Journal Home > Volume 15 , Issue 7
Nano Research 2022, 15(7): 6184-6191 https://doi.org/10.1007/s12274-022-4275-9
Research Article | Issue | Published: 26 April 2022

Synthesis of carbon nanotubes-supported porous silicon microparticles in low-temperature molten salt for high-performance Li-ion battery anodes

Show Author's Information Qianliang Zhang1,  Baojuan Xi1( ),  Weihua Chen2,  Jinkui Feng3,  Yitai Qian1,  Shenglin Xiong1( )
Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, China
Key Laboratory of Material Processing and Mold of Ministry of Education, Zhengzhou University, Zhengzhou 450001, China
Key Laboratory for Liquid-Solid Structural Evolution & Processing of Materials, Ministry of Education, School of Materials Science and Engineering, Shandong University, Jinan 250061, China
Keywords:
carbon nanotubes, molten salt, lithium-ion batteries, porous Si microparticles
Topics:
Lithium batteries
Cite this article:
Zhang Q, Xi B, Chen W, et al. Synthesis of carbon nanotubes-supported porous silicon microparticles in low-temperature molten salt for high-performance Li-ion battery anodes. Nano Research, 2022, 15(7): 6184-6191. https://doi.org/10.1007/s12274-022-4275-9
Download citation
EndNote(RIS)
BibTeX

776

Views

65

Downloads

Citations

24

Crossref

21

WoS

24

Scopus

0

CSCD

Abstract Full text Electronic supplementary material About this article

Silicon-based materials has attracted attention as a promising candidate for lithium-ion batteries (LIBs) with high energy density. However, severe volume variation, pulverization, and poor conductivity hindered the development of Si based materials. In this study, porous Si microparticles supported by carbon nanotubes (p-Si/CNT) are fabricated through simple molten salt assisted dealloying process at low temperature followed by acid treatment. The ZnCl2 molten salt not only provides the liquid environment to enhance the reaction, but also participates the dealloying process and works as template for porous structure when removes by acid treatment. Additionally, distribution of defect sites in CNTs also increases after molten salt process. Density function theory (DFT) calculations further prove the defects could improve the adsorption of Li+. The participation of CNTs can also contribute to the reaction kinetics and retain the integrity of the electrode. As expected, the p-Si/CNT anode manifests enhanced lithium-storage performance in terms of superior cycling stability and good rate capability. The p-Si/CNT//LiCoO2 full cell assembly further demonstrates its potential as a prospective anode for high-performance LIBs.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

Synthesis of carbon nanotubes-supported porous silicon microparticles in low-temperature molten salt for high-performance Li-ion battery anodes

Show Author's information Qianliang Zhang1, Baojuan Xi1( ), Weihua Chen2, Jinkui Feng3, Yitai Qian1, Shenglin Xiong1( )
Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, China
Key Laboratory of Material Processing and Mold of Ministry of Education, Zhengzhou University, Zhengzhou 450001, China
Key Laboratory for Liquid-Solid Structural Evolution & Processing of Materials, Ministry of Education, School of Materials Science and Engineering, Shandong University, Jinan 250061, China

Abstract

Silicon-based materials has attracted attention as a promising candidate for lithium-ion batteries (LIBs) with high energy density. However, severe volume variation, pulverization, and poor conductivity hindered the development of Si based materials. In this study, porous Si microparticles supported by carbon nanotubes (p-Si/CNT) are fabricated through simple molten salt assisted dealloying process at low temperature followed by acid treatment. The ZnCl2 molten salt not only provides the liquid environment to enhance the reaction, but also participates the dealloying process and works as template for porous structure when removes by acid treatment. Additionally, distribution of defect sites in CNTs also increases after molten salt process. Density function theory (DFT) calculations further prove the defects could improve the adsorption of Li+. The participation of CNTs can also contribute to the reaction kinetics and retain the integrity of the electrode. As expected, the p-Si/CNT anode manifests enhanced lithium-storage performance in terms of superior cycling stability and good rate capability. The p-Si/CNT//LiCoO2 full cell assembly further demonstrates its potential as a prospective anode for high-performance LIBs.

