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.

Origin of lithium whisker formation and growth under stress

Nature Nanotechnology volume 14, pages 1042–1047 (2019)Cite this article

Subjects

Abstract

Lithium metal has the lowest standard electrochemical redox potential and very high theoretical specific capacity, making it the ultimate anode material for rechargeable batteries. However, its application in batteries has been impeded by the formation of Li whiskers, which consume the electrolyte, deplete active Li and may lead to short-circuit of the battery. Tackling these issues successfully is dependent on acquiring sufficient understanding of the formation mechanisms and growth of Li whiskers under the mechanical constraints of a separator. Here, by coupling an atomic force microscopy cantilever into a solid open-cell set-up in environmental transmission electron microscopy, we directly capture the nucleation and growth behaviour of Li whiskers under elastic constraint. We show that Li deposition is initiated by a sluggish nucleation of a single crystalline Li particle, with no preferential growth directions. Remarkably, we find that retarded surface transport of Li plays a decisive role in the subsequent deposition morphology. We then explore the validity of these findings in practical cells using a series of carbonate-poisoned ether-based electrolytes. Finally, we show that Li whiskers can yield, buckle, kink or stop growing under certain elastic constraints.

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

Prices vary by article type

from$1.95

to$39.95

Learn more

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

Fig. 1: The AFM–ETEM solid open-cell set-up for the in-situ study.
Fig. 2: Li whisker formation during electrochemical deposition of Li in a CO2 environment.
Fig. 3: Intentional poisoning of the baseline electrolyte to identify the role of EC in Li whisker formation in coin cells.
Fig. 4: Diverse growth behaviours of Li whisker under AFM constraints.

Data availability

All data that support the findings of this study have been included in the main text, supplementary information and supplementary videos. Original data are kept at the Environmental Molecular Sciences Laboratory at Pacific Northwest National Laboratory and are available from the corresponding authors upon reasonable request.

References

  1. Xu, W. et al. Lithium metal anodes for rechargeable batteries. Energy Environ. Sci. 7, 513–537 (2014).

    CAS  Google Scholar 

  2. Liu, B., Zhang, J. G. & Xu, W. Advancing lithium metal batteries. Joule 2, 833–845 (2018).

    CAS  Google Scholar 

  3. Zhang, J.-G., Xu, W. & Henderson, W. A. Lithium Metal Anodes and Rechargeable Lithium Metal Batteries Ch. 2 (Springer, 2017).

  4. Lin, D., Liu, Y. & Cui, Y. Reviving the lithium metal anode for high-energy batteries. Nat. Nanotechnol. 12, 194–206 (2017).

    CAS  Google Scholar 

  5. Fang, C. et al. Quantifying inactive lithium in lithium metal batteries. Nature 572, 511–515 (2019).

    CAS  Google Scholar 

  6. Wu, F. et al. Perspectives for restraining harsh lithium dendrite growth: towards robust lithium metal anodes. Energy Storage Mater. 15, 148–170 (2018).

    Google Scholar 

  7. Zhang, R. et al. Advanced micro/nanostructures for lithium metal anodes. Adv. Sci. 4, 1600445 (2017).

    Google Scholar 

  8. Lin, C. F., Qi, Y., Gregorczyk, K., Lee, S. B. & Rubloff, G. W. Nanoscale protection layers to mitigate degradation in high-energy electrochemical energy storage systems. Acc. Chem. Res. 51, 97–106 (2018).

    CAS  Google Scholar 

  9. Zhao, J. et al. Surface fluorination of reactive battery anode materials for enhanced stability. J. Am. Chem. Soc. 139, 11550–11558 (2017).

    CAS  Google Scholar 

  10. Aguesse, F. et al. Investigating the dendritic growth during full cell cycling of garnet electrolyte in direct contact with Li metal. ACS Appl. Mater. Interfaces 9, 3808–3816 (2017).

    CAS  Google Scholar 

  11. Porz, L. et al. Mechanism of lithium metal penetration through inorganic solid electrolytes. Adv. Energy Mater. 7, 1701003 (2017).

    Google Scholar 

  12. Cheng, X. B., Zhang, R., Zhao, C. Z. & Zhang, Q. Toward safe lithium metal anode in rechargeable batteries: a review. Chem. Rev. 117, 10403–10473 (2017).

    CAS  Google Scholar 

  13. Ding, F. et al. Dendrite-free lithium deposition via self-healing electrostatic shield mechanism. J. Am. Chem. Soc. 135, 4450–4456 (2013).

    CAS  Google Scholar 

  14. Qian, J. et al. High rate and stable cycling of lithium metal anode. Nat. Commun. 6, 6362 (2015).

    CAS  Google Scholar 

  15. Ghanbari, M., Packirisamy, M. & Geitmann, A. Measuring the growth force of invasive plant cells using flexure integrated lab-on-a-chip (Filoc). Technology 6, 1–9 (2018).

