LiNi3/8Co2/8Mn3/8O2正极材料氟掺杂改性研究

无机材料学报

LiNi_3/8Co_2/8Mn_3/8O₂正极材料氟掺杂改性研究

李建刚^1,2; 万春荣¹; 杨冬平³; 杨张平³

1. 清华大学核能技术设计研究院, 北京 102201; 2. 北京石油化工学院材料与化工分院, 北京 102617; 3. 大陆太极电池有限公司北京 100176

收稿日期:2003-10-21 修回日期:2004-01-29 出版日期:2004-11-20 网络出版日期:2004-11-20

Fluorine Doping of LiNi_3/8Co_2/8Mn_3/8O₂ Cathode Material for Lithium-ion Batteries

LI Jian-Gang^1,2; WAN Chun-Rong¹; YANG Dong-Ping³; YANG Zhang-Ping³

1. Institute of Nuclear Energy Technology; Tsinghua University; Beijing 102201; China; 2. College of Material & Chemical Engineering; Beijian Institute of Petrochemical Technology; Beijing 102617, China; 3. Beijing Continental Battery Corporation Limited; Beijing 100176; China

Received:2003-10-21 Revised:2004-01-29 Published:2004-11-20 Online:2004-11-20

摘要/Abstract

摘要： 以共沉淀氢氧化物为前驱体制备了F-掺杂化合物LiNi_3/8Co_2/8Mn_3/8O_2-yF_y(y:0,0.05,0.10,0.20),采用XRD、XPS、SEM、循环伏安(CV)、充放电测试、DSC等表征了其结构与性能.结果表明,F^-掺杂置换部分O^2-生成固溶体,不改变样品中过渡金属离子的价态. F^-掺杂量y为0.05、0.10时,比容量不受影响,但在充放电过程中c_h方向膨胀率由未掺杂样的2.06％分别下降至1.017％、1.018％,改善了其结构稳定性与循环寿命,30周后容量保持率分别达97.5％、96.2％;而y增至0.20时,离子混乱度升高,且颗粒间烧结过于严重,内阻增加,使容量与循环特性再度恶化.F^-掺杂还促进材料烧结,使该材料粒径通过粉碎分级控制成为可能,有利于该材料电极的制备.另外,F^-掺杂也使LiNi_3/8Co_2/8Mn_3/8O₂热稳定性得到一定程度改善.

关键词: 锂离子电池, LiNi_3/8Co_2/8Mn_3/8O₂正极材料, 氟掺杂

Abstract: The layered LiNi_3/8Co_2/8Mn_3/8O_2-yF__y(y=0, 0.05, 0.10, 0.20) samples were prepared by using the co-precipitated hydroxide as precursor, and characterized by means of XRD,
XPS, SEM, cyclic voltammetry, charge/discharge tests, DSC etc techniques. The results show that fluorine doping can not induce the valence change of transition metal ions in LiNi_3/8Co_2/8Mn_3/8O_2-yF_y
samples. The samples with y=0.05, 0.10 show better cycling performance with no expense of capacity compared with undoped one, 97.5%, 96.2% capacity retention respectively after 30 cycles can be reached.
The c_h lattice expanding of samples with y=0.05, 0.10 reduces from 2.06% of undoped one to 1.017%, 1.018% respectively when lithium is de-intercalated, contributing to the improvement of structure stability
and electrochemical cycle character. However, the sample with y=0.20 exhibits lower capacity and faster capacity fading upon cycling, due to high cation disordering and internal impedance. Fluorine doping also
accelerates agglomeration of particles of the samples, enhancing operability of electrode preparation of the cathodes. In addition, fluorine-doped samples have better thermal stability than LiNi_3/8Co_2/8Mn_3/8O₂.

Key words: lithium ion batteries, LiNi_3/8Co_2/8Mn_3/8O₂ cathode material, fluorine doping

中图分类号:

TM912

李建刚,万春荣,杨冬平,杨张平. LiNi_3/8Co_2/8Mn_3/8O₂正极材料氟掺杂改性研究[J]. 无机材料学报.

