Li4Ti5O12/CMK-3复合材料的制备及其作为锂离子电池负极材料的性能

doi:10.3866/PKU.WHXB201303211

物理化学学报 >> 2013, Vol. 29 >> Issue (06): 1247-1252.doi: 10.3866/PKU.WHXB201303211

Li₄Ti₅O₁₂/CMK-3复合材料的制备及其作为锂离子电池负极材料的性能

武洪彬¹, 张莹¹, 袁聪俐¹, 韦小培¹, 殷金玲¹, 王贵领¹, 曹殿学¹, 张益明², 杨宝峰², 佘佩亮²

1 超轻材料与表面技术教育部重点实验室, 哈尔滨工程大学材料科学与化学工程学院, 哈尔滨 150001;
2 双登集团南京科技发展研究院, 南京 211100

收稿日期:2013-01-08 修回日期:2013-03-20 发布日期:2013-05-17
通讯作者: 曹殿学 E-mail:caodianxue@hrbeu.edu.cn
基金资助:
哈尔滨优秀学术带头人科技创新基金(2012RFXXG103); 中央高校基础研究基金(HEUCFT1205)及江苏省科技支撑计划(BE2012152)资助

Synthesis and Electrochemical Performance of Li₄Ti₅O₁₂/CMK-3 Nanocomposite Negative Electrode Materials for Lithium-Ion Batteries

WU Hong-Bin¹, ZHANG Ying¹, YUAN Cong-Li¹, WEI Xiao-Pei¹, YIN Jin-Ling¹, WANG Gui-Ling¹, CAO Dian-Xue¹, ZHANG Yi-Ming², YANG Bao-Feng², SHE Pei-liang²

1 Key Laboratory of Superlight Material and Surface Technology of Ministry of Education, College of Material Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, P. R. China;
2 Shuangdeng Institute of Science and Techonology, Nanjing, 211000, P. R. China

Received:2013-01-08 Revised:2013-03-20 Published:2013-05-17
Supported by:
The project was supported by Harbin Science and Technology Innovation Fund for Excellent Academic Leaders, China (2012RFXXG103), Fundamental Research Funds for the Central Universities, China (HEUCFT1205), and Science and Technology Support Program of Jiangsu Province, China (BE2012152).

摘要/Abstract

摘要：

将LiNO₃和Ti(OC₄H₉)₄填填充在有序介孔碳CMK-3 孔道中, 然后烧结合成了Li₄Ti₅O₁₂/CMK-3复合材料. 利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)和X射线衍射(XRD)对其结构和微观形貌进行了表征. 利用差热-热重分析(TG-DTA)测试复合材料中Li₄Ti₅O₁₂的含量. 利用充放电测试、循环伏安和电化学阻抗技术考察了复合材料作为锂离子电池负极材料的性能. 发现Li₄Ti₅O₁₂分布在CMK-3孔道中及其周围, 复合材料的高倍率充放电性能显著优于商品Li₄Ti₅O₁₂, 复合材料中Li₄Ti₅O₁₂的比容量明显高于除去CMK-3的样品(在1C倍率时比容量为117.8 mAh·g^-1), 其0.5C、1C和5C倍率的放电比容量分别为160、143 和131 mAh·g^-1, 库仑效率接近100%, 5C倍率时循环100次的容量损失率只有0.62%. 本研究结果表明CMK-3明显提高了Li₄Ti₅O₁₂的高倍率充放电性能, 可能是CMK-3特殊的孔道结构和良好的导电性减小了Li₄Ti₅O₁₂的粒径并提高了其电导率.

关键词: 有序介孔碳, Li₄Ti₅O₁₂, 复合材料, 锂离子电池, 负极材料

Abstract:

