锂离子电池负极材料纳米多孔硅/石墨/碳复合微球的制备与性能

doi:10.7503/cjcu20180856

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (6): 1216.doi: 10.7503/cjcu20180856

锂离子电池负极材料纳米多孔硅/石墨/碳复合微球的制备与性能

林伟国¹, 孙伟航², 曲宗凯², 冯晓磊², 荣峻峰¹(), 陈旭²(), 杨文胜²

1. 中国石油化工股份有限公司石油化工科学研究院, 北京 100083
2. 北京化工大学化工资源有效利用国家重点实验室, 北京 100029

收稿日期:2018-12-20 出版日期:2019-06-10 发布日期:2019-03-27
作者简介:
联系人简介: 荣俊峰, 男, 博士, 教授级高工, 主要从事新能源及相关材料研究. E-mail: rongjf.ripp@sinopec.com;陈旭, 女, 博士, 教授, 主要从事功能材料合成及电化学应用研究. E-mail: chenxu@mail.buct.edu.cn
基金资助:
国家自然科学基金(批准号: 21874005)和中国石油化工股份有限公司项目(批准号: 216805, 218025-2)资助.

Preparation and Performance of Nano-porous Si/Graphite/C Composite Microspheres as Anode Material for Li-ion Batteries^†

LIN Weiguo¹, SUN Weihang², QU Zongkai², FENG Xiaolei², RONG Junfeng¹(), CHEN Xu²(), YANG Wensheng²

1. Research Institute of Petroleum Processing, China Petroleum & Chemical Corporation, Beijing 100083, China;
2. State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Received:2018-12-20 Online:2019-06-10 Published:2019-03-27
Supported by:
† Supported by the National Natural Science Foundation of China(No.21874005) and the Research Institute of Petroleum Processing, China Petroleum & Chemical Corporation(Nos.216805, 218025-2).

摘要/Abstract

摘要：

以硅藻土为原料, 通过镁热还原反应得到多孔硅, 进一步利用砂磨得到纳米多孔硅, 然后通过球磨将其与片状石墨和沥青均匀混合, 采用喷雾干燥技术造粒, 高温煅烧后制备了纳米多孔硅/石墨/碳复合微球. 对所得复合微球的结构和理化性质进行了表征. 纳米多孔硅/石墨/碳复合微球作为锂离子电池负极材料展示出较高的可逆容量、优异的循环稳定性(100次循环后容量仍为790 mA·h/g, 容量保持率可达96.7%)及较好的倍率性能.

关键词: 锂离子电池, 负极材料, 硅碳复合微球, 多级缓冲结构, 纳米多孔

Abstract:

Porous Si was obtained from magnesiothermal reduction method using diatomite as the precursor, sand milling was carried out to prepare nano-porous Si(np-Si), After that, the np-Si was uniformly mixed with flake graphite and pitch by ball milling. Then np-Si/graphite/C composite microspheres were prepared by spray drying technology and calcined at high temperature. The structure and physicochemical properties of the composite microspheres were characterized. As anode material for Li-ion batteries, the results from electrochemical test reveal that the composite microspheres exhibit high reversible capacity(817 mA·h/g), excellent cycle stability(790 mA·h/g with 96.7% capacity retention after 100 cycles) and good rate performance. The superior electrochemical characteristics are mainly attributed to the hierarchical buffer structures composed of nanosized porous Si, graphite and pitch carbonized outer carbon, which effectively suppress the volume expansion of Si.

Key words: Li-ion battery, Anode material, Si/C composite microsphere, Hierarchical buffer structure, Nano-porosity

中图分类号:

O646

TrendMD:

林伟国, 孙伟航, 曲宗凯, 冯晓磊, 荣峻峰, 陈旭, 杨文胜. 锂离子电池负极材料纳米多孔硅/石墨/碳复合微球的制备与性能. 高等学校化学学报, 2019, 40(6): 1216.

LIN Weiguo,SUN Weihang,QU Zongkai,FENG Xiaolei,RONG Junfeng,CHEN Xu,YANG Wensheng. Preparation and Performance of Nano-porous Si/Graphite/C Composite Microspheres as Anode Material for Li-ion Batteries^†. Chem. J. Chinese Universities, 2019, 40(6): 1216.

图/表 5

Scheme 1 Schematic illustration of the synthesis of np-Si(A) and np-Si/G/C(B)

Fig.1 XRD patterns of the products obtained at different steps during the fabrication process(A), SEM image(B), nitrogen adsorption-desorption isotherm(C) and BJH pore size distribution curve(D) of np-Si a. Diatomite; b. sample after magnesiothermic reduction; c. np-Si.

Fig.2 SEM(A—D) and TEM images(E—G) of np-Si/G/C-1(A, C) and np-Si/G/C(B, D, E—G)

Table 1 Comparison of physicochemical properties of np-Si/G/C, np-Si/G/C-1 and np-Si/G/C-2 composite microspheres

Sample	D₅₀/μm	Specific surface area/(m²·g^Symbolm@1)	Tap density/(g·cm^Symbolm@3)
np-Si/G/C-1	11.70	37.0	0.29
np-Si/G/C-2	14.34	11.9	0.47
np-Si/G/C	18.97	4.7	0.70

Fig.3 Columbic efficiency in the first cycle at 0.2 A/g(A), cycling performance at 0.2 A/g(B) and rate capabilities(C) of np-Si/G/C, np-Si/G/C-1 and np-Si/G/C-2 samples