LI Jian-Gang,WAN Chun-Rong,YANG Dong-Ping,YANG Zhang-Ping. Fluorine Doping of LiNi_3/8Co_2/8Mn_3/8O₂ Cathode Material for Lithium-ion Batteries[J]. Journal of Inorganic Materials.

参考文献

[1] Iwahori T, Ozaki Y, Funahashi A, et al. J. Power Sources, 1999, 81--82: 872--876.
[2] Broussely M. J. Power Sources, 1999, 81--82: 140--143.
[3] Tanaka T, Ohta K, Arai N. J. Power Sources, 2001, 97--98: 2--6.
[4] Nishi Y. J. Power Sources, 2001, 100: 101--106.
[5] Leisingh R A, Palazzo M J, Takeuchi E S, et al. J. Electrochem. Soc., 2001, 148: A838--A844.
[6] MacNeil D D, Lu Zh, Chen Zh, et al. J. Power Sources, 2002, 108: 8--14.
[7] Lu Zh, MacNeil D D, Dahn J R. Electrochem. Solid-State Lett., 2001, 4: A191--A194.
[8] Ohzuku T, Makimura Y. Chem. Lett., 2001, 744--755.
[9] Kang S -H, Kim J, Stoll M E, et al. J. Power Sources, 2002, 112: 41--48.
[10] Lu Zh, MacNeil D D, Dahn J R. Electrochem. Solid-State Lett., 2001, 4: A200--A203.
[11] Kim J -S, John C S, Thackeray M M. Electrochem. Commun., 2002, 4: 205--209.
[12] Shaju K M, Subba Rao G V, Chowdari B V R, et al. Electrochimica Acta, 2002, 48: 145--151.
[13] Kubo K, Fujiwara M, Yamada S, et al. J. Power Sources, 1997, 68: 553--557.
[14] Amatucci G G, Pereira N, Zheng T, et al. J. Power Sources, 1999, 81-82: 39--43.
[15] Whitfield P S, Davidson I J. J. Electrochem. Soc., 2000, 147: 4476--4484.
[16] Ohzuku T, Ueda A, Nagayama M, et al. Electrochimica Acta, 1993, 38: 1159--1167.
[17] 陆佩文. 无机材料科学基础. 武汉: 武汉大学出版社, 1996. 65--72.
[18] Rougier A, Gravereau P, Delmas C. J. Electrochem. Soc., 1996, 143: 1168--1175.
[19] Wang H, Jang Y -I, Huang B, et al. J. Electrochem. Soc., 1999, 146: 473--480.
[20] Cho J, Park B. J. Power Sources, 2001, 92: 35--39.
[21] Yu A, Subba Rao G V, Chowdari B V R. Solid State Ionics, 2000, 135: 131--135.
[22] Cho J, Jung H-S, Park Y-C, et al. J. Electrochem. Soc., 2000, 147: 15--20.
[23] Chowdari B V R, Subba Rao G V, Chow S Y. Solid State Ionics, 2001, 140: 55--62.
[24] Paulsen J M, Thomas C L, Dahn J R. J. Electrochem. Soc., 2000, 147: 861--868.
[25] Moshtev R, Zlatilova P, Manev V, et al. J. Power Sources, 1996, 62: 59--66.
[26] 李建刚, 万春荣, 杨冬平, 等(LI Jian-Gang, et al). 物理化学学报(Acta Phys. -Chim. Sin.), 2003, 19: 1030--1034.
[27] Wagner C, Riggs W, Davis L, et al. Handbook of X-ray Photoelectron Spectroscopy, Edited by: Muilenberg G E. Perkin Elmer Corporation, Eden Prairie, Minnesota, 1979. 74--80.