    Google Scholar 

  16. Zhang, X. et al. Direction-specific van der Waals attraction between rutile TiO2 nanocrystals. Science 356, 434–437 (2017).

    CAS  Google Scholar 

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

    CAS  Google Scholar 

  18. He, Y. et al. Atomistic conversion reaction mechanism of WO3 in secondary ion batteries of Li, Na and Ca. Angew. Chem. Int. Ed. Engl. 55, 6244–6247 (2016).

    CAS  Google Scholar 

  19. Zhang, G. R., Chen, Y. F. & Ross, J. P. N. The reaction of lithium with carbon dioxide studied by photoelectron spectroscopy. Surf. Sci. 418, 139–149 (1998).

    Google Scholar 

  20. Tran, R. et al. Surface energies of elemental crystals. Sci. Data 3, 160080 (2016).

    CAS  Google Scholar 

  21. Koch, S. L., Morgan, B. J., Passerini, S. & Teobaldi, G. Density functional theory screening of gas-treatment strategies for stabilization of high energy-density lithium metal anodes. J. Power Sources 296, 150–161 (2015).

    CAS  Google Scholar 

  22. Kelton, K. F. Crystal nucleation in liquids and glasses. Solid State Phys. 45, 75–177 (1991).

    CAS  Google Scholar 

  23. Kushima, A. et al. Liquid cell transmission electron microscopy observation of lithium metal growth and dissolution: root growth, dead lithium and lithium flotsams. Nano Energy 32, 271–279 (2017).

    CAS  Google Scholar 

  24. Yamaki, J. et al. A consideration of the morphology of electrochemically deposited lithium in an organic electrolyte. J. Power Sources 74, 219–227 (1998).

    CAS  Google Scholar 

  25. Li, Y. et al. Atomic structure of sensitive battery materials and interfaces revealed by cryo-electron microscopy. Science 358, 506–510 (2017).

    CAS  Google Scholar 

  26. Mosqueda, H. A., Vazquez, C., Bosch, P. & Pfeiffer, H. Chemical sorption of carbon dioxide (CO2) on lithium oxide (Li2O). Chem. Mater. 18, 2307–2310 (2006).

    CAS  Google Scholar 

  27. Dologlou, E. Self-diffusion in solid lithium. Glass Phys. Chem. 36, 570–574 (2010).

    CAS  Google Scholar 

  28. Benitez, L. & Seminario, J. M. Ion diffusivity through the solid electrolyte interphase in lithium-ion batteries. J. Electrochem. Soc. 164, E3159–E3170 (2017).

    CAS  Google Scholar 

  29. Zheng, F., Kotobuki, M., Song, S., Lai, M. O. & Lu, L. Review on solid electrolytes for all-solid-state lithium-ion batteries. J. Power Sources 389, 198–213 (2018).

    CAS  Google Scholar 

  30. Matsuda, Y., Fukushima, T., Hashimoto, H. & Arakawa, R. Solvation of lithium ions in mixed organic electrolyte solutions by electrospray ionization mass spectroscopy. J. Electrochem. Soc. 149, A1045–A1048 (2002).

    CAS  Google Scholar 

  31. Zhang, Y. et al. Investigation of ion-solvent interactions in nonaqueous electrolytes using in situ liquid SIMS. Anal. Chem. 90, 3341–3348 (2018).

    CAS  Google Scholar 

  32. Aurbach, D. & Zaban, A. Impedance spectroscopy of lithium electrodes: part 1. General behaviour in propylene carbonate solutions and the correlation to surface chemistry and cycling efficiency. J. Electroanal. Chem. 348, 155–179 (1993).

    CAS  Google Scholar 

  33. Zhuang, G. V., Xu, K., Yang, H., Jow, T. R. & Ross, P. N. Lithium ethylene dicarbonate identified as the primary product of chemical and electrochemical reduction of EC in 1.2 M LiPF6/EC:EMC electrolyte. J. Phys. Chem. B 109, 17567–17573 (2005).

    CAS  Google Scholar 

  34. Aurbach, D., Gofer, Y., Ben-Zion, M. & Aped, P. The behaviour of lithium electrodes in propylene and ethylene carbonate: the major factors that influence Li cycling efficiency. J. Electroanal. Chem. 339, 451–471 (1992).

    CAS  Google Scholar 

  35. Borodin, O., Zhuang, G. V., Ross, P. N. & Xu, K. Molecular dynamics simulations and experimental study of lithium ion transport in dilithium ethylene dicarbonate. J. Phys. Chem. C 117, 7433–7444 (2013).

    CAS  Google Scholar 

  36. Xu, C., Ahmad, Z., Aryanfar, A., Viswanathan, V. & Greer, J. R. Enhanced strength and temperature dependence of mechanical properties of Li at small scales and its implications for Li metal anodes. Proc. Natl Acad. Sci. USA 114, 57–61 (2017).

