AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
Powered by AMiner. Clicking this button will take you away from SciOpen.
Home Nano Research Article
Article Link
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Outline
Show full outline
Hide outline
Outline
Show full outline
Hide outline
Research Article

Synergistic protection of Si anode based on multi-dimensional graphitic carbon skeletons

Qitao Shi1,§, Haiming Wang1,§, Junhua Zhou1, Huy Quang Ta1,2, Jiaqi Wang1, Xueyu Lian1, Klaudia Kurtyka3, Barbara Trzebicka3, Thomas Gemming4, Mark H. Rümmeli1,2,3,4( )
Soochow Institute for Energy and Materials Innovation, College of Energy, Key Laboratory of Advanced Carbon Materials and Wearable Energy Technologies of Jiangsu Province, Soochow University, Suzhou 215006, China
Institute for Complex Materials, IFW Dresden, 20 Helmholtz Strasse, Dresden 01069, Germany
Centre of Polymer and Carbon Materials, Polish Academy of Sciences, M. Curie-Sklodowskiej 34, Zabrze 41-819, Poland
Thomas Gemming - Institute of Environmental Technology, VSB-Technical University of Ostrava, 17. Listopadu 15, Ostrava 70833, Czech Republic

§ Qitao Shi and Haiming Wang contributed equally to this work.

Show Author Information

Graphical Abstract

This work proposes a bottom-up method synthesized hollow graphene shell as an elastic skeleton and employs graphene as an extra armor to synergistically prepare advanced corn-like Si@hollow graphene shell@graphene (Si@GS@G) anode. Improved conductivity and structural stability are harvested attributed to the porous and rigid conductive network.

Abstract

Inspired by the natural corn structure, a Si@hollow graphene shell@graphene (Si@GS@G) anode material was prepared in which silicon nanoparticles were preliminarily anchored onto the surface of an elastic graphene shell and further constrained using graphene sheets. Hollow graphene oxide shells with abundant surficial hydrogen bonds, which were synthesized using a novel bottom-up method, were used as an intermediate material to anchor positively charged silicon nanoparticles via electrostatic attraction and achieve a rational spatial distribution. The inner hollow graphene shell anchorage and outer graphene constraint synergistically constituted a porous and robust conductive corn-like structure. The as-fabricated Si@GS@G anode afforded efficient electron and ion transport pathways and improved structural stability, thereby enhancing Li+ storage capability (505 mAh·g−1 at 10 A·g−1) and extending the lifespan compared to the single hollow graphene shell or graphene sheet-protected Si anode (72% capacity retention after 500 cycles). The improved kinetics of the Si@GS@G anode were investigated using electro impedance spectroscopy, galvanostatic intermittent titration, and pseudocapacitance contribution rate analysis, and the structural evolution was analyzed using ex situ electron microscopy. This study proposes a novel hollow graphene oxide shell as an activated intermediate material for designing a porous electrode structure that facilitates an enhanced electrochemical performance.

Keywords

synergistic protectionmulti-dimensional graphitic carbonscorn-like structureelastic skeletonSi/C anode

Electronic Supplementary Material

Download File(s)
12274_2022_4518_MOESM1_ESM.pdf (1.1 MB)

References

1

Dühnen, S.; Betz, J.; Kolek, M.; Schmuch, R.; Winter, M.; Placke, T. Toward green battery cells: Perspective on materials and technologies. Small Methods 2020, 4, 2000039.
Crossref Google Scholar
2

Li, H. T.; Li, Y. G.; Zhang, L. Designing principles of advanced sulfur cathodes toward practical lithium-sulfur batteries. SusMat 2022, 2, 34–64.
Crossref Google Scholar
3

Shao, C. X.; Zhao, Y.; Qu, L. T. Recent advances in highly integrated energy conversion and storage system. SusMat 2022, 2, 142–160.
Crossref Google Scholar
4

Li, P.; Kim, H.; Myung, S. T.; Sun, Y. K. Diverting exploration of silicon anode into practical way: A review focused on silicon-graphite composite for lithium ion batteries. Energy Storage Mater. 2021, 35, 550–576.
Crossref Google Scholar
5

Guo, J. P.; Dong, D. Q.; Wang, J.; Liu, D.; Yu, X. Q.; Zheng, Y.; Wen, Z. R.; Lei, W.; Deng, Y. H.; Wang, J. et al. Silicon-based lithium ion battery systems: State-of-the-art from half and full cell viewpoint. Adv. Funct. Mater. 2021, 31, 2102546.
Crossref Google Scholar
6

Chen, X.; Li, H. X.; Yan, Z. H.; Cheng, F. Y.; Chen, J. Structure design and mechanism analysis of silicon anode for lithium-ion batteries. Sci. China Mater. 2019, 62, 1515–1536.
Crossref Google Scholar
7

Shi, Q. T.; Zhou, J. H.; Ullah, S.; Yang, X. Q.; Tokarska, K.; Trzebicka, B.; Ta, H. Q.; Rümmeli, M. H. A review of recent developments in Si/C composite materials for Li-ion batteries. Energy Storage Mater. 2021, 34, 735–754.
Crossref Google Scholar
8

Mao, E. Y.; Wang, W. Y.; Wan, M. T.; Wang, L.; He, X. M.; Sun, Y. M. Confining ultrafine Li3P nanoclusters in porous carbon for high-performance lithium-ion battery anode. Nano Res. 2020, 13, 1122–1126.
Crossref Google Scholar
9

Guan, P.; Li, J. J.; Lu, T. G.; Guan, T.; Ma, Z. L.; Peng, Z.; Zhu, X. Y.; Zhang, L. Facile and scalable approach to fabricate granadilla-like porous-structured silicon-based anode for lithium ion batteries. ACS Appl. Mater. Interfaces 2018, 10, 34283–34290.
Crossref Google Scholar
10

Wu, X. R.; Yu, C. H.; Li, C. C. Carbon-encapsulated gigaporous microsphere as potential Si anode-active material for lithium-ion batteries. Carbon 2020, 160, 255–264.
Crossref Google Scholar
11

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.
Crossref Google Scholar
12

Wang, B. R.; Li, W. W.; Wu, T.; Guo, J.; Wen, Z. Y. Self-template construction of mesoporous silicon submicrocube anode for advanced lithium ion batteries. Energy Storage Mater. 2018, 15, 139–147.
Crossref Google Scholar
13

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.
Crossref Google Scholar
14

Yang, J. P.; Wang, Y. X.; Chou, S. L.; Zhang, R. Y.; Xu, Y. F.; Fan, J. W.; Zhang, W. X.; Liu, H. K.; Zhao, D. Y.; Dou, S. X. Yolk–shell silicon-mesoporous carbon anode with compact solid electrolyte interphase film for superior lithium-ion batteries. Nano Energy 2015, 18, 133–142.
Crossref Google Scholar
15

Liu, N.; Wu, H.; McDowell, M. T.; Yao, Y.; Wang, C. M.; Cui, Y. A yolk–shell design for stabilized and scalable Li-ion battery alloy anodes. Nano Lett. 2012, 12, 3315–3321.
Crossref Google Scholar
16

Hwang, T. H.; Lee, Y. M.; Kong, B. S.; Seo, J. S.; Choi, J. W. Electrospun core–shell fibers for robust silicon nanoparticle-based lithium ion battery anodes. Nano Lett. 2012, 12, 802–807.
Crossref Google Scholar
17

Liu, N. T.; Liu, J.; Jia, D. Z.; Huang, Y. D.; Luo, J.; Mamat, X.; Yu, Y.; Dong, Y. M.; Hu, G. Z. Multi-core yolk–shell like mesoporous double carbon-coated silicon nanoparticles as anode materials for lithium-ion batteries. Energy Storage Mater. 2019, 18, 165–173.
Crossref Google Scholar
18

Hu, L.; Luo, B.; Wu, C. H.; Hu, P. F.; Wang, L. Z.; Zhang, H. J. Yolk–shell Si/C composites with multiple Si nanoparticles encapsulated into double carbon shells as lithium-ion battery anodes. J. Energy Chem. 2019, 32, 124–130.
Crossref Google Scholar
19

Yao, Y.; McDowell, M. T.; Ryu, I.; Wu, H.; Liu, N. A.; Hu, L. B.; Nix, W. D.; Cui, Y. Interconnected silicon hollow nanospheres for lithium-ion battery anodes with long cycle life. Nano Lett. 2011, 11, 2949–2954.
Crossref Google Scholar
20

Tian, H.; Tian, H. J.; Yang, W.; Zhang, F.; Yang, W.; Zhang, Q. B.; Wang, Y.; Liu, J.; Silva, S. R. P.; Liu, H. et al. Stable hollow-structured silicon suboxide-based anodes toward high-performance lithium-ion batteries. Adv. Funct. Mater. 2021, 31, 2101796.
Crossref Google Scholar
21

Chen, X. X.; Ge, G. F.; Wang, W. Y.; Zhang, B.; Jiang, J. J.; Yang, X. L.; Li, Y. Z.; Wang, L.; He, X. M.; Sun, Y. M. In situ formation of ionically conductive nanointerphase on Si particles for stable battery anode. Sci. China Chem. 2021, 64, 1417–1425.
Crossref Google Scholar
22

Dou, F.; Shi, L. Y.; Song, P. A.; Chen, G. R.; An, J.; Liu, H. J.; Zhang, D. S. Design of orderly carbon coatings for SiO anodes promoted by TiO2 toward high performance lithium-ion battery. Chem. Eng. J. 2018, 338, 488–495.
Crossref Google Scholar
23

Li, Z. H.; Wan, Z. W.; Zeng, X. Q.; Zhang, S. M.; Yan, L. J.; Ji, J. P.; Wang, H. X.; Ma, Q. X.; Liu, T. F.; Lin, Z. et al. A robust network binder via localized linking by small molecules for high-areal-capacity silicon anodes in lithium-ion batteries. Nano Energy 2021, 79, 105430.
Crossref Google Scholar
24

Jiao, X. X.; Yin, J. Q.; Xu. X. Y.; Wang, J. L.; Liu, Y. Y.; Xiong, S. Z.; Zhang, Q. L.; Song, J. X. Highly energy-dissipative, fast self-healing binder for stable Si anode in lithium-ion batteries. Adv. Funct. Mater. 2021, 31, 2005699.
Crossref Google Scholar
25

Zhang, Y. X.; Wu, B. R.; Mu, G.; Ma, C. W.; Mu, D. B.; Wu, F. Recent progress and perspectives on silicon anode: Synthesis and prelithiation for LIBs energy storage. J. Energy Chem. 2022, 64, 615–650.
Crossref Google Scholar
26

Kim, N.; Chae, S.; Ma, J.; Ko, M.; Cho, J. Fast-charging high-energy lithium-ion batteries via implantation of amorphous silicon nanolayer in edge-plane activated graphite anodes. Nat. Commun. 2017, 8, 812.
Crossref Google Scholar
27

Guo, J. G.; Zhai, W.; Sun, Q.; Ai, Q.; Li, J.; Cheng, J.; Dai, L. N.; Ci, L. J. Facilely tunable core–shell Si@SiOx nanostructures prepared in aqueous solution for lithium ion battery anode. Electrochim. Acta 2020, 342, 136068.
Crossref Google Scholar
28

Zhang, M.; Zhang, T. F.; Ma, Y. F.; Chen, Y. S. Latest development of nanostructured Si/C materials for lithium anode studies and applications. Energy Storage Mater. 2016, 4, 1–14.
Crossref Google Scholar
29

Shi, L. R.; Pang, C. L.; Chen, S. L.; Wang, M. Z.; Wang, K. X.; Tan, Z. J.; Gao, P.; Ren, J. G.; Huang, Y. Y.; Peng, H. L. et al. Vertical graphene growth on SiO microparticles for stable lithium ion battery anodes. Nano Lett. 2017, 17, 3681–3687.
Crossref Google Scholar
30

Son, I. H.; Park, J. H.; Kwon, S.; Park, S.; Rümmeli, M. H.; Bachmatiuk, A.; Song, H. J.; Ku, J.; Choi, J. W.; Choi, J. M. et al. Silicon carbide-free graphene growth on silicon for lithium-ion battery with high volumetric energy density. Nat. Commun. 2015, 6, 7393.
Crossref Google Scholar
31

Lin, G. H.; Wang, H. C.; Zhang, L.; Cheng, Q. J.; Gong, Z. L.; Ostrikov, K. K. Graphene nanowalls conformally coated with amorphous/nanocrystalline Si as high-performance binder-free nanocomposite anode for lithium-ion batteries. J. Power Sources 2019, 437, 226909.
Crossref Google Scholar
32

Zhou, J.; Jiang, S.; Li, Y.; Pan, Z.; Qian, Y.; Zhao, Y.; Lin, N.; Qian, Y. T. Chemical fixation of CO2 on activated Si: Producing graphitic carbon-stabilized Si particles for Li-storage. Energy Storage Mater. 2020, 31, 36–43.
Crossref Google Scholar
33

Yan, Y. T.; Xu, Z. X.; Liu, C. C.; Dou, H. L.; Wei, J. J.; Zhao, X. L.; Ma, J. J.; Dong, Q.; Xu, H. S.; He, Y. S. et al. Rational design of the robust Janus shell on silicon anodes for high-performance lithium-ion batteries. ACS Appl. Mater. Interfaces 2019, 11, 17375–17383.
Crossref Google Scholar
34

Zhou, X. M.; Liu, Y.; Du, C. Y.; Ren, Y.; Xiao, R.; Zuo, P. J.; Yin, G. P.; Ma, Y. L.; Cheng, X. Q.; Gao, Y. Z. Layer-by-layer engineered silicon-based sandwich nanomat as flexible anode for lithium-ion batteries. ACS Appl. Mater. Interfaces 2019, 11, 39970–39978.
Crossref Google Scholar
35

Yun, Q. B.; Qin, X. Y.; Lv, W.; He, Y. B.; Li, B. H.; Kang, F. Y.; Yang, Q. H. “Concrete” inspired construction of a silicon/carbon hybrid electrode for high performance lithium ion battery. Carbon 2015, 93, 59–67.
Crossref Google Scholar
36

Lu, C.; Sun, Z. T.; Yu, L. H.; Lian, X. Y.; Yi, Y. Y.; Li, J.; Liu, Z. F.; Dou, S. X.; Sun, J. Y. Enhanced kinetics harvested in heteroatom dual-doped graphitic hollow architectures toward high rate printable potassium-ion batteries. Adv. Energy Mater. 2020, 10, 2001161.
Crossref Google Scholar
37

Dai, X.; Wu, J.; Qian, Z. C.; Wang, H. Y.; Jian, J.; Cao, Y. J.; Rummeli, M. H.; Yi, Q. H.; Liu, H. Y.; Zou, G. F. Ultra-smooth glassy graphene thin films for flexible transparent circuits. Sci. Adv. 2016, 2, e1601574.
Crossref Google Scholar
38

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.
Crossref Google Scholar
39

Xi, Y. B.; Wang, Y. Y.; Yang, D. J.; Zhang, Z. K.; Liu, W. F.; Li, Q.; Qiu, X. Q. K2CO3 activation enhancing the graphitization of porous lignin carbon derived from enzymatic hydrolysis lignin for high performance lithium-ion storage. J. Alloys Compd. 2019, 785, 706–714.
Crossref Google Scholar
40

Qiao, Z.; Hwang, S.; Li, X.; Wang, C. Y.; Samarakoon, W.; Karakalos, S.; Li, D. G.; Chen, M. J.; He, Y. H.; Wang, M. Y. et al. 3D porous graphitic nanocarbon for enhancing the performance and durability of Pt catalysts: A balance between graphitization and hierarchical porosity. Energy Environ. Sci. 2019, 12, 2830–2841.
Crossref Google Scholar
41

Shen, C. F.; Fang, X.; Ge, M. Y.; Zhang, A. Y.; Liu, Y. H.; Ma, Y. Q.; Mecklenburg, M.; Nie, X.; Zhou, C. W. Hierarchical carbon-coated ball-milled silicon: Synthesis and applications in free-standing electrodes and high-voltage full lithium-ion batteries. ACS Nano 2018, 12, 6280–6291.
Crossref Google Scholar
42

Zhu, X. Q.; Shen, J. L.; Chen, X. F.; Li, Y.; Peng, W. C.; Zhang, G. L.; Zhang, F. B.; Fan, X. B. Enhanced cycling performance of Si-MXene nanohybrids as anode for high performance lithium ion batteries. Chem. Eng. J. 2019, 378, 122212.
Crossref Google Scholar
43

Schroder, K.; Alvarado, J.; Yersak, T. A.; Li, J. C.; Dudney, N.; Webb, L. J.; Meng, Y. S.; Stevenson, K. J. The effect of fluoroethylene carbonate as an additive on the solid electrolyte interphase on silicon lithium-ion electrodes. Chem. Mater. 2015, 27, 5531–5542.
Crossref Google Scholar
44

Chen, L. B.; Wang, K.; Xie, X. H.; Xie, J. Y. Effect of vinylene carbonate (VC) as electrolyte additive on electrochemical performance of Si film anode for lithium ion batteries. J. Power Sources 2007, 174, 538–543.
Crossref Google Scholar
45

Cao, D.; Ren, M. X.; Xiong, J.; Pan, L. M.; Wang, Y.; Ji, X. Z.; Qiu, T.; Yang, J.; Zhang, C. F. J. Self-assembly of hierarchical Ti3C2Tx-CNT/SiNPs resilient films for high performance lithium ion battery electrodes. Electrochim. Acta 2020, 348, 136211.
Crossref Google Scholar
46

