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 (11): 39-44.doi: 10.19964/j.issn.1006-4990.2024-0235

• 新能源电池材料 • 上一篇    下一篇

采用两步固相法配合表面活性剂制备LiMn0.7Fe0.3PO4/C正极材料的研究

马镰仁1,2,3(), 谢红艳1,2,3()   

  1. 1.贵州大学材料与冶金学院,贵州 贵阳 550025
    2.贵州省冶金工程与过程节能重点实验室,贵州 贵阳 550025
    3.贵州省高等学校高性能电池材料重点实验室,贵州 贵阳 550025
  • 收稿日期:2024-04-26 出版日期:2024-11-10 发布日期:2024-05-22
  • 通讯作者: 谢红艳(1983— ),女,博士,教授,研究方向为锰资源综合利用、锰系电池材料制备研究工作;E-mail:xiehongyanxy@163.com
  • 作者简介:马镰仁(1996— ),男,硕士,研究方向为锂离子正极材料;E-mail:867925152@qq.com
  • 基金资助:
    国家地区科学基金项目(52364045)

Study on preparation of LiMn0.7Fe0.3PO4/C cathode materials by two-step solid-phase method with surfactant

MA Lianren1,2,3(), XIE Hongyan1,2,3()   

  1. 1.School of Materials and Metallurgy,Guizhou University,Guiyang 550025,China
    2.Guizhou Provincial Key Laboratory of Metallurgical Engineering and Process Energy Conservation,Guiyang 550025,China
    3.Key Laboratory of High;Performance Battery Materials,Guizhou Provincial Universities,Guiyang 550025,China
  • Received:2024-04-26 Published:2024-11-10 Online:2024-05-22

摘要:

磷酸锰铁锂复合材料能够兼具磷酸铁锂和磷酸锰锂优点,得到较高的能量密度,但锰铁比过高反而会降低材料的离子电导率和电子电导率。为了提高电导率并降低材料阻抗,采用表面活性剂油酸辅助的两步固相方法,制备了粒径较小、孔隙分布均匀且碳包覆薄厚均匀适中的LiMn0.7Fe0.3PO4/C正极材料(LFMP/C-3)。循环充放电测试表明,该材料在1C下放电比容量为119.6 mA·h/g,循环100次后为102.8 mA·h/g,循环效率为88.87%。经倍率测试得出,在0.1C、0.5C、1C、2C、5C和10C倍率下的平均放电比容量分别为141.08、132.70、128.44、105.86、89.10、83.40 mA·h/g,在之后的0.1C倍率下仍能恢复到开始5次的平均水平。循环伏安(CV)和交流阻抗(EIS)测试表明,LFMP/C-3样品具备较小的极化程度、最低的电荷转移阻抗(139.75 Ω/s1/2)和较高的锂离子扩散系数(1.46×10-14 cm2/s)。结果表明,油酸的加入可获得良好的形貌特征,从而促进锂离子的脱嵌,提高材料的离子电导率和电子电导率,提高磷酸锰铁锂正极材料的电化学性能。

关键词: LiMn0.7Fe0.3PO4/C, 碳包覆, 固相法, 电化学, 正极材料

Abstract:

The olivine structure of lithium manganese iron phosphate lithium composite materials can combine the advantages of lithium iron phosphate and lithium manganese phosphate,achieving higher energy density.However,an excessively high manganese iron ratio can reduce the materials's ionic and electronic conductivity.To improve conductivity and reduce material impedance,a two-step solid-phase method with the surfactant oleic acid was used to obtain LiMn0.7Fe0.3PO4/C cathode material(LFMP/C-3) with smaller morphology,uniform pore distribution,and moderately even carbon coating thickness.Cycling charge and discharge test results showed that cycling discharge capacity at 1C was 119.6 mA·h/g,which decreased to 102.8 mA·h/g after 100 cycles with a cycling efficiency of 88.87%.Rate capability testing revealed average discharge capacities at 0.1C,0.5C,1C,2C,5C,and 10C rates were 141.08,132.70,128.44,105.86,89.10 and 83.40 mA·h/g respectively,and it could recover to the initial 5-cycle average at 0.1C rate.Cyclic voltammetry and electrochemical impedance spectroscopy showed that the LFMP/C-3 sample exhibited the lower polarization degree,the lowest charge transfer impedance(139.75 Ω/s1/2),and a higher lithium ion diffusion coefficient(1.46×10-14 cm2/s).The results indicated that the addition of oleic acid could improve the morphology characteristics,facilitate lithium ion intercalation,enhance material ionic and electronic conductivity,and improve the electrochemical performance of lithium manganese iron phosphate cathode materials.

Key words: LiMn0.7Fe0.3PO4/C, carbon coating, solid-phase method, electrochemistry, cathode materials

中图分类号: