Skip to main content
SpringerLink
Log in

Composites of graphene and encapsulated silicon for practically viable high-performance lithium-ion batteries

  • Research Article
  • Published:
Nano Research Aims and scope Submit manuscript

Abstract

A facile and scalable approach to synthesize silicon composite anodes has been developed by encapsulating Si particles via in situ polymerization and carbonization of phloroglucinol-formaldehyde gel, followed by incorporation of graphene nanoplatelets. As a result of its structural integrity, high packing density and an intimate electrical contact consolidated by the conductive networks, the composite anode yielded excellent electrochemical performance in terms of charge storage capability, cycling life and coulombic efficiency. A half cell achieved reversible capacities of 1,600 mAh·g−1 and 1,000 mAh·g−1 at 0.5 A·g−1 and 2.1 A·g−1, respectively, while retaining more than 70% of the initial capacities over 1,000 cycles. Complete lithium-ion pouch cells coupling the anode with a lithium metal oxide cathode demonstrated excellent cycling performance and energy output, representing significant advance in developing Si-based electrode for practical application in high-performance lithium-ion batteries.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Boukamp, B. A.; Lesh, G. C.; Huggins, R. A. All-solid lithium electrodes with mixed-conductor matrix. J. Electrochem. Soc. 1981, 128, 725–729.

    Article  Google Scholar 

  2. Larcher, D.; Beattie, S.; Morcrette, M.; Edström, K.; Jumas, J.-C.; Tarascon, J.-M. Recent finds and prospects in the field of pure metals as negative electrodes for Li-ion batteries. J. Mater. Chem. 2007, 17, 3759–3772.

    Article  Google Scholar 

  3. Obrovac, M. N.; Christensen, L. Structural changes in silicon anodes during lithium insertion/extraction. Electrochem. Solid-State Lett. 2004, 7, A93–A96.

    Article  Google Scholar 

  4. Key, B.; Bhattacharyya, R.; Morcrette, M.; Seznéc, V.; Tarascon, J.-M.; Grey, C. P. Real-time NMR investigations of structural changes in silicon electrodes for lithium-ion batteries. J. Am. Chem. Soc. 2009, 131, 9239–9249.

    Article  Google Scholar 

  5. Chan, C. K.; Peng, H.; Liu, G.; McIlwrath, K.; Zhang, X. F.; Huggins, R. A.; Cui, Y. High-performance lithium battery anodes using silicon nanowires. Nat. Nanotechnol. 2008, 3, 31–35.

    Article  Google Scholar 

  6. Oumellal, Y.; Delpuech, N.; Mazouzi, D.; Dupré, N.; Gaubicher, J.; Moreau, P.; Soudan, P.; Lestriez, B.; Guyomard, D. The failure mechanism of nano-sized Si-based negative electrodes for lithium ion batteries. J. Mater. Chem. 2011, 21, 6201–6208.

    Article  Google Scholar 

  7. Kim, H.; Han, B.; Choo, J.; Cho, J. Three-dimensional porous silicon particles for use in high-performance lithium secondary batteries. Angew. Chem. Int. Ed. 2008, 47, 10151–10154.

    Article  Google Scholar 

  8. Kim, H.; Seo, M.; Park, M.-H.; Cho, J. A critical size of silicon nano-anodes for lithium rechargeable batteries. Angew. Chem. Int. Ed. 2010, 49, 2146–2149.

    Article  Google Scholar 

  9. Bruce, P. G.; Scrosati, B.; Tarascon, J.-M. Nanomaterials for rechargeable lithium batteries. Angew. Chem. Int. Ed. 2008, 47, 2930–2946.

    Article  Google Scholar 

  10. Yi, R.; Dai, F.; Gordin, M. L.; Chen, S.; Wang, D. Micro-sized Si-C composite with interconnected nanoscale building blocks as high-performance anodes for practical application in lithium-ion batteries. Adv. Energy Mater. 2013, 3, 295–300.

    Article  Google Scholar 

  11. Jeong, G.; Kim, Y.-U.; Kim, H.; Kim, Y.-J.; Sohn, H.-J. Prospective materials and applications for Li secondary batteries. Energy Environ. Sci. 2011, 4, 1986–2002.

    Article  Google Scholar 

  12. Luo, J.; Zhao, X.; Wu, J.; Jang, H. D.; Kung, H. H.; Huang, J. Crumpled graphene-encapsulated Si nanoparticles for lithium ion battery anodes. J. Phys. Chem. Lett. 2012, 3, 1824–1829.

    Article  Google Scholar 

  13. Wu, H.; Chan, G.; Choi, J. W.; Ryu, I.; Yao, Y.; McDowell, M. T.; Lee, S. W.; Jackson, A.; Yang, Y.; Hu, L.; Cui, Y. Stable cycling of double-walled silicon nanotube battery anodes through solid-electrolyte interphase control. Nat. Nanotechnol. 2012, 7, 310–315.

    Article  Google Scholar 

  14. Wu, H.; Zheng, G.; Liu, N.; Carney, T. J.; Yang, Y.; Cui, Y. Engineering empty space between Si nanoparticles for lithium-ion battery anodes. Nano Lett. 2012, 12, 904–909.

    Article  Google Scholar 

  15. Liu, G.; Xun, S.; Vukmirovic, N.; Song, X.; Olalde-Velasco, P.; Zheng, H.; Battaglia, V. S.; Wang, L.; Yang, W. Polymers with tailored electronic structure for high-capacity lithium battery electrodes. Adv. Mater. 2011, 23, 4579–4683.

    Google Scholar 

  16. Wu, M.; Xiao, X.; Vukmirovic, N.; Xun, S.; Das, P. K.; Song, X.; Olalde-Velasco, P.; Wang, D.; Weber, A. Z.; Wang, L.-W.; et al. Toward an ideal polymer binder design for high-capacity battery anodes. J. Am. Chem. Soc. 2013, 135, 12048–12056.

    Article  Google Scholar 

  17. Evanoff, K.; Benson, J.; Schauer, M.; Kovalenko, I.; Lashmore, D.; Ready, W. J.; Yushin, G. Ultra strong silicon-coated carbon nanotube nonwoven fabric as a multifunctional lithium-ion battery anode. ACS Nano 2012, 6, 9837–9845.

    Article  Google Scholar 

  18. Liu, B.; Wang, X.; Chen, H.; Wang, Z.; Chen, D.; Cheng, Y.-B.; Zhou, C.; Shen, G. Hierarchical silicon nanowires-carbon textiles matrix as a binder-free anode for high-performance advanced lithium-ion batteries. Sci. Rep. 2013, 3, 1622.

    Google Scholar 

  19. Wu, H.; Yu, G.; Pan, L.; Liu, N.; McDowell, M. T.; Bao, Z.; Cui, Y. Stable Li-ion battery anodes by in-situ polymerization of conducting hydrogel to conformally coat silicon nanoparticles. Nat. Commun. 2013, 4, 1943.

    Google Scholar 

  20. Ji, L.; Zheng, H.; Ismach, A.; Tan, Z.; Xun, S.; Lin, E.; Battaglia, V.; Srinivasan, V.; Zhang, Y. Graphene/Si multilayer structure anodes for advanced high and full lithium-ion cells. Nano Energy 2012, 1, 164–171.

    Article  Google Scholar 

  21. Piper, D. M.; Yersak, T. A.; Son, S.-B.; Kim, S. C.; Kang, C. S.; Oh, K. H.; Ban, C.; Dillon, A. C.; Lee, S.-H. Conformal coatings of cyclized-PAN for mechanically resilient Si nano-composite anodes. Adv. Energy Mater. 2013, 3, 697–702.

    Article  Google Scholar 

  22. Forney, M. W.; Ganter, M. J.; Staub, J. W.; Ridgley, R. D.; Landi, B. J. Prelithiation of silicon-carbon nanotube anodes for lithium ion batteries by stabilizing lithium metal powders (SLMP). Nano Lett. 2013, 13, 4158–4163.

    Article  Google Scholar 

  23. Wang, K.; He, X.; Wang, L.; Ren, J.; Liang, C.; Wan, C. Si, Si/Cu core in carbon shell composite as anode material in lithium-ion batteries. Solid State Ionics 2007, 178, 115–118.

    Article  Google Scholar 

  24. Zhao, X.; Hayner, C. M.; Kung, M. C.; Kung, H. H. In-plane vacancy-enabled high-power Si-graphene composite electrode for lithium-ion batteries. Adv. Energy Mater. 2011, 1, 1079–1084.