Keywords: carbon nanotubes, molten salt, lithium-ion batteries, porous Si microparticles

References(50)

1

Liu, J.; Bao, Z. N.; Cui, Y.; Dufek, E. J.; Goodenough, J. B.; Khalifah, P.; Li, Q. Y.; Liaw, B. Y.; Liu, P.; Manthiram, A. et al. Pathways for practical high-energy long-cycling lithium metal batteries. Nat. Energy 2019, 4, 180–186.
DOI Google Scholar
2

Zu, C. X.; Yu, H. G.; Li, H. Enabling the thermal stability of solid electrolyte interphase in Li-ion battery. InfoMat 2021, 3, 648–661.
DOI Google Scholar
3

Parekh, M. H.; Parikh, V. P.; Kim, P. J.; Misra, S.; Qi, Z. M.; Wang, H. Y.; Pol, V. G. Encapsulation and networking of silicon nanoparticles using amorphous carbon and graphite for high performance Li-ion batteries. Carbon 2019, 148, 36–43.
DOI Google Scholar
4

Zhang, Q. L.; Xi, B. J.; Xiong, S. L.; Qian, Y. T. Carbon coated SiO nanoparticles embedded in hierarchical porous N-doped carbon nanosheets for enhanced lithium storage. Inorg. Chem. Front. 2021, 8, 4282–4290.
DOI Google Scholar
5

Wang, L. B.; Lin, N.; Zhou, J. B.; Zhu, Y. C.; Qian, Y. T. Silicon nanoparticles obtained via a low temperature chemical “metathesis” synthesis route and their lithium-ion battery properties. Chem. Commun. 2015, 51, 2345–2348.
DOI Google Scholar
6

Zhou, J. B.; Liu, X. Y.; Cai, W. L.; Zhu, Y. C.; Liang, J. W.; Zhang, K. L.; Lan, Y.; Jiang, Z. H.; Wang, G. M.; Qian, Y. T. Wet-chemical synthesis of hollow red-phosphorus nanospheres with porous shells as anodes for high-performance lithium-ion and sodium-ion batteries. Adv. Mater. 2017, 29, 1700214.
DOI Google Scholar
7

Zhang, S. J.; Liu, C.; Wang, H. L.; Wang, H. P.; Sun, J. T.; Zhang, Y. M.; Han, X. P.; Cao, Y.; Liu, S.; Sun, J. A covalent P–C bond stabilizes red phosphorus in an engineered carbon host for high-performance lithium-ion battery anodes. ACS Nano 2021, 15, 3365–3375.
DOI Google Scholar
8

Liu, X. Y.; Zhang, L.; Liu, Z.; Zheng, Y. P.; Zhao, Y.; Yang, Y. C.; Zhang, Q. L.; Li, S. Y. Alkaliphilic Cu(OH)2 nanowires on copper foam for dendrite-free alkali metal anodes. J. Alloys Compd. 2022, 898, 162815.
DOI Google Scholar
9

Wei, C. L.; Fei, H. F.; An, Y. L.; Tao, Y.; Feng, J. K.; Qian, Y. T. Uniform Li deposition by regulating the initial nucleation barrier via a simple liquid-metal coating for a dendrite-free Li-metal anode. J. Mater. Chem. A 2019, 7, 18861–18870.
DOI Google Scholar
10

Feng, X. Y.; Wu, H. H.; Gao, B.; Świętosławski, M.; He, X.; Zhang, Q. B. Lithiophilic N-doped carbon bowls induced Li deposition in layered graphene film for advanced lithium metal batteries. Nano Res. 2022, 15, 352–360.
DOI Google Scholar
11

Sun, Y. M.; Liu, N.; Cui, Y. Promises and challenges of nanomaterials for lithium-based rechargeable batteries. Nat. Energy 2016, 1, 16071.
DOI Google Scholar
12

Hou, G. L.; Cheng, B. L.; Yang, Y. J.; Du, Y.; Zhang, Y. H.; Li, B. Q.; He, J. P.; Zhou, Y. Z.; Yi, D.; Zhao, N. N. et al. Multiscale buffering engineering in silicon-carbon anode for ultrastable Li-ion storage. ACS Nano 2019, 13, 10179–10190.
DOI Google Scholar
13

Chen, M.; Zhou, Q. N.; Zai, J. T.; Iqbal, A.; Tsega, T.; Dong, B. X.; Liu, X. J.; Zhang, Y. C.; Yan, C. Y.; Zhao, L. et al. High power and stable P-doped yolk–shell structured Si@C anode simultaneously enhancing conductivity and Li+ diffusion kinetics. Nano Res. 2021, 14, 1004–1011.
DOI Google Scholar
14

Han, Y.; Zhou, J.; Li, T. Q.; Yi, Z.; Lin, N.; Qian, Y. T. Molten-salt chemical exfoliation process for preparing two-dimensional mesoporous Si nanosheets as high-rate Li-storage anode. Nano Res. 2018, 11, 6294–6303.
DOI Google Scholar
15

Zhao, Y. M.; Yue, F. S.; Li, S. C.; Zhang, Y.; Tian, Z. R.; Xu, Q.; Xin, S.; Guo, Y. G. Advances of polymer binders for silicon-based anodes in high energy density lithium-ion batteries. InfoMat 2021, 3, 460–501.
DOI Google Scholar
16

Tian, Y.; An, Y. L.; Feng, J. K. Flexible and freestanding silicon/MXene composite papers for high-performance lithium-ion batteries. ACS Appl. Mater. Interfaces 2019, 11, 10004–10011.
DOI Google Scholar
17

Lin, N.; Han, Y.; Zhou, J.; Zhang, K. L.; Xu, T. J.; Zhu, Y. C.; Qian, Y. T. A low temperature molten salt process for aluminothermic reduction of silicon oxides to crystalline Si for Li-ion batteries. Energy Environ. Sci. 2015, 8, 3187–3191.
DOI Google Scholar
18

Zong, L. Q.; Zhu, B.; Lu, Z. D.; Tan, Y. L.; Jin, Y.; Liu, N.; Hu, Y.; Gu, S.; Zhu, J.; Cui, Y. Nanopurification of silicon from 84% to 99. 999% purity with a simple and scalable process. Proc. Natl. Acad. Sci. USA 2015, 112, 13473–13477.
DOI Google Scholar
19

Yi, Z.; Qian, Y.; Cao, C. H.; Lin, N.; Qian, Y. T. Porous Si/C microspheres decorated with stable outer carbon interphase and inner interpenetrated Si@C channels for enhanced lithium storage. Carbon 2019, 149, 664–671.
DOI Google Scholar
20

Sohn, M.; Lee, D. G.; Park, H. I.; Park, C.; Choi, J. H.; Kim, H. Microstructure controlled porous silicon particles as a high capacity lithium storage material via dual step pore engineering. Adv. Funct. Mater. 2018, 28, 1800855.
DOI Google Scholar
21

Ge, M. Y.; Lu, Y. H.; Ercius, P.; Rong, J. P.; Fang, X.; Mecklenburg, M.; Zhou, C. W. Large-scale fabrication, 3D tomography, and lithium-ion battery application of porous silicon. Nano Lett. 2014, 14, 261–268.
DOI Google Scholar
22

An, W. L.; Gao, B.; Mei, S. X.; Xiang, B.; Fu, J. J.; Wang, L.; Zhang, Q. B.; Chu, P. K.; Huo, K. F. Scalable synthesis of ant-nest-like bulk porous silicon for high-performance lithium-ion battery anodes. Nat. Commun. 2019, 10, 1447.
DOI Google Scholar
23

Zhai, W.; Ai, Q.; Chen, L. N.; Wei, S. Y.; Li, D. P.; Zhang, L.; Si, P. C.; Feng, J. K.; Ci, L. J. Walnut-inspired microsized porous silicon/graphene core–shell composites for high-performance lithium-ion battery anodes. Nano Res. 2017, 10, 4274–4283.
DOI Google Scholar
24

