高倍率球形锂离子电池正极材料LiNi0.5Co0.2Mn0.3O2的制备及其电化学性能研究

doi:10.6023/A16110594

化学学报 ›› 2017, Vol. 75 ›› Issue (5): 501-507.DOI: 10.6023/A16110594 上一篇下一篇

研究论文

高倍率球形锂离子电池正极材料LiNi_0.5Co_0.2Mn_0.3O₂的制备及其电化学性能研究

郑卓^a, 吴振国^b, 向伟^c, 郭孝东^b

a. 四川大学高分子研究所成都 610065;
b. 四川大学化学工程学院成都 610065;
c. 成都理工大学材料与化学化工学院成都 610065

投稿日期:2016-11-10 发布日期:2017-04-25
通讯作者: 郭孝东 E-mail:xiaodong2009@scu.edu.cn
基金资助:
项目受国家自然科学基金（No.21506133）资助.

Preparation and Electrochemical Performance of High Rate Spherical Layered LiNi_0.5Co_0.2Mn_0.3O₂ Cathode Material for Lithium-Ion Batteries

Zheng Zhuo^a, Wu Zhenguo^b, Xiang Wei^c, Guo Xiaodong^b

a. Polymer Research Institute, Sichuan University, Chengdu 610065;
b. School of Chemical Engineering, Sichuan University, Chengdu 610065;
c. College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, Chengdu 610065

Received:2016-11-10 Published:2017-04-25
Contact: 10.6023/A16110594 E-mail:xiaodong2009@scu.edu.cn
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21506133).

文章分享

摘要/Abstract

采用碳酸盐共沉淀-高温固相法制备得到了颗粒平均尺寸约5 μm振实密度为2.1 g·cm^-3的均匀微球形高镍LiNi_0.5Co_0.2Mn_0.3O₂材料.X射线衍射（XRD）分析和透射电镜（TEM）结果表明这种微球状LiNi_0.5Co_0.2Mn_0.3O₂材料具有完善的层状α-NaFeO₂结构，过渡金属层原子呈[√3×√3]R30°排布.电化学性能测试结果证实了该材料具有优异的循环稳定性和高倍率性能.具体而言，在2.7~4.3 V，1C下循环100次后的放电比容量为150 mAh·g^-1，容量保持率为94.6%，在30C的超高倍率下，放电比容量还能达到96 mAh·g^-1.同时，该材料的储能能力也非常突出，在0.1C时比能量密度为687.83 Wh·kg^-1（体积能量密度为1444.45 Wh·L^-1），在30C时仍达335.27 Wh·kg^-1（体积能量密度为704.07 Wh·L^-1），非常有潜力应用于商业化高能量密度锂离子电池.

关键词: 锂离子电池, 正极材料, 碳酸盐共沉淀法, LiNi_0.5Co_0.2Mn_0.3O₂, 高倍率性能

Layered Ni-rich compound LiNi_0.5Co_0.2Mn_0.3O₂ has drawn considerable attention recently because high Ni content contributes to the improvement of specific capacity and the reduction of cost. However, it is a challenge to obtain the Ni-rich LiNi_0.5Co_0.2Mn_0.3O₂ cathode with both high rate performance and high tap density because the rate capability is often improved at the expense of volumetric energy density, which is mostly dependent on the tap density. In our work, an uniform Ni-rich LiNi_0.5Co_0.2Mn_0.3O₂ microsphere with an average diameter of ca. 5 μm and tap density of 2.1 g·cm^-3 was successfully prepared using carbonate co-precipitation method, which can meet the commercial requirement for lithium-ion batteries (tap density≥2.1 g·cm^-3, Lithium Nickel Cobalt Manganese Oxides from CETC International Co., Ltd). In this synthetic route, the 2 mol·L^-1 mixture of NiSO₄·6H₂O, MnSO₄·H₂O and CoSO₄·7H₂O (Ni:Co:Mn=5:2:3, molar ratio) are the starting materials, 2 mol·L^-1 Na₂CO₃ and 4 mol·L^-1 NH₃·H₂O are the precipitant and chelating agent, respectively. In order to achieve high tap density, the stirring speed of continuous stirred tank reactor (CSTR) is as high as 1500 r/min, and the powder was preheated at 550 ℃ for 6 h and then calcined at 850 ℃ for 14 h in flowing oxygen. Powder X-ray diffraction (XRD) and transmission electron microscopy (TEM) results indicate that the microsphere LiNi_0.5Co_0.2Mn_0.3O₂ material has a well-ordered α-NaFeO₂ structure with stable in-plane [√3×√3]R30° ordering in the transition-metal layers. Electrochemical results also confirm that this cathode has excellent cycling stability and high rate capability. Specifically, it exhibits a discharge capacity of 150 mAh·g^-1 between 2.7 and 4.3 V at 1C after 100 cycles, with outstanding capacity retention of 94.6%. At 30C rate, it can still deliver a high discharge capacity of 96 mAh·g^-1. Meanwhile, the energy storage capacity for this cathode is also encouraging. At 0.1C rate, the specific energy (E_s) is 687.83 Wh·kg^-1 (volumetric energy density is 1444.45 Wh·L^-1); at 30C rate, the specific energy (E_s) is 335.27 Wh·kg^-1 (volumetric energy density is 704.07 Wh·L^-1). These excellent features will make this microsphere LiNi_0.5Co_0.2Mn_0.3O₂ material as a potential positive electrode material for commercial high energy density lithium-ion batteries.

Key words: lithium-ion battery, cathode material, carbonate co-precipitation method, LiNi_0.5Co_0.2Mn_0.3O₂, high rate performance

引用此文

郑卓, 吴振国, 向伟, 郭孝东. 高倍率球形锂离子电池正极材料LiNi_0.5Co_0.2Mn_0.3O₂的制备及其电化学性能研究[J]. 化学学报, 2017, 75(5): 501-507.

Zheng Zhuo, Wu Zhenguo, Xiang Wei, Guo Xiaodong. Preparation and Electrochemical Performance of High Rate Spherical Layered LiNi_0.5Co_0.2Mn_0.3O₂ Cathode Material for Lithium-Ion Batteries[J]. Acta Chim. Sinica, 2017, 75(5): 501-507.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

参考文献

[1] Tarascon, J. M.; Armand, M. Nature 2001, 414, 359.
[2] Dunn, B.; Kamath, H.; Tarascon, J. M. Sience 2011, 334, 928.
[3] Mahmood, N.; Zhang, C. Z.; Yin, H.; Hou, Y. L. J. Mater. Chem. A 2014, 2, 15.
[4] Yu, X. Q.; Lyu, Y. C.; Gu, L.; Wu, H. M.; Bak, S. M.; Zhou, Y. N.; Amine, K.; Ehrlich, S. N.; Li, H.; Nam, K. W.; Yang, X. Q. Adv. Energy Mater. 2014, 4, 1300950.
[5] Lv, Z. Y.; Feng, R.; Zhao, J.; Fan, H.; Xu, D.; Wu, Q.; Yang, L. J.; Chen, Q.; Wang, X. Z.; Hu, Z. Acta Chim. Sinica 2015, 73, 1013. (吕之阳, 冯瑞, 赵进, 范豪, 徐丹, 吴强, 杨立军, 陈强, 王喜章, 胡征, 化学学报, 2015, 73, 1013.)
[6] Qiu, Z. P.; Zhang, Y. J.; Xia, S. B.; Dong, P. Acta Chim. Sinica 2015, 73, 992. (邱振平, 张英杰, 夏书标, 董鹏, 化学学报, 2015, 73, 992.)
[7] Bi, Y.; Yang, W.; Du, R.; Zhou, J.; Liu, M.; Liu, Y.; Wang, D. J. Power Sources 2015, 283, 211.
[8] Kim, Y. ACS Appl. Mater. Interfaces 2012, 4, 2329.
[9] Lin, H. C.; Yang, Y. Acta Chim. Sinica 2009, 67, 104. (林和成, 杨勇, 化学学报, 2009, 67, 104.)
[10] Sun, Y. K.; Myung, S. T.; Park, B. C.; Prakash, J.; Belharouak, I.; Amine, K. Nat. Mater. 2009, 8, 320.
[11] Cho, J.; Jung, H.; Park, Y.; Kim, G.; Lim, H. S. J. Electrochem. Soc. 2000, 147, 15.
[12] Abraham, D. P.; Twesten, R. D.; Balasubramanian, M.; Petrov, I.; McBreen, J.; Amine, K. Electrochem. Commun. 2002, 4, 620.
[13] Woo, S. U.; Yoon, C. S.; Amine, K.; Belharouak, I.; Sun, Y. K. J. Electrochem. Soc. 2007, 154, A1005.
[14] Lin, B.; Wen, Z.; Gu, Z.; Huang, S. J. Power Sources 2008, 175, 564.
[15] Whitfield, P. S.; Davidson, I. J.; Cranswick, L. M. D.; Swainson, I. P.; Stephens, P. W. Solid State Ionics 2005, 176, 463.
