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Growth of conformal graphene cages on micrometre-sized silicon particles as stable battery anodes

Nature Energy volume 1, Article number: 15029 (2016) Cite this article

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An Erratum to this article was published on 01 February 2016

Abstract

Nanostructuring has been shown to be fruitful in addressing the problems of high-capacity Si anodes. However, issues with the high cost and poor Coulombic efficiencies of nanostructured Si still need to be resolved. Si microparticles are a low-cost alternative but, unlike Si nanoparticles, suffer from unavoidable particle fracture during electrochemical cycling, thus making stable cycling in a real battery impractical. Here we introduce a method to encapsulate Si microparticles (∼1–3 µm) using conformally synthesized cages of multilayered graphene. The graphene cage acts as a mechanically strong and flexible buffer during deep galvanostatic cycling, allowing the microparticles to expand and fracture within the cage while retaining electrical connectivity on both the particle and electrode level. Furthermore, the chemically inert graphene cage forms a stable solid electrolyte interface, minimizing irreversible consumption of lithium ions and rapidly increasing the Coulombic efficiency in the early cycles. We show that even in a full-cell electrochemical test, for which the requirements of stable cycling are stringent, stable cycling (100 cycles; 90% capacity retention) is achieved with the graphene-caged Si microparticles.

Rechargeable lithium-based batteries with high energy density have been the subject of intense research to meet the ever-growing demands of portable electronics and electrical vehicles1,2,3. A variety of emerging anode and cathode materials has attracted much attention, including Si, Sn and Li metal for anodes4,5,6,7, and S and O2 for cathodes8,9,10,11. Among these materials, Si is an attractive anode material for next-generation lithium-ion batteries (LIBs; refs 12,13,14), having greater than ten times the theoretical capacity of commercial graphite anodes. However, challenges arise due to the large volume expansion of silicon (∼300%) during battery operation, which causes mechanical fracture, loss of inter-particle electrical contact, and repeated chemical side reactions with the electrolyte.

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Figure 1: Design and structure of graphene cage encapsulation.
Figure 2: Synthesis and characterization of graphene cage structure.
Figure 3: Particle-level characterization of graphene cage by in situ TEM.
Figure 4: In situ TEM observation of graphene cage Si lithiation.
Figure 5: Electrochemical characterization of graphene cage Si anodes.

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Acknowledgements

Y.L. acknowledges the National Science Foundation Graduate Fellowship Program for funding and M. Hanna for fruitful discussions. H.-W.L. acknowledges the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (contract no. 2012038593). Y.C. acknowledges the support from the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy under the Battery Materials Research (BMR) Program.

Author information

Author notes

  1. Yuzhang Li and Kai Yan: These authors contributed equally to this work.

Authors and Affiliations

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

    Yuzhang Li, Kai Yan, Hyun-Wook Lee, Zhenda Lu & Yi Cui

  2. Department of Chemistry, Stanford University, Stanford, California 94305, USA

    Nian Liu

  3. Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025, USA

    Yi Cui

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  1. Yuzhang Li
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Contributions

Y.L., K.Y. and Y.C. conceived and designed the experiments. Y.L. and K.Y. carried out materials synthesis and electrochemical characterization. Z.L. and N.L. participated in part of the synthesis and materials characterization. H.-W.L. and Y.L. conducted in situ TEM lithiation and electrical measurements. Y.L., K.Y. and Y.C. co-wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Yi Cui.

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Supplementary information

Supplementary Information

Supplementary Methods, Supplementary Figures 1-13, Supplementary. (PDF 1406 kb)

Supplementary Video 1

External load testing for empty amorphous carbon shell. The fragile coating breaks after only a slight deformation. (MP4 1577 kb)

Supplementary Video 2

External load testing for empty graphene cage. Despite extreme compression, the graphene cage is able to fully collapse its shape and still returns to its original structure after deloading. (MP4 2429 kb)

Supplementary Video 3

Lithiation of a graphene-encapsulated SiMP. Note that the particle expansion and fracture are quite violent and anisotropic. Despite this, the graphene cage remains undamaged and electrically connects the fractured particles within. Movie is x10 speed. (MOV 9095 kb)

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Li, Y., Yan, K., Lee, HW. et al. Growth of conformal graphene cages on micrometre-sized silicon particles as stable battery anodes. Nat Energy 1, 15029 (2016). https://doi.org/10.1038/nenergy.2015.29

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