The composite of ordered mesoporous carbon (CMK-3) and Li₄Ti₅O₁₂ (Li₄Ti₅O₁₂/CMK-3) was prepared by the wet impregnation of CMK-3 with LiNO₃ and Ti(OC₄H₉)₄ solution followed by calcination. Its morphology and structure were examined using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). The content of Li₄Ti₅O₁₂ in the mesoporous nanocomposite was determined by thermogravimetric analysis. Its electrochemical performance as the negative electrode material of lithium-ion batteries was investigated by galvanostatic charge-discharge tests, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The results show that Li₄Ti₅O₁₂ is formed inside the mesopore channels of CMK-3 and some particles are located on the surface of CMK-3. The composite shows significantly greater high-rate performance than commercial Li₄Ti₅O₁₂. The specific capacity of Li₄Ti₅O₁₂ in the composite is higher than Li₄Ti₅O₁₂ without CMK-3 (117.8 mAh·g^-1 at 1C rate), and its stabilized specific capacity reached 160, 143, and 131 mAh·g^-1 at 0.5C, 1C, and 5C charge-discharge rates, respectively, with a columbic efficiency of nearly 100%. The capacity loss after 100 cycles at 5C rate was less than 0.62%. This result clearly indicates that CMK-3 improves the high rate performance of Li₄Ti₅O₁₂, likely by reducing the particle size of Li₄Ti₅O₁₂ and increasing its electronic conductivity owing to the unique structure and good electronic conduction nature of CMK-3.

Key words: Ordered mesoporous carbon, Lithium titanate oxide, Composite, Lithium-ion battery, Negative electrode material

MSC2000:

O646

武洪彬, 张莹, 袁聪俐, 韦小培, 殷金玲, 王贵领, 曹殿学, 张益明, 杨宝峰, 佘佩亮. Li₄Ti₅O₁₂/CMK-3复合材料的制备及其作为锂离子电池负极材料的性能[J]. 物理化学学报, 2013, 29(06): 1247-1252.

WU Hong-Bin, ZHANG Ying, YUAN Cong-Li, WEI Xiao-Pei, YIN Jin-Ling, WANG Gui-Ling, CAO Dian-Xue, ZHANG Yi-Ming, YANG Bao-Feng, SHE Pei-liang. Synthesis and Electrochemical Performance of Li₄Ti₅O₁₂/CMK-3 Nanocomposite Negative Electrode Materials for Lithium-Ion Batteries[J]. Acta Phys. -Chim. Sin., 2013, 29(06): 1247-1252.