    Article  Google Scholar 

  25. Evanoff, K.; Magasinski, A.; Yang, J.; Yushin, G. Nanosilicon-coated graphene granules as anode for Li-ion batteries. Adv. Energy Mater. 2011, 1, 495–498.

    Article  Google Scholar 

  26. Liang, C.; Dai, S. Synthesis of mesoporous carbon materials via enhanced hydrogen-bonding interaction. J. Am. Chem. Soc. 2006, 128, 5316–5317.

    Article  Google Scholar 

  27. Tuinstra, F.; Koenig, J. L. Raman spectrum of graphite. J. Chem. Phys. 1970, 53, 1126–1130.

    Article  Google Scholar 

  28. Magasinski, A.; Dixon, P.; Hertzberg, B.; Kvit, A.; Ayala, J.; Yushin, G. High-performance lithium-ion anodes using a hierarchical bottom-up approach. Nat. Mater. 2010, 9, 353–358.

    Article  Google Scholar 

  29. McDowell, M. T.; Lee, S. W.; Nix, W. D.; Cui, Y. Understanding the lithiation of silicon and other alloying anodes for lithium-ion batteries. Adv. Mater. 2013, 25, 4966–4985.

    Article  Google Scholar 

  30. Pistoia, G. Lithium Batteries: New Materials, Developments and Perspectives; Elsevier Science: Amsterdam, 1994.

    Google Scholar 

  31. Li, D.; Müller, M. B.; Gilje, S.; Kaner, R. B.; Wallace, G. G. Processable aqueous dispersions of graphene nanosheets. Nat. Nanotechnol. 2008, 3, 101–105.

    Article  Google Scholar 

  32. Jeon, I.-Y.; Choi, H.-J.; Choi, M.; Seo, J.-M.; Jung, S.-M.; Kim, M.-J.; Zhang, S.; Zhang, L.; Xia, Z.; Dai, L.; et al. Facile, scalable synthesis of edge-halogenated graphene nanoplatelets as efficient metal-free electrocatalysts for oxygen reduction reaction. Sci. Rep. 2013, 3, 1810.

    Google Scholar 

  33. Park, S.; Ruoff, R. S. Chemical methods for the production of graphenes. Nat. Nanotechnol. 2009, 4, 217–224.

    Article  Google Scholar 

  34. Dreyer, D. R.; Park, S.; Bielawski, C. W.; Ruoff, R. S. The chemistry of graphene oxide. Chem. Soc. Rev. 2010, 39, 228–240.

    Article  Google Scholar 

  35. Chang, W.-S.; Park, C.-M.; Kim, J.-H.; Kim, Y.-U.; Jeong, G.; Sohn, H.-J. Quartz (SiO2): A new energy storage anode material for Li-ion batteries. Energy & Environ. Sci. 2012, 5, 6895–6899.

    Article  Google Scholar 

  36. Song, S.-W.; Baek, S.-W. Silane-derived SEI stabilization on thin-film electrodes of nanocrystalline Si for lithium batteries. Electrochem. Solid-State Lett. 2009, 12, A23–27.

    Article  Google Scholar 

  37. Hassan, F. M.; Chabot, V.; Elsayed, A. R.; Xiao, X.; Chen, Z. Engineered Si electrode nanoarchitecture: A scalable postfabrication treatment for the production of next-generation Li-ion batteries. Nano Lett. 2014, 14, 277–283.

    Article  Google Scholar 

  38. Lee, J. K.; Smith, K. B.; Hayner, C. M.; Kung, H. H. Silicon nanoparticles-graphene paper composites for Li ion battery anodes. Chem. Commun. 2010, 46, 2025–2027.

    Article  Google Scholar 

  39. Zhou, X.; Yin, Y.-X.; Wan, L.-J.; Guo, Y.-G. Self-assembled nanocomposite of silicon nanoparticles encapsulated in graphene through electrostatic attraction for lithium-ion batteries. Adv. Energy Mater. 2012, 2, 1086–1090.

    Article  Google Scholar 

  40. Wang, B.; Li, X.; Zhang, X.; Luo, B.; Jin, M.; Liang, M.; Dayeh, S. A.; Picraux, S. T.; Zhi, L. Adaptable silicon-carbon nanocables sandwiched between reduced graphene oxide sheets as lithium ion battery anodes. ACS Nano 2013, 7, 1437–1445.