[16] Li, W. W.; Li, L.; Yang, L. Nonferrous Met. 2014, 7, 53. (李伟伟, 李丽, 杨理, 有色金属(冶炼部分), 2014, 7, 53.)
[17] Kong, J. Z.; Zhai, H. F.; Ren, C.; Gao, M. Y.; Zhang, X.; Li, H.; Li, J. X.; Tang, Z.; Zhou, F. J. Alloys Compd. 2013, 577, 507.
[18] Xie, L. S.; Lin, Q. Q.; Li, H. C.; Wang, Z. G.; Wang, C. F.; Hu, M. C.; Huang, R. H. Mater. Sci. 2017, 7, 72.
[19] Li, Y. J.; Han, Q.; Ming, X. Q.; Ren, M. M.; Li, L.; Ye, W. Q.; Zhang, X. Z.; Xu, H.; Li, L. Ceram. Int. 2014, 40, 14933.
[20] Yang, Z. G.; Guo, X. D.; Xiang, W.; Hua, W. B.; Zhang, J.; He, F. R.; Wang, K.; Xiao, Y.; Zhong, B. H. J. Alloys Compd. 2017, 699, 358.
[21] Zhang, J. B.; Zhong, Y. J.; Shi, X. X.; Zheng, Z.; Hua, W. B.; Chen, Y. X.; Liu, W. Y.; Zhong, B. H. Chin. J. Chem. 2015, 33, 1303.
[22] Hua, W. B.; Wang, Y. J.; Zhong, Y. J.; Wang, G. P.; Zhong, B. H.; Fang, B. Z.; Guo, X. D.; Liao, S. X.; Wang, H. J. Chin. J. Chem. 2015, 33, 261.
[23] Ahn, W.; Lim, S. N.; Jung, K. N.; Yeon, S. H.; Kim, K. B.; Song, H. S.; Shin, K. H. J. Alloys Compd. 2014, 609, 143.
[24] Li, J.; Xiong, S.; Liu, Y.; Ju, Z.; Qian, Y. Nano Energy 2013, 2, 1249.
[25] Yabuuchi, N.; Koyama, Y.; Nakayama, N.; Ohzuku, T. J. Electrochem. Soc. 2005, 152, A1434.
[26] Gabrisch, H.; Yi, T.; Yazami, R. Electrochem. Solid-State Lett. 2008, 11, A119.
[27] Koyama, Y.; Tanaka, I.; Adachi, H.; Makimura, Y.; Ohzuku, T. J. Power Sources 2003, 119~121, 644.
[28] Zhu, Z.; Yan, H.; Zhang, D.; Li, W.; Lu, Q. J. Power Sources 2013, 224, 13.
[29] Shaju, K. M.; Bruce, P. G. Adv. Mater. 2006, 18, 2330.
[30] Wu, F.; Li, N.; Su, Y. F.; Shou, H. F.; Bao, L. Y.; Yang, W.; Zhang, L. J.; An, R.; Chen, S. Adv. Mater. 2013, 25, 3722.
[31] Striebel, K. A.; Sakai, E.; Cairns, E. J. J. Electrochem. Soc. 2002, 149, A61.
[32] Wang, L.; Zhao, J.; He, X.; Gao, J.; Li, J.; Wan, C.; Jiang, C. Int. J. Electrochem. Sci. 2012, 7, 345.
[33] Mai, L.; Li, S.; Dong, Y.; Zhao, Y.; Luo, Y.; Xu, H. Nanoscale 2013, 5, 4864.
[34] Li, B.; Han, C.; He, Y. B.; Yang, C.; Du, H.; Yang, Q. H.; Kang, F. Energy Environ. Sci. 2012, 5, 9595.
[35] Zhou, P. F.; Meng, H. J.; Zhang, Z.; Chen, C. C.; Lu, Y. Y.; Cao, J.; Cheng, F. Y.; Chen, J. J. Mater. Chem. A 2017, 5, 2724.

