高容量锂离子电池核壳型硅/碳复合电极材料的制备与性能

doi:10.7503/cjcu20140482

摘要/Abstract

摘要：

通过自组装方式采用一步法制备了锂离子电池硅碳复合电极材料. 使用X射线衍射仪(XRD)、透射电子显微镜(TEM)和扫描电子显微镜(SEM)等对样品结构进行表征. 结果表明, 聚乙烯吡咯烷酮(PVP)包覆的纳米硅颗粒(Si@PVP)均匀嵌入到具有三维网络纳米孔结构的导电石墨化炭黑(GCB)骨架中, 形成核壳复合型(Si@PVP-GCB)纳米颗粒, 既提高了该复合电极材料的导电性能, 又改善了材料的机械强度. 在纳米级GCB颗粒内部存在的中空石墨环结构和包覆在纳米Si颗粒外面的PVP包覆层都有效缓冲了纳米Si颗粒在充放电过程中较大的体积变化, 从而使纳米Si颗粒更加稳定. 电化学测试结果表明, Si@PVP-GCB 电极材料在电流密度为50 mA/g时, 经过100次循环后其可逆容量仍达到545 mA·h/g时, 远高于商品化的石墨微球(GMs)电极材料的容量(理论容量为372 mA·h/g).

关键词: 聚乙烯吡咯烷酮, 纳米硅, 炭黑, 核壳结构电极材料, 锂离子电池

Abstract:

Si/C composite electrode material, Si@PVP-GCB[GCB=graphitized carbon black, PVP=poly(N-vinyl-2-pyrrolidone] was prepared at room temperature by one step-assembly technique. The samples were characterized by X-ray diffraction(XRD), transmission electron microscopy(TEM), scanning electron microscopy(SEM), thermogravimetric analysis(TG) and Raman spectroscopy. It is found that a well-connected three dimensional(3D) nanoporous GCB network uniformly embedded with core-shell nanoparticles of the silicon nanoparticles(SiNPs) core and the PVP shell was formed. The GCB 3D network not only contributes to the high electrical conductivity of Si@PVP-GCB, but also strengthens the mechanical properties of the electrode material. Apart from that, the special hollow structure of GCB nanoparticles and PVP coating shell can buffer the volume variation of SiNPs much more effectively. The electrochemical results show that the Si@PVP-GCB delivered a reversible capacity of 545 mA·h/g at the current density of 50 mA/g after 100 cycles, much higher than that of the commercial graphite microspheres(GMs, 372 mA·h/g).

Key words: Poly(N-vinyl-2-pyrrolidone), Silicon nanoparticles, Carbon black, Core-shell structure electrode material, Lithium ion battery

中图分类号:

O646.21

TrendMD:

王存国, 潘璇, 张雷, 朱孟康, 李德凯, 刁玲博, 李伟彦. 高容量锂离子电池核壳型硅/碳复合电极材料的制备与性能. 高等学校化学学报, 2015, 36(2): 368.

WANG Cunguo, PAN Xuan, ZHANG Lei, ZHU Mengkang, LI Dekai, DIAO Lingbo, LI Weiyan. Preparation and Properties of the High Capacity Si@PVP-GCB Core-shell Composite Anode Material Used in Li-ion Batteries^†. Chem. J. Chinese Universities, 2015, 36(2): 368.

图/表 6

Fig.1 SEM images of raw GCB(A), SiNPs(B) and Si@PVP-GCB(C and D) (D) is the magnified image of the area framed in (C).

Fig.2 TEM images of GCB(A), Si@PVP-GCB(B) and Si@PVP(C)

Fig.3 XRD patterns(A), Raman spectra(B) and TG curves in air(C) of SiNPs(a), GCB(b) and Si@PVP-GCB(c)

Fig.4 First discharge(a'—c')-charge(a—c) curves(A) and cycling property(B) for SiNPs, GMs and Si@PVP-GCB between 2.0 and 0.005 V at the current density of 50 mA/g (A) a, a'. SiNPs; b, b'. GMs; c, c'. Si@PVP-GCB.

