用作锂离子电池负极材料的包碳螺旋结构碳纳米管

doi:10.3724/SP.J.1077.2011.00631

无机材料学报 ›› 2011, Vol. 26 ›› Issue (6): 631-637.DOI: 10.3724/SP.J.1077.2011.00631

用作锂离子电池负极材料的包碳螺旋结构碳纳米管

邵进^1,2, 任玉荣^1,3, 李国强^1,2, 黄小兵^1,2, 周固民¹, 瞿美臻¹

(1. 中国科学院成都有机化学研究所, 成都610041; 2. 中国科学院研究生院, 北京100039, 3. 常州大学材料科学与工程学院, 常州 213164)

收稿日期:2010-08-18 修回日期:2010-09-29 出版日期:2011-06-20 网络出版日期:2011-06-07
作者简介:邵进(1985-), 男, 硕士研究生. E-mail: wosj-no.1@163.com
基金资助:
国家“863”计划项目(2009AA03Z337)

Carbon Coated Helical Carbon Nanotubes used as Anode Materials of Li-ion Battery

SHAO Jin^1,2, REN Yu-Rong^1,3, LI Guo-Qiang^1,2, HUANG Xiao-Bing^1,2, ZHOU Gu-Min¹, QU Mei-zhen¹

(1. Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, China; 2. Graduate University of Chinese Academy of Sciences, Beijing 100039, China; 3. School of Materials Science and Engineering, Changzhou University, Changzhou 213164, China)

Received:2010-08-18 Revised:2010-09-29 Published:2011-06-20 Online:2011-06-07
Supported by:
National High-tech R&D Program of China (2009AA03Z337)

摘要/Abstract

摘要： 以苯为碳源, 在900 ℃下采用TVD(thermal vapor deposition)法对螺旋结构碳纳米管(Helical carbon nanotubes, HCNTs)进行了包碳修饰, 采用XRD、SEM、TEM、BET 等检测方法对所制备材料进行了表征分析. 包碳后HCNTs的比表面积明显降低. 研究了包碳HCNTs用作锂离子电池负极材料的性能, 结果显示适量包碳不仅提高了HCNTs的首次库仑效率, 而且改善了其循环稳定性和倍率充放电性能. 当TVD包碳45 min、HCNTs增重约220 wt%时, 首次库仑效率从59.2%提高到77.8%, 在1.0C、2.0C、5.0C以及10.0C倍率下的放电比容量分别为265.6、245.7、196.0、163.2 mAh/g, 在10.0C下循环95次后放电比容量保持率为93.3%. 过多的碳包覆虽然会进一步提高材料的首次库仑效率和循环稳定性, 但会导致其倍率性能变差.

关键词: 螺旋结构碳纳米管, 首次库仑效率, TVD, 锂离子电池

Abstract: The helical carbon nanotubes (HCNTs) was modified with carbon through thermal vapor deposition (TVD) of benzene at 900 ℃, and characterized by X-ray powder diffraction, transmission electronic microscope, scanning electronic microscope and Brunau-Emmertt-Teller method. The specific surface area of the HCNTs decreased after carbon coating. The obtained carbon coated HCNTs used as anode materials of Li-ion battery were studied. The results revealed that appropriate amount of carbon coating could improve the first columbic efficiency, the cycling stability and rate charge/discharge performance of the HCNTs. After 45 min carbon coating, HCNTs gained a weight increase approximately 220wt%, with its first columbic efficiency increasing from 59.2% to 77.8%, and delivered a discharge capacity of 265.6, 245.7, 196.0, 163.2 mAh/g at the rates of 1.0C, 2.0C, 5.0C and 10.0C, respectively. After 95 cycles at 10.0C, its discharge capacity retention was 93.3%. Although excessive carbon coating could further improve the first coulumbic efficiency and cycling stability of HCNTs, it also degraded the rate capability.

Key words: helical carbon nanotubes, first columbic efficiency, TVD, Li-ion battery

中图分类号:

O646
TB383

邵进, 任玉荣, 李国强, 黄小兵, 周固民, 瞿美臻. 用作锂离子电池负极材料的包碳螺旋结构碳纳米管[J]. 无机材料学报, 2011, 26(6): 631-637.