高倍率球形锂离子电池正极材料LiNi_0.5Co_0.2Mn_0.3O₂的制备及其电化学性能研究

Preparation and Electrochemical Performance of High Rate Spherical Layered LiNi_0.5Co_0.2Mn_0.3O₂ Cathode Material for Lithium-Ion Batteries

PDF

可视化

摘要/Abstract

引用此文

分享此文

参考文献

相关文章 15

编辑推荐

相关统计

本文评价

[1]	顾晓瑜, 李进, 孙千, 王朝阳. 微量量热法分析锂离子电池热失控过程[J]. 化学学报, 2024, 82(2): 146-151.
[2]	贾洋刚, 陈诗洁, 邵霞, 程婕, 林娜, 方道来, 冒爱琴, 李灿华. 高性能无钴化钙钛矿型高熵氧化物负极材料的制备及储锂性能研究[J]. 化学学报, 2023, 81(5): 486-495.
[3]	张雅岚, 苑志祥, 张浩, 张建军, 崔光磊. 高镍三元高比能固态锂离子电池的研究进展[J]. 化学学报, 2023, 81(12): 1724-1738.
[4]	常婉莹, 谭莹瑛, 吴静怡, 刘英杰, 蔡金海, 赖春艳. 三维结构Li_6.28La₃Zr₂Al_0.24O₁₂增强聚氧化乙烯基固态电解质的性能研究[J]. 化学学报, 2023, 81(12): 1708-1715.
[5]	张爽, 杨成飞, 杨玉波, 冯宁宁, 杨刚. 基于废旧锂电池回收制备Li_xMO (x=0.79, 0.30, 0.08; M=Ni/Co/Mn)材料作为锂-氧气电池正极催化剂的电化学性能研究[J]. 化学学报, 2022, 80(9): 1269-1276.
[6]	何家伟, 焦柳, 程雪怡, 陈光海, 吴强, 王喜章, 杨立军, 胡征. 金属有机框架衍生的空心碳纳米笼的结构调控与锂硫电池性能研究[J]. 化学学报, 2022, 80(7): 896-902.
[7]	陈守潇, 刘君珂, 郑伟琛, 魏国祯, 周尧, 李君涛. 电/离子导体双包覆的LiNi_0.8Co_0.1Mn_0.1O₂锂离子电池阴极材料及其电化学性能[J]. 化学学报, 2022, 80(4): 485-493.
[8]	黄擎, 丁瑞, 陈来, 卢赟, 石奇, 张其雨, 聂启军, 苏岳锋, 吴锋. Na₂PO₃F对LiNi_0.83Co_0.11Mn_0.06O₂材料的复合改性及机理分析[J]. 化学学报, 2022, 80(2): 150-158.
[9]	薛晓兰, 张洋, 石美瑜, 李天琳, 黄天龙, 戚继球, 委福祥, 隋艳伟, 金钟. 有机电极材料在非水系金属镁二次电池中的研究进展[J]. 化学学报, 2022, 80(12): 1618-1628.
[10]	邱凯, 严铭霞, 赵守旺, 安胜利, 王玮, 贾桂霄. Al掺杂的锂离子电池层状正极材料Li(Li_0.17Ni_0.17Al_0.04Fe_0.13Mn_0.49)O₂结构稳定性及氧离子氧化的理论研究[J]. 化学学报, 2021, 79(9): 1146-1153.
[11]	徐平, 张西华, 马恩, 饶富, 刘春伟, 姚沛帆, 孙峙, 王景伟. 退役锂离子电池碳/硫协同选择性提锂技术[J]. 化学学报, 2021, 79(8): 1073-1081.
[12]	李童心, 李东林, 张清波, 高建行, 孔祥泽, 樊小勇, 苟蕾. 大孔高镍LiNi_0.8Co_0.1Mn_0.1O₂正极材料的制备及其电化学性能研究[J]. 化学学报, 2021, 79(5): 678-684.
[13]	林碧霞, 黄颖珊, 陈帅, 邢震宇. 钠硒电池关键材料的研究进展[J]. 化学学报, 2021, 79(5): 641-648.
[14]	李燕丽, 于丹丹, 林森, 孙东飞, 雷自强. α-MnO₂纳米棒/多孔碳正极材料的制备及水系锌离子电池性能研究[J]. 化学学报, 2021, 79(2): 200-207.
[15]	张璐, 王文凤, 张洪明, 韩树民, 王利民. 水系锌离子电池研究进展和挑战[J]. 化学学报, 2021, 79(2): 158-175.