Fig.5 Rate performance of GMs and Si@PVP-GCB anodes at different current densities

Fig.6 Electrochemical impedance plots of Si@PVP- GCB(a), Si@PVP(b) and GMs(c)

参考文献 53

[1]	Kovalenko I., Zdyrko B., Magasinski A., Hertzberg B., Milicev Z., Burtovyy R., Luzinov I., Yushin G., Science, 2011, 334, 75—79
[2]	Armand M., Tarascon J. M., Nature, 2008, 451, 652—657
[3]	Chockla A. M., Harris J. T., Akhavan V. A., Bogart T. D., Holmberg V. C., Steinhagen C., Mullins C. B., Stevenson K. J., Korgel B. A., J. Am. Chem. Soc., 2011, 133, 20914—20921
[4]	Wang C. G., He L. X., Dong X. G., Wang Y. Z., Zhao S. G., Sun L., Lin L., Xiao H. J., Chem. J. Chinese Universities, 2007, 28(12), 2373—2376
	(王存国, 何丽霞, 董献国, 王怡臻, 赵树高, 孙琳, 林琳, 肖红杰. 高等学校化学学报, 2007, 28(12), 2373—2376)
[5]	Yuan W. N., Wang C. G., Chemistry Bullitin, 2010, 66(3), 15—18
	(袁维娜, 王存国. 化学通报, 2010, 66(3), 15—18)
[6]	Wang C.G., Lin L., Lu N.Q., Zhao Q., Sun L., Zhao S. G., Wang R. S., Acta Chim. Sinica, 2008, 16, 1909—1914
	(王存国, 林琳, 路乃群, 赵强, 孙琳, 赵树高, 王荣顺. 化学学报, 2008, 16, 1909—1914)
[7]	Zhang L., Zhang M. J., Wang Y. H., Zhang Z. L., Kan G. W., Wang C. G., Zhong Z. Y., Su F. B., J. Mater. Chem. A, 2014, 2, 10161—10168
[8]	Yu H. Y., Xie H. M., Zhang L. Y., Yan X. D., Yang G. L., Wang R. S., Chem. J. Chinese Universities, 2006, 27(7), 1315—1318
	(于海英, 谢海明, 张凌云, 颜雪冬, 杨桂玲, 王荣顺. 高等学校化学学报, 2006, 27(7), 1315—1318)
[9]	Zhang L., Wang Y. H., Kan G. W., Zhang Z. L., Wang C. G., Zhong Z. Y., Su F. B., RCS Advances, 2014, 4, 43114—43120
[10]	Yu J., Zhan H. H., Wang Y. H., Zhang Z. L., Chen H., Li H., Zhong Z. Y., Su F. B., J. Power Sources, 2013, 228, 112—119
[11]	Wang W., Kumta P. N., ACS Nano, 2010, 4, 2233—2241
[12]	Liu X. H., Zhong L., Huang S., Mao S. X., Zhu T., Huang J. Y., Acs Nano, 2012, 6, 1522—1531
[13]	Kohandehghan A., Kalisvaart P., Cui K., Kupsta M., Memarzadeh E., Mitlin D., J. Mater. Chem. A, 2013, 1, 12850—12861
[14]	Ge M., Rong J., Fang X., Zhou C., Nano Lett., 2012, 12, 2318—2323
[15]	Song T., Xia J., Lee J. H., Lee D. H., Kwon M. S., Choi J. M., Wu J., Doo S. K., Chang H., Park W. I., Zang D. S., Kim H., Huang Y., Hwang K. C., Rogers J. A., Paik U., Nano Lett., 2010, 10, 1710—1716
[16]	Kalnaus S., Rhodes K., Daniel C., J. Power Sources, 2011, 196, 8116—8124
[17]	Ge M. Y., Rong J. P., Fang X., Zhang A. Y., Lu Y. H., Zhou C. W., Nano Res., 2013, 6, 174—181
[18]	Liu B., Soares P., Checkles C., Zhao Y., Yu G., Nano Lett., 2013, 13, 3414—3419
[19]	Kong J. H., Yee W. A., Wei Y. F., Yang L. P., Ang J. M., Phua S. L., Wong S. Y., Zhou R., Dong Y. L., Li X., Lu X. H., Nanoscale, 2013, 5, 2967—2973
[20]	De Guzman R. C., Yang J. H., Cheng M. M. C., Salley S. O., Ng K. Y. S., J. Mater. Sci., 2013, 48, 4823—4833
[21]	Wu H., Yu G.H., Pan L. J., Liu N., McDowell M. T., Bao Z., Cui Y., Nat. Commun., 2013, 4, 1943—1948
[22]	Li W., Zhang Q., Zheng G., Seh Z. W., Yao H., Cui Y., Nano Lett., 2013, 13, 5534—5540
