无机盐工业
主管:中海油天津化工研究设计院有限公司
主办:中海油天津化工研究设计院有限公司
   中海油炼油化工科学研究院(北京)有限公司
   中国化工学会无机酸碱盐专业委员会
ISSN 1006-4990 CN 12-1069/TQ

无机盐工业 ›› 2024, Vol. 56 ›› Issue (4): 50-56.doi: 10.19964/j.issn.1006-4990.2023-0313

• 研究与开发 • 上一篇    下一篇

纳米级LiNi0.05Mn1.95O4正极材料制备及电化学性能研究

钱志慧1(), 朱琴1, 马姣1, 郭昱娇1,2(), 向明武1, 郭俊明1()   

  1. 1.云南民族大学化学与环境学院, 云南省高校绿色化学材料重点实验室, 云南 昆明 650500
    2.昆明理工大学环境科学与工程学院, 云南 昆明 650093
  • 收稿日期:2023-06-08 出版日期:2024-04-10 发布日期:2024-04-18
  • 通讯作者: 郭昱娇,女,高级工程师;E-mail:guoyujiao1988@163.com
    郭俊明,男,教授,硕士生导师;E-mail:guojunming@tsinghua.org.cn
  • 作者简介:钱志慧(1999— ),女,硕士,研究方向为锂离子电池正极材料;E-mail:1138562350@qq.com
  • 基金资助:
    国家自然科学基金项目(51972282);国家自然科学基金项目(U1602273)

Study on preparation and electrochemical properties of nano-sized LiNi0.05Mn1.95O4 cathode materials

QIAN Zhihui1(), ZHU Qin1, MA Jiao1, GUO Yujiao1,2(), XIANG Mingwu1, GUO Junming1()   

  1. 1.Key Laboratory of Green-Chemistry Materials in University of Yunnan Province,School of Chemistry and Environment,Yunnan Minzu University,Kunming 650500,China
    2.Faculty of Environmental Science and Engineering,Kunming University of Science and Technology,Kunming 650093,China
  • Received:2023-06-08 Published:2024-04-10 Online:2024-04-18

摘要:

为有效抑制尖晶石锰酸锂的Jahn-Teller效应,改善其在高倍率充放电循环中容量衰减快的问题,采取熔盐燃烧法和不同焙烧温度成功制得LiNi0.05Mn1.95O4样品。实验结果表明,Ni掺杂和不同的焙烧温度没有改变LiMn2O4的晶体结构,随焙烧温度升高,结晶性增加,颗粒尺寸增大,逐渐由纳米级变为亚微米级。在优化焙烧温度650 ℃下制备的样品电化学性能最优,5C下初始放电比容量及500次循环后容量保持率分别为100.8 mA·h/g和80.0%,更高倍率(10C)下500次循环容量仅衰减7.5%。动力学性能测试结果表明,其具有较大锂离子扩散系数(3.26×10-16 cm2/s)和较小表观活化能(25.67 kJ/mol)。Ni掺杂和不同的焙烧温度抑制了LiMn2O4材料的Jahn-Teller效应,提高了材料的倍率性能和循环寿命。

关键词: 尖晶石型LiMn2O4, Ni掺杂, 熔盐燃烧法, Jahn-Teller效应, 焙烧温度

Abstract:

To effectively suppress Jahn-Teller effect of spinel lithium manganate and improve the problem of rapid capacity decay during high-rate charge discharge cycles,the LiNi0.05Mn1.95O4 samples were successfully prepared by using a molten salt combustion method and different calcination temperatures.The experiment results demonstrated that the crystal structure of LiMn2O4 did not change under Ni-doping and different calcination temperatures.With the rise of calcination temperature,the crystallinity and particle size of the samples were increased continuously.Besides,the particle sizes were gradually increased from nanoscales to submicron scales.The optimal calcination temperature of 650 ℃ delivered excellent electrochemical performance.The initial discharge specific capacity at 5C and the capacity retention rate after 500 cycles were 100.8 mA·h/g and 80.0%,respectively.At a higher rate of 10C,the capacity of 500 cycles only attenuated by 7.5%.The dynamic performance test results indicated that it had a large lithium-ion diffusion coefficient of 3.26×10-16 cm2/s and a smaller apparent activation energy of 25.67 kJ/mol.Ni doping and different calcination temperatures inhibited the Jahn-Teller effect of LiMn2O4 materials,thereby promoted the rate performance and cycle life of LiMn2O4 materials.

Key words: spinel LiMn2O4, Ni-doping, molten-salt combustion method, Jahn-Teller effect, calcination temperature

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