Yi, Z.; Lin, N.; Xu, T. J.; Qian, Y. T. TiO2 coated Si/C interconnected microsphere with stable framework and interface for high-rate lithium storage. Chem. Eng. J. 2018, 347, 214–222.
DOI Google Scholar
25

An, Y. L.; Tian, Y.; Wei, H.; Xi, B. J.; Xiong, S. L.; Feng, J. K.; Qian, Y. T. Porosity- and graphitization-controlled fabrication of nanoporous silicon@carbon for lithium storage and its conjugation with MXene for lithium-metal anode. Adv. Funct. Mater. 2020, 30, 1908721.
DOI Google Scholar
26

Chae, S.; Xu, Y. B.; Yi, R.; Lim, H. S.; Velickovic, D.; Li, X. L.; Li, Q. Y.; Wang, C. M.; Zhang, J. G. A micrometer-sized silicon/carbon composite anode synthesized by impregnation of petroleum pitch in nanoporous silicon. Adv. Mater. 2021, 33, 2103095.
DOI Google Scholar
27

Huang, Y. H.; Luo, J.; Peng, J.; Shi, M. H.; Li, X. X.; Wang, X. Y.; Chang, B. B. Porous silicon-graphene-carbon composite as high performance anode material for lithium ion batteries. J. Energy Storage 2020, 27, 101075.
DOI Google Scholar
28

Zhou, W. Y.; Lian, Q. H.; Huang, X. K.; Ding, W. Q.; Jiang, C. H.; Zou, Z. M.; Su, X. D. Introducing SiC/C dual-interface on porous silicon anode by a conventional exothermic displacement reaction for improved cycle performance. J. Power Sources 2021, 508, 230326.
DOI Google Scholar
29

Salvetat, J. P.; Bonard, J. M.; Thomson, N. H.; Kulik, A. J.; Forró, L.; Benoit, W.; Zuppiroli, L. Mechanical properties of carbon nanotubes. Appl. Phys. A 1999, 69, 255–260.
DOI Google Scholar
30

Zeng, Y. F.; Huang, Y. D.; Liu, N. T.; Wang, X. C.; Zhang, Y.; Guo, Y.; Wu, H. H.; Chen, H. X.; Tang, X. C.; Zhang, Q. B. N-doped porous carbon nanofibers sheathed pumpkin-like Si/C composites as free-standing anodes for lithium-ion batteries. J. Energy Chem. 2021, 54, 727–735.
DOI Google Scholar
31

Liang, J. W.; Li, X. N.; Hou, Z. G.; Guo, C.; Zhu, Y. C.; Qian, Y. T. Nanoporous silicon prepared through air-oxidation demagnesiation of Mg2Si and properties of its lithium ion batteries. Chem. Commun. 2015, 51, 7230–7233.
DOI Google Scholar
32

Kresse, G.; Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 1996, 6, 15–50.
DOI Google Scholar
33

Kresse, G.; Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 1996, 54, 11169–11186.
DOI Google Scholar
34

Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 1994, 50, 17953–17979.
DOI Google Scholar
35

Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865–3868.
DOI Google Scholar
36

Monkhorst, H. J.; Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 1976, 13, 5188–5192.
DOI Google Scholar
37

Peng, X. D.; Xiong, C.; Lin, Y. K.; Zhao, C.; Zhao, T. S. Honeycomb-like hierarchical porous silicon composites with dual protection for ultrastable Li-ion battery anodes. SmartMat 2021, 2, 579–590.
DOI Google Scholar
38

Acres, R. G.; Ellis, A. V.; Alvino, J.; Lenahan, C. E.; Khodakov, D. A.; Metha, G. F.; Andersson, G. G. Molecular structure of 3-aminopropyltriethoxysilane layers formed on silanol-terminated silicon surfaces. J. Phys. Chem. C 2012, 116, 6289–6297.
DOI Google Scholar
39

Xu, K. Q.; Ben, L. B.; Li, H.; Huang, X. J. Silicon-based nanosheets synthesized by a topochemical reaction for use as anodes for lithium ion batteries. Nano Res. 2015, 8, 2654–2662.
DOI Google Scholar
40

