, Volume 25, Issue 2, pp 467–473 | Cite as

High-performance anode materials based on 3D orderly and vertically macroporous graphene-Si framework for Li-ion batteries

  • Fengjuan MiaoEmail author
  • Wanjuan Cong
  • Rui Miao
  • Na Wang
  • Wenyi Wu
  • Yu Zang
  • Cuiping Shi
  • Lei Zhu
  • Bairui TaoEmail author
  • Paul K. Chu
Original Paper


Porous graphene/Si-MCP (microchannel plate) microstructures are fabricated using electrochemical exfoliation and microelectronic machining. The few-layer graphene nanosheets with a lateral size of 600–850 nm and thickness of 2–3 nm are uniformed anchored on the surface and channels of the Si-MCP substrate. The as-prepared graphene/Si-MCP is used as the anode in lithium ion batteries and demonstrated to have a higher reversible capacity, better cycling retention, and excellent higher rate cycling performance compared to graphene/Si and Si-MCP. The good properties are attributed to the large surface-to-volume ratio of the structure and the better electrical contact with graphene. This silicon-based composite has large potential as anodes in integrated batteries.


Graphene/Si-MCP Anode Li-ion batteries Electrochemical exfoliation 


Funding information

This work was jointly supported by the Postdoctoral scientific research developmental fund of Heilongjiang Province (Grant No. LBH-Q15142, LBH-Q14157), Science and Technology Project of Qiqihar (Grant No. GYGG-201409, GYGG-201619), Higher School Science and Technology Achievements Industrialization Pre-Research and Development Foundation of Heilongjiang Province (Grant No. 1254CGZH04), University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province (Grant No. UNPYSCT-2016087), Scientific Research Foundation for the Returned Overseas Chinese Scholars in Heilongjiang Province, and Hong Kong Research Grants Council General Research Funds CityU 11301215.