Jeong, M. G.; Du, H. L.; Islam, M.; Lee, J. K.; Sun, Y. K.; Jung, H. G. Self-rearrangement of silicon nanoparticles embedded in MicroCarbon sphere framework for high-energy and long-life lithium-ion batteries. Nano Lett. 2017, 17, 5600–5606.
Crossref Google Scholar
47

Chen, F. Q.; Han, J. W.; Kong, D. B.; Yuan, Y. F.; Xiao, J.; Wu, S. C.; Tang, D. M.; Deng, Y. Q.; Lv, W.; Lu, J. et al. 1,000 Wh·L−1 lithium-ion batteries enabled by crosslink-shrunk tough carbon encapsulated silicon microparticle anodes. Natl. Sci. Rev. 2021, 8, nwab012.
Crossref Google Scholar
48

Jin, Y.; Li, S.; Kushima, A.; Zheng, X. Q.; Sun, Y. M.; Xie, J.; Sun, J.; Xue, W. J.; Zhou, G. M.; Wu, J. et al. Self-healing SEI enables full-cell cycling of a silicon-majority anode with a Coulombic efficiency exceeding 99.9%. Energy Environ. Sci. 2017, 10, 580–592.
Crossref Google Scholar
49

Ma, Q.; Zhao, Z. Q.; Zhao, Y.; Xie, H. W.; Xing, P. F.; Wang, D. H.; Yin, H. Y. A self-driven alloying/dealloying approach to nanostructuring micro-silicon for high-performance lithium-ion battery anodes. Energy Storage Mater. 2021, 34, 768–777.
Crossref Google Scholar
50

Pu, X. J.; Zhao, D.; Fu, C. L.; Chen, Z. X.; Cao, S. N.; Wang, C. S.; Cao, Y. L. Understanding and calibration of charge storage mechanism in cyclic voltammetry curves. Angew. Chem., Int. Ed. 2021, 133, 21480–21488.
Crossref Google Scholar
51

Jiang, Y. Q.; Liu, J. P. Definitions of pseudocapacitive materials: A brief review. Energy Environ. Mater. 2019, 2, 30–37.
Crossref Google Scholar
52

Zhang, Q.; Wang, D. F.; Yang, B. W.; Cui, X.; Li, X. Electrochemical model of lithium-ion battery for wide frequency range applications. Electrochim. Acta 2020, 343, 136094.
Crossref Google Scholar
53

Zhang, S. P.; Wang, G.; Zhang, Z. L.; Wang, B. B. ; Bai, J. T.; Wang, H. 3D graphene networks encapsulated with ultrathin SnS nanosheets@hollow mesoporous carbon spheres nanocomposite with pseudocapacitance-enhanced lithium and sodium storage kinetics. Small 2019, 15, 1900565.
Crossref Google Scholar
54

Mathis, T. S.; Kurra, N.; Wang, X. H.; Pinto, D.; Simon, P.; Gogotsi, Y. Energy storage data reporting in perspective-guidelines for interpreting the performance of electrochemical energy storage systems. Adv. Energy Mater. 2019, 9, 1902007.
Crossref Google Scholar
55

Mao, Z.; Farkhondeh, M.; Pritzker, M.; Fowler, M.; Chen, Z. Dynamics of a blended lithium-ion battery electrode during galvanostatic intermittent titration technique. Electrochim. Acta 2016, 222, 1741–1750.
Crossref Google Scholar
56

Shen, Z.; Cao, L.; Rahn, C. D.; Wang, C. Y. Least squares galvanostatic intermittent titration technique (LS-GITT) for accurate solid phase diffusivity measurement. J. Electrochem. Soc. 2013, 160, A1842–A1846.
Crossref Google Scholar
Nano Research
Volume 15 Issue 9,
September 2022
Pages 8146-8155
DOI: 10.1007/s12274-022-4518-9
Cite this article:
Shi Q, Wang H, Zhou J, et al. Synergistic protection of Si anode based on multi-dimensional graphitic carbon skeletons. Nano Research, 2022, 15(9): 8146-8155. https://doi.org/10.1007/s12274-022-4518-9
Topics:
Batteries

1012

Views

23

Crossref

23

Web of Science

23

Scopus

0

CSCD

Altmetrics
Received: 18 March 2022
Revised: 25 April 2022
Accepted: 09 May 2022
Published: 22 June 2022
© Tsinghua University Press 2022
Return