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

Authors

Mei-ling YOU, Department of Chemistry, Fujian Normal University, Fuzhou 35007, China;
Qing-song TONG, Department of Chemistry, Fujian Normal University, Fuzhou 35007, China;
Xiu-hua LI, Department of Chemistry, Fujian Normal University, Fuzhou 35007, China;
Min LIN, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China;
Xing-kang HUANG, Department of Chemistry, Fujian Normal University, Fuzhou 35007, China;Follow
Yong YANG, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China;Follow

Corresponding Author

Xing-kang HUANG(xkhuang@126.com);
Yong YANG(yyang@xmu.edu.cn)

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_0.02MnO₄ and LiCo_0.98Al_0.02MnO₄ delivered 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.

Graphical Abstract

Keywords

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

DOI Link

https://doi.org/10.13208/j.electrochem.121122

Publication Date

2014-02-25

Online Available Date

2014-02-24

Revised Date

2013-01-10

Received Date

2012-11-22

Recommended Citation

Mei-ling YOU, Qing-song TONG, Xiu-hua LI, Min LIN, Xing-kang HUANG, Yong YANG. 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.
DOI: 10.13208/j.electrochem.121122
Available at: https://jelectrochem.xmu.edu.cn/journal/vol20/iss1/5

References

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.