参考文献 26

[1]	Chen D. Y., Mei X., Ji G., Lu M. H., Xie J. P., Lu J. M., Lee J. Y., Angew. Chem. Int. Ed.,2012, 51, 2409-2413
[2]	Liu M. X., Ma X. M., Gan L. H., Xu Z. J., Zhu D. Z., Chen L. W., J. Mater. Chem. A,2014, 2, 17107-17114
[3]	Huang H. M., Zhang S. Q., Wang W., Wang C., Yu J., Chem. J. Chinese Universities,2012, 33(7), 1619-1623
	(黄绘敏,张苏强,王威,王策,于杰.高等学校化学学报, 2012, 33(7), 1619-1623)
[4]	Su X., Wu Q. L., Li J. C., Xiao X. C., Lott A., Lu W. Q., Sheldon B. W., Wu J., Adv. Energy Mater.,2014, 4, 1300882
[5]	Luo F., Liu B. N., Zheng J. Y., Chu G., Zhong K. F., Li H., Huang X. J., Chen L. Q., J. Electrochem. Soc.,2015, 162, A2509-A2528
[6]	Wang J. J., Xu T. T., Huang X., Li H., Ma T. L., RSC Adv.,2016, 6, 87778-87790
[7]	Nadimpalli S. P. V., Sethuraman V. A., Dalavi S., Lucht B., Chon M. J., Shenoy V. B., Guduru P. R., J. Power Sources,2012, 215, 145-151
[8]	Chang J., Huang X., Zhou G., Cui S., Mao S., Chen J., Nano Energy,2015, 15, 679-687
[9]	Feng K., Li M., Liu W.W., Kashkooli A. G., Xiao X. C., Cai M., Chen Z. W.,Small, 2018, 1702737
[10]	Chan C. K., Peng H. L., Liu G., McIlwrath K., Zhang X. F., Huggins R. A., Cui Y., Nat. Nanotechnol.,2008, 3, 31-35
[11]	Du C. Y., Gao C. H., Yin G. P., Chen M., Wang L., Energy Environ. Sci.,2011, 4, 1037-1042
[12]	Ko M., Chae S., Ma J., Kim N., Lee H. W., Cui Y., Cho J., Nat. Energy,2016, 1, 16113
[13]	Jaumann T., Balach J., Klose M., Oswald S., Langklotz U., Michaelis A., Eckert J., Giebeler L., Phys. Chem. Chem. Phys.,2015, 17, 24956-24967
[14]	Ma X. M., Liu M. X., Gan L. H., Tripathi P. K., Zhao Y. H., Zhu D. Z., Xu Z. J., Chen L. W., Phys. Chem. Chem. Phys.,2014, 16, 4135-4142
[15]	Jo Y. N., Kim Y., Kim J. S., Song J. H., Kim K. J., Kwag C. Y., Lee D. J., Park C. W., Kim Y. J., J. Power Sources,2010, 195, 6031-6036
[16]	Liu J., Zhang Q., Wu Z. Y., Li J. T., Huang L., Sun S. G., Chem. Electro. Chem.,2015, 2, 611-616
[17]	Yu Y. L., Li G., Zhou S., Chen X., Lee H. W., Yang W. S., Carbon,2017, 120, 397-404
[18]	Xu Q., Sun J. K., Li J. Y., Yin Y. X., Guo Y. G., Energy Storage Mater.,2018, 12, 54-60
[19]	Yin H., Zhou D., Cong L. N., Xie H. M., Qiu Y. Q., Chem. J. Chinese Universities,2015, 36(10), 1990-1994
	(尹红,周丹,丛丽娜,谢海明,仇永清.高等学校化学学报, 2015, 36(10), 1990-1994)
[20]	Kim S. Y., Lee J., Kim B. H., Kim Y. J., Yang K. S., Park M. S., ACS Appl. Mater.Interfaces,2016, 8, 12109-12117
[21]	Xu Q., Li J.Y., Sun J. K., Yin Y. X., Wan L. J., Guo Y. G.,Adv. Energy Mater., 2016, 1601481
[22]	Chen H. D., Wang S. F., Liu X. J., Hou X. H., Chen F. M., Pan H., Qin H. Q., Lam K. H., Xia Y. C., Zhou G. F., Electrochim. Acta,2018, 288, 134-143
[23]	Zuo X. X., Xia Y. G., Ji Q., Gao X., Yin S. S., Wang M. M., Wang X. Y., Qiu B., Wei A. X., Sun Z. C., Liu Z. P., Zhu J., Cheng Y. J., ACS Nano,2017, 11, 889-899
[24]	Liu H. T., Shan Z. Q., Huang W. L., Wang D. D., Lin Z. J., Cao Z. J., Chen P., Meng S. X., Chen Li., ACS Appl. Mater. Interfaces,2018, 10, 4715-4725
[25]	Sun L., Su T. T., Xu L., Du H. B., Phys. Chem. Chem. Phys.,2016, 18, 1521-1525
[26]	Liu J., Li N., Goodman M.D., Zhang H. G., Epstein E. S., Huang B., Pan Z., Kim J., Choi J. H., Huang X., Liu J., Hsia K. J., Dillon S. J., Braun P. V., ACS Nano, 2015, 9, 1985—1994

锂离子电池负极材料纳米多孔硅/石墨/碳复合微球的制备与性能

Preparation and Performance of Nano-porous Si/Graphite/C Composite Microspheres as Anode Material for Li-ion Batteries^†

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锂离子电池负极材料纳米多孔硅/石墨/碳复合微球的制备与性能

Preparation and Performance of Nano-porous Si/Graphite/C Composite Microspheres as Anode Material for Li-ion Batteries†

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Preparation and Performance of Nano-porous Si/Graphite/C Composite Microspheres as Anode Material for Li-ion Batteries^†