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In situ atomic-scale imaging of electrochemical lithiation in silicon

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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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.

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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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