  1. 1.
    Etacheri V, Marom R, Elazari R, Salitra G, Aurbach D (2011) Challenges in the development of advanced Li-ion bdd: a review. Energy Environ Sci 4:3243–3262CrossRefGoogle Scholar
  2. 2.
    Wang CY, Zhang GS, Ge SH, Xu T, Ji Y, Yang XG, Leng YJ (2018) Lithium-ion battery structure that self-heats at low temperatures. Nature 529(7587):515CrossRefGoogle Scholar
  3. 3.
    Qie L, Chen WM, Wang ZH, Shao QG, Li X, Yuan LX, Hu XL, Zhang WX, Huang YH (2012) Nitrogen-doped porous carbon nanofiber webs as anode for lithium ion battery with superhigh capacity and rate capability. Adv Mater 24:2047–2050CrossRefGoogle Scholar
  4. 4.
    Pan ZY, Sun H, Pan J, Zhang J, Wang BJ, Peng HS (2018) The creation of hollow walls in carbon nanotubes for high-performance lithium ion batteries. Carbon 133:384–389CrossRefGoogle Scholar
  5. 5.
    Munzer A, Xiao LS, Sehlleier YH, Schulz C, Wiggers H (2018) All gas-phase synthesis of graphene: characterization and its utilization for silicon-based lithium-ion batteries. Electrochem Acta 272:52–59CrossRefGoogle Scholar
  6. 6.
    Jung CH, Choi J, Kim WS, Hong SH (2018) A nanopore-embedded graphitic carbon shell on silicon anode for high performance lithium ion batteries. J Mater Chem A 6:8013–8020CrossRefGoogle Scholar
  7. 7.
    Magasinski A, Dixon P, Hertzberg B, Kvit A, Ayala J, Yushin G (2010) High-performance lithium-ion anodes using a hierarchical bottom-up approach. Nat Mater 9:353–358CrossRefGoogle Scholar
  8. 8.
    Xing Y, Shen T, Guo T, Wang XL, Xia XH, Gu CD, Tu JP (2018) A novel durable double-conductive core-shell structure applying to the synthesis of silicon anode for lithium ion batteries. J Power Sources 384:207–213CrossRefGoogle Scholar
  9. 9.
    Zhao X, Xia D, Gu L, Yue J, Li B, Wei H, Yan H, Zou R, Wang Y, Wang X, Zhang Z, Li J (2014) High-performance self-organized Si nanocomposite anode for lithium-ion batteries. J Energy Chem 23:291–300CrossRefGoogle Scholar
  10. 10.
    Kim T, Leyden MR, Ono LK, Qi YB (2018) Stacked-graphene layers as engineered solid-electrolyte interphase (SEI) grown by chemical vapour deposition for lithium-ion batteries. Carbon 132:678–690CrossRefGoogle Scholar
  11. 11.
    Li D, Müller MB, Gilje S, Kaner RB, Wallace GG (2008) Processable aqueous dispersions of graphene nanosheets. Nat Nanotechnol 3:101–105CrossRefGoogle Scholar
  12. 12.
    Xie QS, Liu PF, Zeng DQ, Xu WJ, Wang LS, Zhu ZZ, Mai LQ, Peng DL (2018) Dual electrostatic assembly of graphene encapsulated nanosheet-assembled ZnO-Mn-C hollow microspheres as a lithium ion battery anode. Adv Funct Mater 28:1707433CrossRefGoogle Scholar
  13. 13.
    He ZJ, Wua XW, Yi ZJ, Wang XY, Xiang YH (2017) Silicon/graphene/carbon hierarchical structure nanofibers for high performance lithium ion batteries. Mater Lett 200:128–131CrossRefGoogle Scholar
  14. 14.
    Cai HY, Han K, Jiang H, Wang JW, Liu H (2017) Self-standing silicon-carbon nanotube/graphene by a scalable in situ approach from low-cost Al-Si alloy powder for lithium ion batteries. J Phys Chem Solids 109:9–17CrossRefGoogle Scholar
  15. 15.
    Lee B, Liu TY, Kim S, Chang H, Eom K, Xie LX, Chen S, Jang HD, Lee SW (2017) Submicron silicon encapsulated with graphene and carbon as a scalable anode for lithium-ion batteries. Carbon 119:438–445CrossRefGoogle Scholar
  16. 16.
    Chen XM, Lin JL, Yuan D, Ci PL, Xin PS, Xu SH, Wang LW (2008) Obtaining a high area ratio free-standing silicon microchannel plate via a modified electrochemical procedure. J Micromech Microeng 18(3):037003CrossRefGoogle Scholar
  17. 17.
    Parvez K, Wu ZS, Li RJ, Liu X, Graf R, Feng XL, Müllen K (2014) Exfoliation of graphite into graphene in aqueous solutions of inorganic salts. J Am Chem Soc 136:6083–6091CrossRefGoogle Scholar
  18. 18.
    Miao FJ, Tao BR, Ci PL, Shi J, Wang LW (2009) 3D ordered NiO/silicon MCP array electrode materials for electrochemical supercapacitors. Mater Res Bull 44:1920–1925CrossRefGoogle Scholar
  19. 19.
    Chabot V, Kim B, Sloper B, Tzoganakis C, Yu A (2013) High yield production and purification of few layer graphene by gum arabic assisted physical sonication. Sci Rep 3:1378–1385CrossRefGoogle Scholar
  20. 20.
    Feng H, Cheng R, Zhao X, Duan X, Li J (2013) Corrigendum: a low-temperature method to produce highly reduced graphene oxide. Nat Commun 4:1539CrossRefGoogle Scholar
  21. 21.
    Ji JY, Ji HX, Zhang LL, Zhao X, Bai X, Fan XB, Zhang FB, Ruoff RS (2013) Graphene-encapsulated Si on ultrathin-graphite foam as anode for high capacity lithium-ion batteries. Adv Mater 25:4673–4677CrossRefGoogle Scholar
  22. 22.
    Miao FJ, Li QQ, Tao BR, Chu PK (2014) Fabrication of highly ordered porous nickel oxide anode materials and their electrochemical characteristics in lithium storage. J Alloys Compd 594:65–69CrossRefGoogle Scholar
  23. 23.
    Byon HR, Gallant BM, Lee SW, Yang SH (2013) Role of oxygen functional groups in carbon nanotube/graphene freestanding electrodes for high performance lithium batteries. Adv Funct Mater 23(8):1037–1045CrossRefGoogle Scholar
  24. 24.
    Cao HL, Zhou XF, Zheng C, Liu ZP (2015) Metal etching method for preparing porous graphene as high performance anode material for lithium-ion batteries. Carbon 89:41–46CrossRefGoogle Scholar
  25. 25.
    Tang H, Tu JP, Liu XY, Zhang YJ, Huang S, Li WZ, Wang XL, Gu CD (2014) Self-assembly of Si/honeycomb reduced graphene oxide composite film as a binder-free and flexible anode for Li-ion batteries. J Mater Chem A 2:5834–5840CrossRefGoogle Scholar
  26. 26.
    Kempton W (2016) Electric vehicles: driving range. Nat Energy 1:16131CrossRefGoogle Scholar
  27. 27.
    Gomez-Camer JL, Bunzli C, Hantel MM, Poux T, Novak P (2016) On the correlation between electrode expansion and cycling stability of graphite/Si electrodes for Li-ion batteries. Carbon 105:42–51CrossRefGoogle Scholar
  28. 28.
    Wang Q, Jiang B, Li B, Yan Y (2016) A critical review of thermal management models and solutions of lithium-ion batteries for the development of pure electric vehicles. Renew Sust Energ Rev 64:106–128CrossRefGoogle Scholar
  29. 29.
    Tang H, Zhang YJ, Xiong QQ, Cheng JD, Zhang Q, Wang XL, Gu CD, Tu JP (2015) Self-assembly silicon/porous reduced graphene oxide composite film as a binder-free and flexible anode for lithium-ion batteries. Electrochim Acta 156:86–93CrossRefGoogle Scholar
  30. 30.
    Yu HJ, Liu XL, Chen YX, Liu HB (2016) Carbon-coated Si/graphite composites with combined electrochemical properties for high-energy-density lithium-ion batteries. Ionics 22:1847–1853CrossRefGoogle Scholar
  31. 31.
    Tang H, Zhang J, Zhang YJ, Xiong QQ, Tong YY, Li Y, Wang XL, Gu CD, Tu JP (2015) Porous reduced graphene oxide sheet wrapped silicon composite fabricated by steam etching for lithium-ion battery application. J Power Sources 286:431–437CrossRefGoogle Scholar
  32. 32.
    Tao HC, Yang XL, Zhang LL, Ni SB (2015) Reduced graphene oxide/porous Si composite as anode for high-performance lithium ion batteries. Ionics 21:617–622CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Fengjuan Miao
    • 1
    Email author
  • Wanjuan Cong
    • 1
  • Rui Miao
    • 1
  • Na Wang
    • 1
  • Wenyi Wu
    • 1
  • Yu Zang
    • 2
  • Cuiping Shi
    • 1
  • Lei Zhu
    • 1
  • Bairui Tao
    • 1
    Email author
  • Paul K. Chu
    • 3
  1. 1.College of Communications and Electronics EngineeringQiqihar UniversityHeilongjiangChina
  2. 2.College of Materials Science and EngineeringQiqihar UniversityQiqiharChina
  3. 3.Department of Physics and Department of Materials Science and EngineeringCity University of Hong KongKowloonChina

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