    Article  Google Scholar 

  41. Zhou, M.; Pu, F.; Wang, Z.; Cai, T.; Chen, H.; Zhang, H.; Guan, S. Facile synthesis of novel Si nanoparticles-graphene composites as high-performance anode materials for Li-ion batteries. Phys. Chem. Chem. Phys. 2013, 15, 11394–11401.

    Article  Google Scholar 

  42. Liu, X. H.; Zhong, L.; Huang, S.; Mao, S. X.; Zhu, T.; Huang, J. Y. Size-dependent fracture of silicon nanoparticles during lithiation. ACS Nano 2012, 6, 1522–1531.

    Article  Google Scholar 

  43. Dahn, J. R.; Seel, J. A. Energy and capacity projections for practical dual-graphite cells. J. Electrochem. Soc. 2000, 147, 899–901.

    Article  Google Scholar 

  44. Zhang, S. S.; Jow, T. R. Study of poly(acrylonitrile-methyl methacrylate) as binder for graphite anode and LiMn2O4 cathode of Li-ion batteries. J. Power Sources 2002, 109, 422–426.

    Article  Google Scholar 

  45. Wang, B.; Li, X.; Qiu, T.; Luo, B.; Ning, J.; Li, J.; Zhang, X.; Liang, M.; Zhi, L. High volumetric capacity silicon-based lithium battery anodes by nanoscale system engineering. Nano Lett. 2013, 13, 5578–5584.

    Article  Google Scholar 

  46. Kovalenko, I.; Zdyrko, B.; Magasinski, A.; Hertzberg, B.; Milicev, Z.; Burtovyy, R.; Luzinov, I.; Yushin, G. A major constituent of brown algae for use in high-capacity Li-ion batteries. Science, 2011, 334, 75–79.

    Article  Google Scholar 

  47. Lee, J.-I.; Choi, N.-S.; Park, S. Highly stable Si-based multicomponent anodes for practical use in lithium-ion batteries. Energy Environ. Sci. 2012, 5, 7878–7882.

    Article  Google Scholar 

  48. Gauthier, M.; Mazouzi, D.; Reyter, D.; Lestriez, B.; Moreau, P.; Guyomard, D.; Roué, L. A low-cost and high performance ball milled Si-based negative electrodefor high energy Li-ion batteries. Energy Environ. Sci. 2013, 6, 2145–2155.

    Article  Google Scholar 

  49. Ge, M.; Rong, J.; Fang, X.; Zhou, C. Porous doped silicon nanowires for lithium ion battery anode with long cycle life. Nano Lett. 2012, 12, 2318–2323.

    Article  Google Scholar 

  50. Deng, J.; Ji, H.; Yan, C.; Zhang, J.; Si, W.; Baunack, S.; Oswald, S.; Mei, Y.; Schmidt, O. G. Naturally rolled-up C/Si/C trilayer nanomembranes as stable anodes for lithium-ion batteries with remarkable cycling performance. Angew. Chem. Int. Ed. 2013, 52, 2326–2330.

    Article  Google Scholar 

  51. Barsoukov, E.; Macdonald, J. R. Impedance Spectroscopy: Theory, Experiment, and Applications; John Wiley & Sons: Hoboken, New Jersey, 2005.

    Book  Google Scholar 

  52. Hassoun, J.; Lee, K.-S.; Sun, Y.-K.; Scrosati, B. An advanced lithium ion battery based on high performance electrode materials. J. Am. Chem. Soc. 2011, 133, 3139–3143.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Bluestone Global Tech, 169 Myers Corners Road, Wappingers Falls, NY, 12590, USA

    Xin Zhao, Minjie Li, Kuo-Hsin Chang & Yu-Ming Lin

Authors
  1. Xin Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Minjie Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Kuo-Hsin Chang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yu-Ming Lin
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Xin Zhao or Yu-Ming Lin.

Electronic supplementary material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhao, X., Li, M., Chang, KH. et al. Composites of graphene and encapsulated silicon for practically viable high-performance lithium-ion batteries. Nano Res. 7, 1429–1438 (2014). https://doi.org/10.1007/s12274-014-0463-6

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-014-0463-6

Keywords

Search

Navigation