    CAS  Google Scholar 

  37. Luo, L. et al. Surface coating constraint induced self-discharging of silicon nanoparticles as anodes for lithium ion batteries. Nano Lett. 15, 7016–7022 (2015).

    CAS  Google Scholar 

  38. McDowell, M. T. et al. Studying the kinetics of crystalline silicon nanoparticle lithiation with in situ transmission electron microscopy. Adv. Mater. 24, 6034–6041 (2012).

    CAS  Google Scholar 

  39. Zhao, K. et al. Concurrent reaction and plasticity during initial lithiation of crystalline silicon in lithium-ion batteries. J. Electrochem. Soc. 159, A238–A243 (2012).

    CAS  Google Scholar 

  40. Gu, M. et al. Bending-induced symmetry breaking of lithiation in germanium nanowires. Nano Lett. 14, 4622–4627 (2014).

    CAS  Google Scholar 

  41. Yin, X. et al. Insights into morphological evolution and cycling behaviour of lithium metal anode under mechanical pressure. Nano Energy 50, 659–664 (2018).

    CAS  Google Scholar 

  42. Hirai, T., Yoshimatsu, I. & Yamaki, J. Influence of electrolyte on lithium cycling efficiency with pressurized electrode stack. J. Electrochem. Soc. 141, 611–614 (1994).

    CAS  Google Scholar 

  43. Harrison, K. L. et al. Lithium self-discharge and its prevention: direct visualization through in situ electrochemical scanning transmission electron microscopy. ACS Nano 11, 11194–11205 (2017).

    CAS  Google Scholar 

  44. Niu, C. et al. High-energy lithium metal pouch cells with limited anode swelling and long stable cycles. Nat. Energy 4, 551–559 (2019).

    CAS  Google Scholar 

  45. Cannarella, J. et al. Mechanical properties of a battery separator under compression and tension. J. Electrochem. Soc. 161, F3117–F3122 (2014).

    CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy (DOE) under contract no. DE-AC02-05CH11231, subcontract no. 6951379 under the Advanced Battery Materials Research (BMR) Program and the US–Germany Cooperation on Energy Storage. The work was conducted in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by DOE Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the Department of Energy under contract DE-AC05-76RLO1830. The authors acknowledge D. Lv, S. Hu, B. Liu and R. Yi from PNNL for helpful discussions.

Author information

Authors and Affiliations

  1. Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA, USA

    Yang He, Yaobin Xu, Mark H. Engelhard & Chongmin Wang

  2. Energy and Environmental Directorate, Pacific Northwest National Laboratory, Richland, WA, USA

    Xiaodi Ren, Xiaolin Li, Jie Xiao, Jun Liu, Ji-Guang Zhang & Wu Xu

Authors
  1. Yang He
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xiaodi Ren
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yaobin Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Mark H. Engelhard
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Xiaolin Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Jie Xiao
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Jun Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Ji-Guang Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Wu Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Chongmin Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

C.W. and W.X. conceived the project. Y.H. conducted the in-situ ETEM, cryo-TEM and SEM characterizations and drafted the manuscript under the direction of C.W. and W.X. Y.X. assisted on the cryo-TEM experiments. X.R. performed the coin-cell tests. M.E. carried out the XPS measurements. X.L., J.X., J.L. and J.-G.Z. contributed to the discussion and revision of the manuscript.

Corresponding authors

Correspondence to Wu Xu or Chongmin Wang.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Peer review statement Nature Nanotechnology thanks Xiao-Qing Yang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figs. 1–10 and discussion.

Supplementary Video 1

In-situ TEM observation of the Li whisker formation in CO2 environment.

Supplementary Video 2

In-situ TEM observation of the Li deposition in N2 environment.

Supplementary Video 3

In-situ TEM observation of the Li whisker ‘failure’ by buckling.

Supplementary Video 4

In-situ TEM observation of the Li whisker ‘failure’ by buckling.

Supplementary Video 5

In-situ TEM observation of the Li whisker ‘failure’ by cessation of Li deposition on the solid electrolyte–whisker interface.

Supplementary Video 6

In-situ TEM observation of the Li whisker ‘failure’ by cessation of Li deposition on the solid electrolyte–whisker interface.

Supplementary Video 7

In-situ TEM observation of the Li whisker ‘failure’ by kink formation.

Supplementary Video 8

In-situ TEM observation of the Li whisker ‘failure’ by a combined effect of yielding and buckling.

Rights and permissions

Reprints and Permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

He, Y., Ren, X., Xu, Y. et al. Origin of lithium whisker formation and growth under stress. Nat. Nanotechnol. 14, 1042–1047 (2019). https://doi.org/10.1038/s41565-019-0558-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41565-019-0558-z

This article is cited by

Search

Advanced search

Quick links

Find nanotechnology articles, nanomaterial data and patents all in one place. Visit Nano by Nature Research