LiNi_3/8Co_2/8Mn_3/8O₂正极材料氟掺杂改性研究

Fluorine Doping of LiNi_3/8Co_2/8Mn_3/8O₂ Cathode Material for Lithium-ion Batteries

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	刘鹏东, 王桢, 刘永锋, 温广武. 硅泥在锂离子电池中的应用研究进展[J]. 无机材料学报, 2024, 39(9): 992-1004.
[2]	程节, 周月, 罗薪涛, 高美婷, 骆思妃, 蔡丹敏, 吴雪垠, 朱立才, 袁中直. 蛋黄壳结构FeF₃·0.33H₂O@N掺杂碳纳米笼正极材料的构筑及其电化学性能[J]. 无机材料学报, 2024, 39(3): 299-305.
[3]	胡梦菲, 黄丽萍, 李贺, 张国军, 吴厚政. 锂/钠离子电池硬碳负极材料的研究进展[J]. 无机材料学报, 2024, 39(1): 32-44.
[4]	苏楠, 邱介山, 王治宇. 高容量氟掺杂碳包覆纳米硅负极材料: 气相氟化法制备及其储锂性能[J]. 无机材料学报, 2023, 38(8): 947-953.
[5]	杨卓, 卢勇, 赵庆, 陈军. X射线衍射Rietveld精修及其在锂离子电池正极材料中的应用[J]. 无机材料学报, 2023, 38(6): 589-605.
[6]	宿拿拿, 韩静茹, 郭印毫, 王晨宇, 石文华, 吴亮, 胡执一, 刘婧, 李昱, 苏宝连. 基于ZIF-8的三维网络硅碳复合材料锂离子电池性能研究[J]. 无机材料学报, 2022, 37(9): 1016-1022.
[7]	王洋, 范广新, 刘培, 尹金佩, 刘宝忠, 朱林剑, 罗成果. 钾离子掺杂提高锂离子电池正极锰酸锂性能的微观机制[J]. 无机材料学报, 2022, 37(9): 1023-1029.
[8]	朱河圳, 王选朋, 韩康, 杨晨, 万睿哲, 吴黎明, 麦立强. 超高镍LiNi_0.91Co_0.06Al_0.03O₂@Ca₃(PO₄)₂正极材料的储锂稳定性的提升机制[J]. 无机材料学报, 2022, 37(9): 1030-1036.
[9]	冯锟, 朱勇, 张凯强, 陈长, 刘宇, 高彦峰. 勃姆石纳米片增强锂离子电池隔膜性能研究[J]. 无机材料学报, 2022, 37(9): 1009-1015.
[10]	陈莹, 栾伟玲, 陈浩峰, 朱轩辰. 基于应力场的锂离子电池正极多尺度失效研究[J]. 无机材料学报, 2022, 37(8): 918-924.
[11]	江依义, 沈旻, 宋半夏, 李南, 丁祥欢, 郭乐毅, 马国强. 双功能电解液添加剂对锂离子电池高温高电压性能的影响[J]. 无机材料学报, 2022, 37(7): 710-716.
[12]	苏东良, 崔锦, 翟朋博, 郭向欣. 石榴石型Li_6.4La₃Zr_1.4Ta_0.6O₁₂对Si/C负极表面固体电解质中间相的调控机制研究[J]. 无机材料学报, 2022, 37(7): 802-808.
[13]	肖美霞, 李苗苗, 宋二红, 宋海洋, 李钊, 毕佳颖. 表面端基卤化Ti₃C₂ MXene应用于锂离子电池高容量电极材料的研究[J]. 无机材料学报, 2022, 37(6): 660-668.
[14]	王禹桐, 张非凡, 许乃才, 王春霞, 崔立山, 黄国勇. 水系锂离子电池负极材料LiTi₂(PO₄)₃的研究进展[J]. 无机材料学报, 2022, 37(5): 481-492.
[15]	李昆儒, 胡省辉, 张正富, 郭玉忠, 黄瑞安. 源于溪木贼的高性能锂离子电池三维多孔生物质硅/碳复合负极材料[J]. 无机材料学报, 2021, 36(9): 929-935.