Article | Published:

In situ atomic-scale imaging of electrochemical lithiation in silicon

Nature Nanotechnology volume 7, pages 749756 (2012) | Download Citation

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.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

References

  1. 1.

    & Issues and challenges facing rechargeable lithium batteries. Nature 414, 359–367 (2001).

  2. 2.

    et al. Colossal reversible volume changes in lithium alloys. Electrochem. Solid-State Lett. 4, A137–A140 (2001).

  3. 3.

    , , & Electrochemically-driven solid-state amorphization in lithium-silicon alloys and implications for lithium storage. Acta Mater. 51, 1103–1113 (2003).

  4. 4.

    & Battery materials for ultrafast charging and discharging. Nature 458, 190–193 (2009).

  5. 5.

    & Challenges for rechargeable Li batteries. Chem. Mater. 22, 587–603 (2010).

  6. 6.

    et al. Nanoscale mapping of ion diffusion in a lithium-ion battery cathode. Nature Nanotech. 5, 749–754 (2010).

  7. 7.

     et al. In situ observation of the electrochemical lithiation of a single SnO2 nanowire electrode. Science 330, 1515–1520 (2010).

  8. 8.

    et al. High-performance lithium battery anodes using silicon nanowires. Nature Nanotech. 3, 31–35 (2008).

  9. 9.

    et al. High-power lithium batteries from functionalized carbon-nanotube electrodes. Nature Nanotech. 5, 531–537 (2010).

  10. 10.

    , & Three-dimensional bicontinuous ultrafast-charge and -discharge bulk battery electrodes. Nature Nanotech. 6, 277–281 (2011).

  11. 11.

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

  12. 12.

    & In situ TEM electrochemistry of anode materials in lithium ion batteries. Energy Environ. Sci. 4, 3844–3860 (2011).

  13. 13.

    et al. Anisotropic swelling and fracture of silicon nanowires during lithiation. Nano Lett. 11, 3312–3318 (2011).

  14. 14.

    et al. Real-time measurement of stress and damage evolution during initial lithiation of crystalline silicon. Phys. Rev. Lett. 107, 045503 (2011).

  15. 15.

    et al. Size-dependent fracture of silicon nanoparticles during lithiation. ACS Nano 6, 1522–1531 (2012).

  16. 16.

    , , & Anomalous shape changes of silicon nanopillars by electrochemical lithiation. Nano Lett. 11, 3034–3039 (2011).

  17. 17.

    , , & Strain anisotropies and self-limiting capacities in single-crystalline 3D silicon microstructures: models for high energy density lithium-ion battery anodes. Adv. Funct. Mater. 21, 2412–2422 (2011).

  18. 18.

    & Phase Transformations in Metals and Alloys (Chapman and Hall, 1992).

  19. 19.

     et al. In situ TEM experiments of electrochemical lithiation and delithiation of individual nanostructures. Adv. Energy Mater. 2, 722–741 (2012).

  20. 20.

    , & Sawtooth faceting in silicon nanowires. Phys. Rev. Lett. 95, 146104 (2005).

  21. 21.

    Thermodynamic and kinetic aspects of the crystal to glass transformation in metallic materials. Prog. Mater. Sci. 30, 81–134 (1986).

  22. 22.

    Selective growth of metal-rich silicide of near-noble metals. Appl. Phys. Lett. 27, 221–224 (1975).

  23. 23.

    et al. Real-time NMR investigations of structural changes in silicon electrodes for lithium-ion batteries. J. Am. Chem. Soc. 131, 9239–9249 (2009).

  24. 24.

    , , & Pair distribution function analysis and solid state NMR studies of silicon electrodes for lithium ion batteries: understanding the (de)lithiation mechanisms. J. Am. Chem. Soc. 133, 503–512 (2011).

  25. 25.

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

  26. 26.

    et al. Orientation-dependent interfacial mobility governs the anisotropic swelling in lithiated silicon nanowires. Nano Lett. 12, 1953–1958 (2012).

  27. 27.

    , , , & Fracture of crystalline silicon nanopillars during electrochemical lithium insertion. Proc. Natl Acad. Sci. USA 109, 4080–4085 (2012).

  28. 28.

    , & Tapering control of Si nanowires grown from SiCl4 at reduced pressure. ACS Nano 5, 656–664 (2011).

  29. 29.

    & Atomistic mechanisms of lithium insertion in amorphous silicon. J. Power Sources 196, 3664–3668 (2011).

Download references

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).

Author information

Affiliations

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

    • Xiao Hua Liu
    • , Yang Liu
    •  & Jian Yu Huang
  2. Department of Mechanical Engineering and Materials Science, University of Pittsburgh, Pittsburgh, Pennsylvania 15261, USA

    • Jiang Wei Wang
    •  & Scott X. Mao
  3. Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, 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, Maryland 20899, USA

    • Sergiy Krylyuk
    •  & Albert V. Davydov
  6. Institute for Research in Electronics and Applied Physics, University of Maryland, College Park, Maryland 20742, USA

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

    • Jinkyoung Yoo
    • , Shadi A. Dayeh
    •  & S. Tom Picraux
  8. Center for Electron Microscopy, Department of Materials Science and Engineering, 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, Massachusetts 02139, USA

    • Ju Li

Authors

  1. Search for Xiao Hua Liu in:

  2. Search for Jiang Wei Wang in:

  3. Search for Shan Huang in:

  4. Search for Feifei Fan in:

  5. Search for Xu Huang in:

  6. Search for Yang Liu in:

  7. Search for Sergiy Krylyuk in:

  8. Search for Jinkyoung Yoo in:

  9. Search for Shadi A. Dayeh in:

  10. Search for Albert V. Davydov in:

  11. Search for Scott X. Mao in:

  12. Search for S. Tom Picraux in:

  13. Search for Sulin Zhang in:

  14. Search for Ju Li in:

  15. Search for Ting Zhu in:

  16. Search for Jian Yu Huang in:

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.

Competing interests

The authors declare no competing financial interests.

Corresponding authors

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

Supplementary information

PDF files

  1. 1.

    Supplementary information

    Supplementary information

Videos

  1. 1.

    Supplementary Movie S1

    Supplementary Movie S1

  2. 2.

    Supplementary Movie S2

    Supplementary Movie S2

  3. 3.

    Supplementary Movie S3

    Supplementary Movie S3

  4. 4.

    Supplementary Movie S4

    Supplementary Movie S4

About this article

Publication history

Received

Accepted

Published

DOI

https://doi.org/10.1038/nnano.2012.170

Further reading