锂离子正极材料LiCo1-xMgxMnO4与LiCo1-xAlxMnO4 (x = 0, 0.02, 0.05, 0.1)的制备及其电化学性能

doi:10.13208/j.electrochem.121122

电化学（中英文） ›› 2014, Vol. 20 ›› Issue (1): 22-27. doi: 10.13208/j.electrochem.121122

锂离子正极材料LiCo1-xMgxMnO4与LiCo1-xAlxMnO4 (x = 0, 0.02, 0.05, 0.1)的制备及其电化学性能

游美玲¹，童庆松¹，李秀华¹，林忞²，黄行康^1*，杨勇^2*

1. 福建师范大学化学系，福建福州 350007；2. 厦门大学固体表面物理化学国家重点实验室，化学化工学院化学系，福建厦门 361005

收稿日期:2012-11-22 修回日期:2013-01-10 出版日期:2014-02-25 发布日期:2014-02-24
通讯作者: 黄行康，杨勇 E-mail:xkhuang@126.com; yyang@xmu.edu.cn
基金资助:
福建省教育厅科技项目（A类，No. JA10072）、福建省高校杰出青年科研人才计划项目（No. JA11040）以及福建省自然科学基金计划项目（No. 2011J05021）资助

Synthesis and Electrochemical Properties of LiCo_1-xMg_xMnO₄ and LiCo_1-xAl_xMnO₄(x= 0, 0.02, 0.05, 0.1) as Positive Materials for Lithium-ion Batteries

YOU Mei-ling¹, TONG Qing-song¹, LI Xiu-hua¹, LIN Min², HUANG Xing-kang^1*, YANG Yong^2*

1. Department of Chemistry, Fujian Normal University, Fuzhou 35007, China; 2. State Key Laboratory for Physical Chemistry of Solid Surfaces, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China

Received:2012-11-22 Revised:2013-01-10 Published:2014-02-25 Online:2014-02-24
Contact: HUANG Xing-kang, YANG Yong E-mail:xkhuang@126.com; yyang@xmu.edu.cn

摘要/Abstract

摘要： 采用固相法合成掺杂镁和铝尖晶石LiCoMnO₄材料，研究镁和铝掺杂量对尖晶石LiCoMnO₄电极的初始容量、放电平台以及循环性能的影响. 利用扫描电子显微镜、粉末X-射线衍射仪观察分析材料形貌及结构. 结果表明，所合成材料的粒径分布均匀，结晶性较佳. LiCoMnO₄电极初始容量为87.0 mAh.g^-1，少量镁或铝掺杂使电极初始容量有所增加，LiCo_0.98Mg_0.02MnO₄和LiCo_0.98Al_0.02MnO₄电极初始容量分别为91.3和93.6 mAh.g^-1，提高了其5 V放电平台的比例，过量掺杂则其容量降低. 此外，掺杂Al显著改善了LiCoMnO₄电极的循环性能，而掺杂镁对电极的循环性能其影响不明显.

关键词: 固相合成, 尖晶石LiCoMnO₄, 镁掺杂, 铝掺杂, 锂离子电池, 正极材料

Abstract: The Al-doped and Mg-doped LiCoMnO₄ materials were synthesized through solid-state reaction. The effects of doping amounts of Mg and Al on the initial capacities, discharge plateaus, and cycle performances were investigated. The morphologies and structures of the as-prepared materials were studied by scanning electron microscopy and powder X-ray diffraction. The results indicate that the as-prepared samples were composed of uniform, well-crystallized particles. The pristine LiCoMnO₄ possessed an initial capacity of 87.0 mAh·g^-1, while LiCo_0.98Mg_0.02MnO₄and LiCo_0.98Al_0.02MnO₄delivered 91.3 and 93.6 mAh·g^-1, respectively. The proper doping amount increased the capacity and the ratio of discharge plateau at 5 V, while over-doping decreased the discharge capacity of LiCoMnO₄. In addition, Al doping significantly improved the cycle performance of LiCoMnO₄, while no apparent influence with Mg doping.

Key words: solid state reaction, spinel LiCoMnO4, Mg-doped, Al-doped, lithium-ion battery, cathode material

中图分类号:

TM911

游美玲，童庆松，李秀华，林忞，黄行康*，杨勇*. 锂离子正极材料LiCo1-xMgxMnO4与LiCo1-xAlxMnO4 (x = 0, 0.02, 0.05, 0.1)的制备及其电化学性能[J]. 电化学（中英文）, 2014, 20(1): 22-27.

YOU Mei-ling, TONG Qing-song, LI Xiu-hua, LIN Min, HUANG Xing-kang*, YANG Yong*. Synthesis and Electrochemical Properties of LiCo_1-xMg_xMnO₄ and LiCo_1-xAl_xMnO₄(x= 0, 0.02, 0.05, 0.1) as Positive Materials for Lithium-ion Batteries[J]. Journal of Electrochemistry, 2014, 20(1): 22-27.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.121122

https://electrochem.xmu.edu.cn/CN/Y2014/V20/I1/22

参考文献

Zhecheva E, Stoyanova R, Alcantara R, et al. EPR studies of Li deintercalation from LiCoMnO4 spinel-type electrode active material[J]. Journal of Power Sources, 2006, 159(2): 1389-1394.
Huang X K, Lin M, Tong Q S, et al. Synthesis of LiCoMnO4 via a sol-gel method and its application in high power LiCoMnO4/Li4Ti5O12 lithium-ion batteries[J]. Journal of Power Sources, 2012, 202: 352-356.
Zhang R G(张仁刚), Zhao S X(赵世玺), Xia J L(夏君磊), et al. Study on modification of spinel LiMn2O4 by overcoating[J]. Journal of Electrochemistry (电化学), 2002, 8(3): 269-274.
Zhou D Q(周大桥). Preparation and performance of Co and La Co-doped Li-rich lithium Manganate[J]. Journal of Electrochemistry(电化学), 2009, 15(1): 74-78.
Pasero D, de Souza S, Reeves N, et al. Oxygen content and electrochemical activity of LiCoMnO4-δ[J]. Journal of Materials Chemistry, 2005, 15(41): 4435-4440.
Strobel P,Tillier J, Diaz A, et al. Search for new manganese-cobalt oxides as positive electrode materials for lithium batteries[J]. Journal of Power Sources, 2007, 174(2): 910-915.
Mandal S, Rojas R M, Amarilla J M, et al. High temperature Co-doped LiMn2O4-based spinels. Structural, electrical, and electrochemical characterization[J]. Chemistry of Materials, 2002, 14(4): 1598-1605.
Ohzuku T, Takeda S, Iwanaga M. Solid-state redox potentials for Li[Me1/2Mn3/2]O4 (Me:3d-transition metal) having spinel-framework structures: a series of 5 volt materials for advanced lithium-ion batteries[J]. Journal of Power Sources, 1999, 81: 90-94.
Zhecheva E, Stoyanova R. Effect of allied and alien ions on the EPR spectrum of Mn-containing lithium-manganese spinel oxides [J]. Solid State Communications, 2005, 135(7): 405-410.
Kawai H, Nagata M, Tukamoto H, et al. A new lithium cathode LiCoMnO4: Toward practical 5 V lithium batteries[J]. Electrochemical and Solid-State Letters, 1998, 1(5): 212-214.
Stoyanova R K, Zhecheva E N, Gorova M Y. EPR evidence on short-range Co-Mn order in LiCoMnO4 spinels[J]. Journal of Materials Chemistry, 2000, 10: 1377-1381.
Zhecheva E, Stoyanova R, Gorova M, et al. Co/Mn distribution and electrochemical intercalation of Li into Li[Mn2-yCoy]O4 spinels, 0< y< 1[J]. Solid State Ionics, 2001(1/2), 140:19-33.
Amdouni N, Gendron F, Mauger A, et al. LiMn2-yCoyO4 (0 ≤ y ≤ 1) intercalation compounds synthesized from wet-chemical route[J]. Materials Science and Engineering: B, 2006, 129(1/3): 64-75.
Kawai H, Nagata M, Tukamotob H, et al. A novel cathode Li2CoMn3O8 for lithium ion batteries operating over 5 volts[J]. Journal of Materials Chemistry Communication, 1998, 8(4):837-839.
Rojas R M, Amarilla J M, Pascual, L, et al. Combustion synthesis of nanocrystalline LiNiYCo1-2YMn1+YO4 spinels for 5V cathode materials[J]. Journal of Power Sources, 2006, 160(1): 529-535.
Alcantara R, Jaraba M, Lavela P, et al. Electrochemical, 6Li MAS NMR, and X-ray and neutron diffraction study of LiCoxFeyMn2-(x+y)O4 spinel oxides for high-voltage cathode materials[J]. Chemical Materials, 2003, 15(12): 1210-1216.
Lin Y(林永), Zhao K(赵锟), Wang M L(王曼丽). Study on synthesis of spinel-LiMn2O4 nanoparticles and its electrochemical impedance spectroscopies[J]. Chemical Research and Application(化学研究与应用), 2011, 23(8): 975-979.

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锂离子正极材料LiCo1-xMgxMnO4与LiCo1-xAlxMnO4 (x = 0, 0.02, 0.05, 0.1)的制备及其电化学性能

Synthesis and Electrochemical Properties of LiCo_1-xMg_xMnO₄ and LiCo_1-xAl_xMnO₄(x= 0, 0.02, 0.05, 0.1) as Positive Materials for Lithium-ion Batteries

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锂离子正极材料LiCo1-xMgxMnO4与LiCo1-xAlxMnO4 (x = 0, 0.02, 0.05, 0.1)的制备及其电化学性能

Synthesis and Electrochemical Properties of LiCo1-xMgxMnO4 and LiCo1-xAlxMnO4 (x= 0, 0.02, 0.05, 0.1) as Positive Materials for Lithium-ion Batteries

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Synthesis and Electrochemical Properties of LiCo_1-xMg_xMnO₄ and LiCo_1-xAl_xMnO₄(x= 0, 0.02, 0.05, 0.1) as Positive Materials for Lithium-ion Batteries