SHAO Jin, REN Yu-Rong, LI Guo-Qiang, HUANG Xiao-Bing, ZHOU Gu-Min, QU Mei-zhen. Carbon Coated Helical Carbon Nanotubes used as Anode Materials of Li-ion Battery[J]. Journal of Inorganic Materials, 2011, 26(6): 631-637.

参考文献

[1] Wang J, Wang C Y, Too C O, et al. Highly-flexible fibre battery incorporating polypyrrole cathode and carbon nanotubes anode. J. Power Sources, 2006, 161(2): 1458-1462.

[2] Chew S Y, Ng S H, Wang J Z, et al. Flexible free-standing carbon nanotube films for model lithium-ion batteries. Carbon, 2009, 47(13): 2976-2983.

[3] Ohsaki T, Kanda M, Aoki Y, et al. High-capacity lithium-ion cells using graphitized mesophase-pitch-based carbon fiber anodes. J. Power Sources, 1997, 68(1): 102-105.

[4] Leroux F, Metenier K, Gautier S, et al. Electrochemical insertion of lithium in catalytic multi-walled carbon nanotubes. J. Power Sources, 1999, 81: 317-322.

[5] Gao B, Kleinhammes A, Tang X P, et al. Electrochemical intercalation of single-walled carbon nanotubes with lithium. Chem. Phys. Lett., 1999, 307(3/4): 153-157.

[6] Che G L, Lakshmi B B, Fisher E R, et al. Carbon nanotubule membranes for electrochemical energy storage and production. Nature, 1998, 393(6683): 346-349.

[7] Wu X L, Liu Q, Guo Y G, et al. Superior storage performance of carbon nanosprings as anode materials for lithium-ion batteries. Electrochem. Commun., 2009, 11(7): 1468-1471.

[8] Wang Q, Li H, Huang X J, et al. Investigation of lithium storage in bamboo-like CNTs by HRTEM. J. Electrochem. Soc., 2003, 150(9): A1281-A1286.

[9] Xu Y J, Liu X, Cui G L, et al. A comparative study on the lithium-ion storage performances of carbon nanotubes and tube-in-tube carbon nanotubes. Chem. Sus. Chem., 2010, 3(3): 343-349.

[10] Yang Z H, Feng Y, Li Z F, et al. An investigation of lithium intercalation into the carbon nanotubes by a.c. impedance. J. Electroanal. Chem. , 2005, 580(2): 340-347.

[11] 张爱黎, 翟秀静, 符岩, 等(Zhang Ai-Li, et al)碳纳米管的电化学贮锂性能研究. 无机材料学报(Journal of Inorganic Materials), 2004, 19(1): 244-248.

[12] Shin H C, Liu M L, Sadanadan B, et al. Lithium insertion into chemically etched multi-walled carbon nanotubes. J. Solid State Electro., 2004, 8(11): 908-913.

[13] Wang X X, Wang J N, Chang H, et al. Preparation of short carbon nanotubes and application as an electrode material in Li-ion batteries. Adv. Funct. Mater., 2007, 17(17): 3613-3618.

[14] Yang S B, Huo J P, Song H H, et al. A comparative study of electrochemical properties of two kinds of carbon nanotubes as anode materials for lithium ion batteries. Electrochim. Acta, 2008, 53(5): 2238-2244.

[15] Huang H, Zhang W K, Gan X P, et al. Improved electrochemical storage of lithium into multi-walled carbon nanotubes by light irradiation. Mater. Chem. Phys. , 2007, 104(2/3): 271-275.

[16] Zhao T K, Liu Y N, Li T H, et al. Electrochemical performance of amorphous carbon nanotube as anode materials for lithium ion battery. J. Nanosci. Nanotech., 2010, 10(6): 3873-3877.

[17] S Masarapu C, Subramanian V, Zhu H W, et al. Long-cycle electrochemical behavior of multiwall carbon nanotubes synthesized on stainless steel in Li ion batteries. Adv. Funct. Mater., 2009, 19(7): 1008-1014.

[18] Chen G, Wang Z Y, Xia D G, et al. One-pot synthesis of carbon nanotube@SnO2-Au coaxial nanocable for lithium-ion batteries with high rate capability. Chem. Mater., 2008, 20(22): 6951-6956.

[19] Wang G X, Shen X P, Yao J, et al. Hydrothermal synthesis of carbon nanotube/cobalt oxide core-shell one-dimensional nanoco- mposite and application as an anode material for lithium-ion batteries. Electrochem. Commun., 2009, 11(3): 546-549.

