yttrium ions can partially replace Mn3+ in monoclinic structure LiMnO2 materials and because the radius of Y3+ is bigger than that of Mn3+ , samples doped with yittrium elements have larger lattice constant comparing with that of undoped sample. Doding enables lithium ion to transport more freely in the three dimensional pathway,and all doped with yittrium elements materials show good cycle stability. Experiments of doping ratio and electrochemistry performance were carried out . The compound LiY0.021Mn0.979O2 obtained exhibited a better performance whose initial discharge specific capacity reached 123.4mAh?g-1 respectively. After 100 cycles, the discharge capacity maintains 212.1mAh?g-1,which is much higher the discharge capacity 138 mAh?g-1 of the undoped monoclinic structure LiMnO2 materials. AC analysis shows lower electrochemical impedance and the diffusibility of lithium ion is clearly improved due to Y3+ doping.

Key words: Monoclinic LiMnO2, Li-ion batteries, cathode material, Yttrium doping, electrochemical behaviors

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