Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Scalable synthesis of silicon-nanolayer-embedded graphite for high-energy lithium-ion batteries

Nature Energy volume 1, Article number: 16113 (2016) Cite this article

Subjects

An Author Correction to this article was published on 09 March 2020

Abstract

Existing anode technologies are approaching their limits, and silicon is recognized as a potential alternative due to its high specific capacity and abundance. However, to date the commercial use of silicon has not satisfied electrode calendering with limited binder content comparable to commercial graphite anodes for high energy density. Here we demonstrate the feasibility of a next-generation hybrid anode using silicon-nanolayer-embedded graphite/carbon. This architecture allows compatibility between silicon and natural graphite and addresses the issues of severe side reactions caused by structural failure of crumbled graphite dust and uncombined residue of silicon particles by conventional mechanical milling. This structure shows a high first-cycle Coulombic efficiency (92%) and a rapid increase of the Coulombic efficiency to 99.5% after only 6 cycles with a capacity retention of 96% after 100 cycles, with an industrial electrode density of >1.6 g cm−3, areal capacity loading of >3.3 mAh cm−2, and <4 wt% binding materials in a slurry. As a result, a full cell using LiCoO2 has demonstrated a higher energy density (1,043 Wh l−1) than with standard commercial graphite electrodes.

Lithium-ion batteries (LIBs) are recognized as the most important power supply for mobile electronic devices, with energy densities that have been increasing by 7–10% per year1,2. There is a continuing demand for advanced LIBs with reduced weight, longer life spans, and higher capacity. However, conventional carbonaceous anodes are approaching their theoretical capacity limits3,4,5,6. In this regard, Si (ref. 7) and silicon oxide (SiOx; ref. 8) have been considered as feasible alternatives for the next generation of LIB anodes. Their working potentials are low compared with graphite of <0.5 V versus Li/Li+ (ref. 9). However, Si, which has a high theoretical specific capacity of 3,572 mAh g−1 (Li15Si4) (ref. 10), generally induces extreme volume changes (>300%)11, resulting in disintegration of the electrode during repeated charge/discharge processes12,13. To use Si as a negative electrode against volume expansion and control solid-electrolyte interphase (SEI) formation for high Coulombic efficiency (CE), advanced nanomaterial design strategies as an academic approach have been demonstrated, such as making double-walled Si nanotubes14, Si–C yolk–shell and pomegranate structures15,16,17, or graphene-encapsulated Si particles18,19, suggesting a significant improvement in cycle life with relatively low areal mass loading for industrial implementation. Considering the practical standard, SiOx has captured the interest of the industry due to its relatively low volume expansion (<200%), fewer side reactions with electrolytes, and high capacity retention on electrochemical cycling20,21. Nevertheless, since the included oxygen content of SiOx can produce fatal irreversible products such as Li2O and Li4SiO4 (refs 22,23), exploring the optimum stoichiometry of SiOx and graphite-blended systems has presented formidable challenges24,25. Recently, it was reported that the optimal stoichiometry was SiO1.06, but that the CE at the first cycle was as low as 75%23. Blending 3 wt% of SiO1.06 with graphite achieved a reversible specific capacity of 397 mAh g−1 with 76% capacity retention after 200 cycles in a full-cell system. However, this blending system suffers from SiOx content limitation under 4 wt% because excessive use leads to a large increase of irreversible capacity losses in Li-confined full-cell systems.

This is a preview of subscription content, access via your institution

Relevant articles

Open Access articles citing this article.

Access options

Rent or buy this article

Get just this article for as long as you need it

$39.95

Learn more

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Schematic of fabrication and characterization of the SGC hybrid.
Figure 2: Electrochemical characterization of various electrodes.
Figure 3: Series of SEM images for electrode changes before and after 50 cycles.
Figure 4: Electrochemical comparison of a full cell between graphite (G) and SGC hybrid.
Figure 5: In situ TEM characterization of the SGC hybrid during lithiation.

References

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

    Article  Google Scholar 

  2. Crabtree, G., Kócs, E. & Trahey, L. The energy-storage frontier: lithium-ion batteries and beyond. MRS Bull. 40, 1067–1078 (2015).

    Article  Google Scholar 

  3. Choi, N. S. et al. Challenges facing lithium batteries and electrical double-layer capacitors. Angew. Chem. Int. Ed. 51, 9994–10024 (2012).

    Article  Google Scholar 

  4. Thackeray, M. M., Wolverton, C. & Isaacs, E. D. Electrical energy storage for transportation—approaching the limits of, and going beyond, lithium-ion batteries. Energy Environ. Sci. 5, 7854–7863 (2012).

    Article  Google Scholar 

  5. Goodenough, J. B. Evolution of strategies for modern rechargeable batteries. Acc. Chem. Res. 46, 1053–1061 (2013).

    Article  Google Scholar 

  6. Rolison, D. R. & Nazar, L. F. Electrochemical energy storage to power the 21st century. MRS Bull. 36, 486–493 (2011).

    Article  Google Scholar 

  7. Zhang, W. J. A review of the electrochemical performance of alloy anodes for lithium-ion batteries. J. Power Sources 196, 13–24 (2011).

