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In situ atomic-scale imaging of electrochemical lithiation in silicon

Nature Nanotechnology volume 7, pages 749–756 (2012)Cite this article

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Abstract

In lithium-ion batteries, the electrochemical reaction between the electrodes and lithium is a critical process that controls the capacity, cyclability and reliability of the battery. Despite intensive study, the atomistic mechanism of the electrochemical reactions occurring in these solid-state electrodes remains unclear. Here, we show that in situ transmission electron microscopy can be used to study the dynamic lithiation process of single-crystal silicon with atomic resolution. We observe a sharp interface (∼1 nm thick) between the crystalline silicon and an amorphous LixSi alloy. The lithiation kinetics are controlled by the migration of the interface, which occurs through a ledge mechanism involving the lateral movement of ledges on the close-packed {111} atomic planes. Such ledge flow processes produce the amorphous LixSi alloy through layer-by-layer peeling of the {111} atomic facets, resulting in the orientation-dependent mobility of the interfaces.

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Figure 1: Progressive migration of the sharp ACI during solid-state amorphization (lithiation) of a crystalline 〈111〉-oriented silicon nanowire.
Figure 2: Ledge mechanism of lithiation in c-Si.
Figure 3: Comparison of the migration speed of the different ACIs.
Figure 4: Atomically resolved structure of the ACI.
Figure 5: Ledge mechanism observed in a 〈110〉-oriented silicon nanowire during lithiation.

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Acknowledgements

Portions of this work were supported by a Laboratory Directed Research and Development (LDRD) project at Sandia National Laboratories (SNL) and partly by Nanostructures for Electrical Energy Storage (NEES), an Energy Frontier Research Center (EFRC) funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences (award no. DESC0001160). The LDRD supported the development and fabrication of platforms. The NEES centre supported the development of TEM techniques. The Sandia-Los Alamos Center for Integrated Nanotechnologies (CINT) supported the TEM capability. Sandia National Laboratories is a multiprogramme laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Company, for the US Department of Energy's National Nuclear Security Administration (contract DE-AC04-94AL85000). T.Z. acknowledges support from the NSF (grants CMMI-0758554 and 1100205). J.L. acknowledges support from the NSF (DMR-1008104 and DMR-1120901) and AFOSR (FA9550-08-1-0325). S.L.Z. acknowledges support from the NSF (grant CMMI-0900692).

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Authors and Affiliations

  1. Center for Integrated Nanotechnologies, Sandia National Laboratories, Albuquerque, 87185, New Mexico, USA

    Xiao Hua Liu, Yang Liu & Jian Yu Huang

  2. Department of Mechanical Engineering and Materials Science, University of Pittsburgh, Pittsburgh, 15261, Pennsylvania, USA

    Jiang Wei Wang & Scott X. Mao

  3. Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, 30332, Georgia, USA

    Shan Huang, Feifei Fan & Ting Zhu

  4. Department of Engineering Science and Mechanics, Pennsylvania State University, University Park, Pennsylvania, 16802, USA

    Xu Huang & Sulin Zhang

  5. Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, 20899, Maryland, USA

    Sergiy Krylyuk & Albert V. Davydov

  6. Institute for Research in Electronics and Applied Physics, University of Maryland, College Park, 20742, Maryland, USA

    Sergiy Krylyuk

  7. Center for Integrated Nanotechnologies, Los Alamos National Laboratory, Los Alamos, 87545, New Mexico, USA

    Jinkyoung Yoo, Shadi A. Dayeh & S. Tom Picraux

  8. Department of Materials Science and Engineering, Center for Electron Microscopy, Zhejiang University, Hangzhou, 310027, China

    Scott X. Mao

  9. Department of Nuclear Science and Engineering and Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, 02139, Massachusetts, USA

    Ju Li

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  1. Xiao Hua Liu
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Contributions

X.H.L. and J.Y.H. conceived and designed the experiments. S.K., J.Y., S.A.D., A.V.D. and S.T.P. synthesized the nanowire samples. X.H.L. and J.W.W. carried out in situ TEM experiments. S.H., F.F., X.H., S.Z. and T.Z. performed MD simulations. X.H.L. performed data analysis. X.H.L., T.Z. and J.Y.H. wrote the paper. S.Z. and J.L. revised the manuscript. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Xiao Hua Liu, Ting Zhu or Jian Yu Huang.

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The authors declare no competing financial interests.

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Liu, X., Wang, J., Huang, S. et al. In situ atomic-scale imaging of electrochemical lithiation in silicon. Nature Nanotech 7, 749–756 (2012). https://doi.org/10.1038/nnano.2012.170

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