[23]	Yang S., Feng X., Zhi L., Cao Q., Maier J., Müllen K., Adv. Mater., 2010, 22, 838—842
[24]	Shi L., Li H., Wang Z., Huang X., Chen L., J. Mater. Chem., 2001, 11, 1502—1505
[25]	Erk C., Brezesinski T., Sommer H., Schneider R., Janek J., ACS Appl. Mater. Interfaces, 2013, 5, 7299—7307
[26]	Lin L., Studies on Prepation and Properties of the Novel Modified Pyrolysis Carbon Materials from Phenol-formaldehyde Resin for Lithium Ion Batteries, Qingdao University of Science and Technology, Qingdao, 2008
	(林琳. 用于锂离子电池的新型酚醛树脂热解碳改性材料的制备与性能研究, 青岛: 青岛科技大学, 2008)
[27]	Lin L., Wang C. G., Yang L., Sun L., Xiao H. J., Yuan T., Chemical and Physics Power Sources, 2008, 1(4), 8—13
[28]	Gu P., Cai R., Zhou Y., Shao Z., Electrochim. Acta, 2010, 55, 3876—3883
[29]	Lee J. I., Lee K. T., Cho J., Kim J., Choi N. S., Park S., Angew. Chem., 2012, 124, 2821—2825
[30]	Ray S., Pao C., Tsai H., Bose B., Chiou J., Pong W., Dasgupta D., Carbon, 2006, 44, 1982—1985
[31]	Ji L., Zhang X., Carbon, 2009, 47, 3219—3226
[32]	Su F., Zhao X., Wang Y., Zeng J., Zhou Z., Lee J. Y., J. Phys. Chem. B, 2005, 109, 20200—20206
[33]	Cuesta A., Dhamelincourt P., Laureyns J., Martinez-Alonso A., Tascón J. M., J. Mater. Chem., 1998, 8, 2875—2879
[34]	Yang Q., Xu W., Tomita A., Kyotani T., J. Am. Chem. Soc., 2005, 127, 8956—8957
[35]	Bokobza L., Bruneel J. L., Couzi M., Chem. Phys. Lett., 2013, 590, 153—159
[36]	Bakandritsos A., Simopoulos A., Petridis D., Chem. Mater., 2005, 17, 3468—3474
[37]	Magasinski A., Dixon P., Hertzberg B., Kvit A., Ayala J., Yushin G., Nat. Mater., 2010, 9, 353—358
[38]	Guo Y. G., Hu J. S., Wan L. J., Adv. Mater., 2008, 20, 2878—2887
[39]	Mabuchi A., Tokumitsu K., Fujimoto H., Kasuh T., J. Electrochem. Soc., 1995, 142, 1041—1046
[40]	Liu Y., Xue J., Zheng T., Dahn J., Carbon, 1996, 34, 193—200
[41]	Buiel E., Dahn J., Electrochim. Acta, 1999, 45, 121—130
[42]	Fujimoto H., Mabuchi A., Tokumitsu K., Kasuh T., J. Power Sources, 1995, 54, 440—443
[43]	Feng X., Yang J., Gao P., Wang J., Nuli Y., RSC Advances, 2012, 2, 5701—5706
[44]	Vu A., Qian Y., Stein A., Adv. Energy Mater., 2012, 2, 1056—1085
[45]	Liu N., Wu H., McDowell M. T., Yao Y., Wang C., Cui Y., Nano Lett., 2012, 12, 3315—3321
[46]	Cetinkaya T., Uysal M., Guler M. O., Akbulut H., Alp A., Powder Technol., 2014, 253, 63—69
[47]	Hu J., Li H., Huang X., Solid State Ionics, 2007, 178, 265—271
[48]	Hu J., Li H., Huang X., Solid State Ionics, 2005, 176, 1151—1159
[49]	Wang Q., Li H., Chen L., Huang X., Carbon, 2001, 39, 2211—2214
[50]	Wang Q., Li H., Chen L., Huang X., Solid State Ionics, 2002, 152, 43—50
[51]	Ebner M., Chung D. W., García R. E., Wood V., Adv. Energy Mater., 2014, 4, 1301278—1301283
[52]	Chen L., Xie X., Wang B., Wang K., Xie J., Mater. Sci. Eng. B, 2006, 131, 186—190
[53]	Fu L., Liu H., Li C., Wu Y., Rahm E., Holze R., Wu H., Solid State Sci., 2006, 8, 113—128
	(Ed.: S, Z, M)