    Article  Google Scholar 

  8. Obrovac, M. N. & Chevrier, V. L. Alloy negative electrodes for Li-ion batteries. Chem. Rev. 114, 11444–11502 (2014).

    Article  Google Scholar 

  9. Nitta, N. & Yushin, G. High-capacity anode materials for lithium-ion batteries: choice of elements and structures for active particles. Part. Part. Syst. Charact. 31, 317–336 (2014).

    Article  Google Scholar 

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

    Article  Google Scholar 

  11. Mcdowell, M. T., Lee, S. W., Nix, W. D. & Cui, Y. 25th anniversary article: understanding the lithiation of silicon and other alloying anodes for lithium-ion batteries. Adv. Mater. 25, 4966–4985 (2013).

    Article  Google Scholar 

  12. Ko, M., Oh, P., Chae, S., Cho, W. & Cho, J. Considering critical factors of Li-rich cathode and Si anode materials for practical Li-ion cell applications. Small 11, 4058–4073 (2015).

    Article  Google Scholar 

  13. Wu, H. & Cui, Y. Designing nanostructured Si anodes for high energy lithium ion batteries. Nano Today 7, 414–429 (2012).

    Article  Google Scholar 

  14. Wu, H. et al. Stable cycling of double-walled silicon nanotube battery anodes through solid-electrolyte interphase control. Nature Nanotech. 7, 309–314 (2012).

    Google Scholar 

  15. Liu, N. et al. A yolk-shell design for stabilized and scalable Li-ion battery alloy anodes. Nano Lett. 12, 3315–3321 (2012).

    Article  Google Scholar 

  16. Lu, Z. et al. Nonfilling carbon coating of porous silicon micrometer-sized particles for high-performance lithium battery anodes. ACS Nano 9, 2540–2547 (2015).

    Article  Google Scholar 

  17. Liu, N. et al. A pomegranate-inspired nanoscale design for large-volume-change lithium battery anodes. Nature Nanotech. 9, 187–192 (2014).

    Article  Google Scholar 

  18. Luo, J. et al. Crumpled graphene-encapsulated Si nanoparticles for lithium ion battery anodes. J. Phys. Chem. Lett. 3, 1824–1829 (2012).

    Article  Google Scholar 

  19. Li, Y. et al. Growth of conformal graphene cages on micrometre-sized silicon particles as stable battery anodes. Nature Energy 1, 15029 (2016).

    Article  Google Scholar 

  20. Lee, J.-I. & Park, S. High-performance porous silicon monoxide anodes synthesized via metal-assisted chemical etching. Nano Energy 2, 146–152 (2013).

    Article  Google Scholar 

  21. Song, J.-W., Nguyen, C. C. & Song, S.-W. Stabilized cycling performance of silicon oxide anode in ionic liquid electrolyte for rechargeable lithium batteries. RSC Adv. 2, 2003–2009 (2012).

    Article  Google Scholar 

  22. Miyachi, M., Yamamoto, H., Kawai, H., Ohta, T. & Shirakata, M. Analysis of SiO anodes for lithium-ion batteries. J. Electrochem. Soc. 152, A2089–A2091 (2005).

    Article  Google Scholar 

  23. Suh, S. S. et al. Electrochemical behavior of SiOx anodes with variation of oxygen ratio for Li-ion batteries. Electrochim. Acta 148, 111–117 (2014).

    Article  Google Scholar 

  24. Dimov, N., Xia, Y. & Yoshio, M. Practical silicon-based composite anodes for lithium-ion batteries: fundamental and technological features. J. Power Sources 171, 886–893 (2007).

    Article  Google Scholar 

  25. Du, Z., Dunlap, R. A. & Obrovac, M. N. High energy density calendered Si alloy/graphite anodes. J. Electrochem. Soc. 161, A1698–A1705 (2014).

    Article  Google Scholar 

  26. Jo, Y. N. et al. Si–graphite composites as anode materials for lithium secondary batteries. J. Power Sources 195, 6031–6036 (2010).

    Article  Google Scholar 

  27. Lee, J.-H., Kim, W.-J., Kim, J.-Y., Lim, S.-H. & Lee, S.-M. Spherical silicon/graphite/carbon composites as anode material for lithium-ion batteries. J. Power Sources 176, 353–358 (2008).

    Article  Google Scholar 

  28. Li, M. et al. Facile spray-drying/pyrolysis synthesis of core–shell structure graphite/silicon-porous carbon composite as a superior anode for Li-ion batteries. J. Power Sources 248, 721–728 (2014).

    Article  Google Scholar 

  29. Yoon, Y. S., Jee, S. H., Lee, S. H. & Nam, S. C. Nano Si-coated graphite composite anode synthesized by semi-mass production ball milling for lithium secondary batteries. Surf. Coat. Technol. 206, 553–558 (2011).

    Article  Google Scholar 

  30. Alias, M. et al. Silicon/graphite nanocomposite electrode prepared by low pressure chemical vapor deposition. J. Power Sources 174, 900–904 (2007).