参考文献

(1) Xiang, H. F.; Zhang, X.; Jin, Q. Y.; Zhang, C. P.; Chen, C. H.;Ge, X.W. J. Power Sources 2008, 183, 355. doi: 10.1016/j.jpowsour.2008.04.091
(2) Koga, C.;Wada, S.; Nakayama, M. Electrochim. Acta 2010, 55,2561. doi: 10.1016/j.electacta.2009.12.034
(3) Dedryvère, R.; Foix, D.; Franger, S.; Patoux, S.; Daniel, L.;Gonbeau, D. J. Phys. Chem. C 2010, 14, 10999.
(4) Capsoni, D.; Bini, M.; Massarotti, V.; Mustarelli, P.; Ferrari, S.;Chiodelli, G.; Mozzati, M. C.; Galinetto, P. J. Phys. Chem. C2009, 113, 19664. doi: 10.1021/jp906894v
(5) Lee, S. C.; Lee, S. M.; Lee, J.W.; Lee, J. B.; Lee, S. M.; Han, S.S.; Lee, H. C.; Kim, H. J. J. Phys. Chem. C 2009, 113, 18420.doi: 10.1021/jp905114c
(6) Yoshikawa, D.; Kadoma, Y.; Kim, J. M.; Ui, K.; Kumagai, N.;Kitamura, N.; Idemoto Y. Electrochim. Acta 2010, 55, 1872.doi: 10.1016/j.electacta.2009.10.082
(7) Rahman, M. M.;Wang, J. Z.; Hassan, M. F.; Chou, S.;Wexler,D.; Liu, H. K. J. Power Sources 2010, 195, 4297. doi: 10.1016/j.jpowsour.2010.01.073
(8) Stournara, M. E.; Shenoy, V. B. J. Power Sources 2011, 196,5697. doi: 10.1016/j.jpowsour.2011.02.024
(9) Ju, S. H.; Kang, Y. C. J. Power Sources 2009, 189, 185.doi: 10.1016/j.jpowsour.2008.09.107
(10) Prakash, A. S.; Manikandan, P.; Ramesha, K.; Sathiya, M.;Tarascon, J. M.; Shukla, A. K. Chem. Mater. 2010, 22, 2857.doi: 10.1021/cm100071z
(11) Huang, S.;Wen, Z.; Zhu, X.; Lin, Z. J. Power Sources 2007,165, 408. doi: 10.1016/j.jpowsour.2006.12.010
(12) Deng, J.; Lu, Z.; Belharouak, I.; Amine, K.; Chung, C. Y.J. Power Sources 2009, 193, 816. doi: 10.1016/j.jpowsour.2009.03.074
(13) He, Y. B.; Ning, F.; Li, B.; Song, Q. S.; Lv,W.; Du, H.; Zhai, D.;Su, F.; Yang, Q. H.; Kang, F. J. Power Sources 2012, 202, 253.doi: 10.1016/j.jpowsour.2011.11.037
(14) Yuan, T.; Yu, X.; Cai, R.; Zhou, Y.; Shao, Z. J. Power Sources2010, 195, 4997. doi: 10.1016/j.jpowsour.2010.02.020
(15) Wang, G. J.; Gao, J.; Fu, L. J.; Zhao, N. H.;Wu,Y. P.; Takamura,T. J. Power Sources 2007, 174, 1109. doi: 10.1016/j.jpowsour.2007.06.107
(16) Lin, Z.; Hu, X.; Huai, Y.; Liu, L.; Deng, Z.; Suo, J. Solid State Ionics 2010, 181, 412. doi: 10.1016/j.ssi.2010.01.019
(17) Yuan, T.; Cai, R.; Ran, R.; Zhou, Y.; Shao, Z. J. Alloy. Compd.2010, 505, 367. doi: 10.1016/j.jallcom.2010.04.253
(18) Jhan, Y. R.; Lin, C. Y.; Duh, J. G. Mater. Lett. 2011, 65, 2502.doi: 10.1016/j.matlet.2011.04.060
(19) Yi, T. F.; Jiang, L. J.; Shu, J.; Yue, C. B.; Zhu, R. S.; Qiao, H. B.J. Phys. Chem. Solids 2010, 71, 1236. doi: 10.1016/j.jpcs.2010.05.001
(20) Venkateswarlu, M.; Chen, C. H.; Do, J. S.; Lin, C.W.; Chou, T.C.; Hwang, B. J. J. Power Sources 2005, 146, 204. doi: 10.1016/j.jpowsour.2005.03.016
(21) Jung, H. G.; Kim, J.; Scrosati, B.; Sun, Y. K. J. Power Sources2011, 196, 7763. doi: 10.1016/j.jpowsour.2011.04.019
(22) Su, L.W.; Jing, Y.; Zhou, Z. Nanoscale 2011, 3, 3967.doi: 10.1039/c1nr10550g
(23) Wang, G.; Liu, H.; Liu, J.; Qiao, S.; Lu, G. M.; Munroe, P.; Ahn,H. Adv. Mater. 2010, 22, 4944. doi: 10.1002/adma.v22.44
(24) Ji, X.; Lee, K. T.; Nazar, L. F. Nat. Mater 2009, 8, 500.doi: 10.1038/nmat2460
(25) Jun, S.; Joo, S. H.; Ryoo, R.; Kruk, M.; Jaroniec, M.; Liu, Z.;Ohsuna, T.; Terasaki, O. J. Am. Chem. Soc. 2000, 122, 10712.doi: 10.1021/ja002261e
(26) Tian, B.; Xiang, H.; Zhang, L.; Li, Z.;Wang, H. Electrochim. Acta 2010, 55, 5453. doi: 10.1016/j.electacta.2010.04.068
(27) Zhang, B.; Huang, Z. D.; Oh, S.W.; Kim, J. K. J. Power Sources2011, 196, 10692. doi: 10.1016/j.jpowsour.2011.08.114
(28) Zhou, X. L.; Huang, R. A.;Wu, Z. C.; Yang, B.; Dai, Y. N. Acta Phys. -Chim. Sin. 2010, 26 (12), 3187. [周晓玲, 黄瑞安, 吴肇聪, 杨斌, 戴永年. 物理化学学报, 2010, 26 (12), 3187.]doi: 10.3866/PKU.WHXB20101212
(29) He, Y. B.; Li, B. H.; Liu, M.; Zhang, C.; Lv,W.; Yang, C.; Li, J.;Du, H. D.; Zhang, B.; Yang, Q. H.; Kim, J. K.; Kang, F. Y.Scientific Reports 2012, 2, 913.

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Li₄Ti₅O₁₂/CMK-3复合材料的制备及其作为锂离子电池负极材料的性能

Synthesis and Electrochemical Performance of Li₄Ti₅O₁₂/CMK-3 Nanocomposite Negative Electrode Materials for Lithium-Ion Batteries

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