[20] Cui G L, Gu L, Kaskhedikar N, et al. A novel germanium/carbon nanotubes nanocomposite for lithium storage material. Electrochim. Acta, 2010, 55(3): 985-988.

[21] 叶茂, 周震, 卞锡奎, 等(YE Mao, et al).CoO填充多壁碳纳米管作为锂离子电池负极材料. 无机化学学报(Chinese J. Inorg. Chem.), 2006, 22(7): 1307-1311.

[22] Ng S H, Wang J, Guo Z P, et al. Single wall carbon nanotube paper as anode for lithium-ion battery. Electrochim. Acta, 2005, 51(1): 23-28.

[23] Su D S, Schlogl R. Nanostructured carbon and carbon nanocomposites for electrochemical energy storage applications. Chem. Sus. Chem., 2010, 3(2): 136-168.

[24] Yoshio M, Wang H Y, Fukuda K, et al. Effect of carbon coating on electrochemical performance of treated natural graphite as lithium-ion battery anode material. J. Electrochem. Soc., 2000, 147(4): 1245-1250.

[25] Zhang H L, Li F, Liu C, et al. Poly(vinyl chloride) (PVC) coated idea revisited: Influence of carbonization procedures on PVC-coated natural graphite as anode materials for lithium ion batteries. J. Phys. Chem. C, 2008, 112(20): 7767-7772.

[26] Lu D, Li W, Zuo X X, et al. Study on electrode kinetics of Li+ insertion in LixMn2O4 (0 ≤ x ≤ 1) by electrochemical impedance spectroscopy. J. Phys. Chem. C, 2007, 111(32): 12067-12074.

[27] Aurbach D, Markovsky B, Levi E, et al. On the correlation between surface chemistry and performance of graphite negative electrodes for Li ion batteries. Electrochim. Acta, 1999, 45(1/2): 67-86.

[28] Wang G P, Zhang B L, Yue M, et al. A modified graphite anode with high initial efficiency and excellent cycle life expectation. Solid State Ionics, 2005, 176(9/10): 905-909.

[29] 吴宇平, 戴晓兵, 马军旗, 等. 锂离子电池-应用与实践. 北京: 化学工业出版社, 2004: 70-79.

[30] Feng L, Zou Q Q, Xia Y Y. CoO-loaded graphitable carbon hollow spheres as anode materials for lithium-ion battery. J. Power Sources, 2008, 177: 546-552.

[31] 左晓希, 李伟善, 刘建生. 锂离子电池液体电解质与电极相容性的研究进展. 化学进展, 2003, 15(6): 441-444.

[32] 陈昌国, 陈佳, 唐燕秋, 等(CHEN Chang-Guo, et al). 锂离子电池炭负极材料结构的研究进展. 无机材料学报(Journal of Inorganic Materials), 2003, 18(6): 1153-1157.

用作锂离子电池负极材料的包碳螺旋结构碳纳米管

Carbon Coated Helical Carbon Nanotubes used as Anode Materials of Li-ion Battery

PDF (PC)

可视化

被引次数

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]	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.
[2]	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.
[3]	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.
[4]	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.
[5]	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.
[6]	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.
[7]	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.
[8]	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.
[9]	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.
[10]	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.
[11]	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.
[12]	王影, 张文龙, 邢彦锋, 曹苏群, 戴新义, 李晶泽. 非晶态磷酸锂包覆钛酸锂电极在0.01~3.00 V电压范围的性能研究[J]. 无机材料学报, 2021, 36(9): 999-1005.
[13]	刘勇, 白海军, 赵奇志, 杨金戈, 李宇杰, 郑春满, 谢凯. LiNi_0.8Co_0.15Al_0.05O₂/石墨锂离子电池高荷电存储老化机理研究[J]. 无机材料学报, 2021, 36(2): 175-180.
[14]	湛菁,徐昌藩,龙怡宇,李启厚. 聚丙烯酰胺凝胶法制备Bi₂Mn₄O₁₀及其电化学性能[J]. 无机材料学报, 2020, 35(7): 827-833.
[15]	郑时有, 董飞, 庞越鹏, 韩盼, 杨俊和. 纳米金属氧化物基锂离子电池负极材料研究进展[J]. 无机材料学报, 2020, 35(12): 1295-1306.