    Article  Google Scholar 

  31. Kasavajjula, U., Wang, C. S. & Appleby, A. J. Nano- and bulk-silicon-based insertion anodes for lithium-ion secondary cells. J. Power Sources 163, 1003–1039 (2007).

    Article  Google Scholar 

  32. Saint, J. et al. Towards a fundamental understanding of the improved electrochemical performance of silicon-carbon composites. Adv. Funct. Mater. 17, 1765–1774 (2007).

    Article  Google Scholar 

  33. Yoshio, M. et al. Carbon-coated Si as a lithium-ion battery anode material. J. Electrochem. Soc. 149, A1598–A1603 (2002).

    Article  Google Scholar 

  34. Yoshio, M. et al. Improvement of natural graphite as a lithium-ion battery anode material, from raw flake to carbon-coated sphere. J. Mater. Chem. 14, 1754–1758 (2004).

    Article  Google Scholar 

  35. Uono, H., Kim, B.-C., Fuse, T., Ue, M. & Yamaki, J.-I. Optimized structure of silicon/carbon/graphite composites as an anode material for Li-ion batteries. J. Electrochem. Soc. 153, A1708–A1713 (2006).

    Article  Google Scholar 

  36. Lee, E. H. et al. Effect of carbon matrix on electrochemical performance of Si/C composites for use in anodes of lithium secondary batteries. Bull. Korean Chem. Soc. 34, 1435–1440 (2013).

    Article  Google Scholar 

  37. Lee, S. W. et al. Kinetics and fracture resistance of lithiated silicon nanopillar pairs controlled by their mechanical interaction. Nature Commun. 6, 7533 (2015).

    Article  Google Scholar 

  38. Liu, X. H. et al. Ultrafast electrochemical lithiation of individual Si nanowire anodes. Nano Lett. 11, 2251–2258 (2011).

    Article  Google Scholar 

  39. Mcdowell, M. T. et al. In situ TEM of two-phase lithiation of amorphous silicon nanospheres. Nano Lett. 13, 758–764 (2013).

    Article  Google Scholar 

  40. Sethuraman, V. A., Chon, M. J., Shimshak, M., Srinivasan, V. & Guduru, P. R. In situ measurements of stress evolution in silicon thin films during electrochemical lithiation and delithiation. J. Power Sources 195, 5062–5066 (2010).

    Article  Google Scholar 

  41. Boylan, J. Smooth operators: carbon-graphite materials. Mater. World 4, 707–708 (1996).

    Google Scholar 

Download references

Acknowledgements

This work was supported by the IT R&D programme of the Ministry of Trade, Industry & Energy/Korea Evaluation Institute of Industrial Technology (MOTIE/KEIT) (Development of Li-rich Cathode and Carbon-free Anode Materials for High Capacity/High Rate Lithium Secondary Batteries, 10046306) and the 2016 Research Fund (1.160033.01) of UNIST (Ulsan National Institute of Science and Technology). Also, Y.C. acknowledges support from the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies, Battery Materials Research Program of the US Department of Energy.

Author information

Authors and Affiliations

  1. Department of Energy Engineering, School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919, Republic of Korea

    Minseong Ko, Sujong Chae, Jiyoung Ma, Namhyung Kim, Hyun-Wook Lee & Jaephil Cho

  2. Department of Materials Science and Engineering, Stanford University, Stanford, California 94305, USA

    Hyun-Wook Lee & Yi Cui

  3. Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA

    Yi Cui

Authors
  1. Minseong Ko
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Sujong Chae
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jiyoung Ma
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Namhyung Kim
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Hyun-Wook Lee
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Yi Cui
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Jaephil Cho
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

M.K. conceived and designed the experiments, and performed data interpretation. M.K. prepared the samples and carried out the main experiments. S.C. assisted with the data interpretation and designed the experimental scheme; H.-W.L. conducted in situ TEM characterization and detailed discussion on analytic results. J.M. assisted with sample preparation and performed the energy-dispersive spectroscopy measurement. N.K. provided data analysis. M.K., S.C., H.-W.L., Y.C. and J.C. co-wrote the paper.

Corresponding authors

Correspondence to Hyun-Wook Lee, Yi Cui or Jaephil Cho.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Figures 1–9, Supplementary Tables 1 and 2, Supplementary Notes, Supplementary References. (PDF 938 kb)

Supplementary Video 1

Lithiation of a Si nanolayer coated on the surface of empty volume space. The Si nanolayer can expand toward empty volume space upon lithiation, leading to no rupture and interference between Si and graphite. The movie is played at 10× speed. (MP4 16592 kb)

Supplementary Video 2

Lithiation of a Si nanolayer located in the gap between graphite layers. The Si nanolayer located in the gap between the graphite layers remains intact without any cracks and contact losses upon lithiation. The movie is played at 7× speed. (MP4 11800 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Ko, M., Chae, S., Ma, J. et al. Scalable synthesis of silicon-nanolayer-embedded graphite for high-energy lithium-ion batteries. Nat Energy 1, 16113 (2016). https://doi.org/10.1038/nenergy.2016.113

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1038/nenergy.2016.113

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing