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

doi:10.7503/cjcu20180856

Abstract

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

CLC Number:

O646

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2019, 40(6): 1216.

Figures/Tables 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

References 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