Yuan, Y.; Chen, Z. W.; Yu, H. X.; Zhang, X. K.; Liu, T. T.; Xia, M. T.; Zheng, R. T.; Shui, M.; Shu, J. Heteroatom-doped carbon-based materials for lithium and sodium ion batteries. Energy Storage Mater. 2020, 32, 65–90.
DOI Google Scholar
41

Yang, Z. X.; Du, Y.; Hou, G. L.; Ouyang, Y. G.; Ding, F.; Yuan, F. L. Nanoporous silicon spheres preparation via a controllable magnesiothermic reduction as anode for Li-ion batteries. Electrochim. Acta 2020, 329, 135141.
DOI Google Scholar
42

An, Y. L.; Fei, H. F.; Zeng, G. F.; Ci, L. J.; Xiong, S. L.; Feng, J. K.; Qian, Y. T. Green, scalable, and controllable fabrication of nanoporous silicon from commercial alloy precursors for high-energy lithium-ion batteries. ACS Nano 2018, 12, 4993–5002.
DOI Google Scholar
43

Li, X. L.; Gu, M.; Hu, S. Y.; Kennard, R.; Yan, P. F.; Chen, X. L.; Wang, C. M.; Sailor, M. J.; Zhang, J. G.; Liu, J. Mesoporous silicon sponge as an anti-pulverization structure for high-performance lithium-ion battery anodes. Nat. Commun. 2014, 5, 4105.
DOI Google Scholar
44

Simon, P.; Gogotsi, Y.; Dunn, B. Where do batteries end and supercapacitors begin? Science 2014, 343, 1210–1211.
DOI Google Scholar
45

Pan, K.; Zou, F.; Canova, M.; Zhu, Y.; Kim, J. H. Systematic electrochemical characterizations of Si and SiO anodes for high-capacity Li-Ion batteries. J. Power Sources 2019, 413, 20–28.
DOI Google Scholar
46

Suh, S.; Choi, H.; Eom, K.; Kim, H. J. Enhancing the electrochemical properties of a Si anode by introducing cobalt metal as a conductive buffer for lithium-ion batteries. J. Alloys Compd. 2020, 827, 154102.
DOI Google Scholar
47

Zhang, H.; Zong, P.; Chen, M.; Jin, H.; Bai, Y.; Li, S. W.; Ma, F.; Xu, H.; Lian, K. In situ synthesis of multilayer carbon matrix decorated with copper particles: Enhancing the performance of Si as anode for Li-ion batteries. ACS Nano 2019, 13, 3054–3062.
DOI Google Scholar
48

Cai, W. L.; Song, Y. Z.; Fang, Y. T.; Wang, W. W.; Yu, S. L.; Ao, H. S.; Zhu, Y. C.; Qian, Y. T. Defect engineering on carbon black for accelerated Li-S chemistry. Nano Res. 2020, 13, 3315–3320.
DOI Google Scholar
49

Fan, X. F.; Zheng, W. T.; Kuo, J. L. Adsorption and diffusion of Li on pristine and defective graphene. ACS Appl. Mater. Interfaces 2012, 4, 2432–2438.
DOI Google Scholar
50

Zheng, J. M.; Ren, Z. Y.; Guo, P.; Fang, L.; Fan, J. Diffusion of Li+ ion on graphene: A DFT study. Appl. Surf. Sci. 2011, 258, 1651–1655.
DOI Google Scholar
File
12274_2022_4275_MOESM1_ESM.pdf (1.4 MB)
Publication history
Copyright
Acknowledgements

Publication history

Received: 05 January 2022
Revised: 18 February 2022
Accepted: 27 February 2022
Published: 26 April 2022
Issue date: July 2022

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

The authors gratefully acknowledge the financial supports provided by the National Natural Science Foundation of China (Nos. U21A2077, 21971145, and 21871164), the Taishan Scholar Project Foundation of Shandong Province (No. ts20190908), the Natural Science Foundation of Shandong Province (Nos. ZR2021ZD05 and ZR2019MB024), and Young Scholars Program of Shandong University (No. 2017WLJH15).

Return