Origin of lithium whisker formation and growth under stress

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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.

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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.


  1. 1.

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

  2. 2.

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

  3. 3.

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

  4. 4.

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

  5. 5.

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

  6. 6.

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

  7. 7.

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

  8. 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).

  9. 9.

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

  10. 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).

  11. 11.

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

  12. 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).

  13. 13.

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

  14. 14.

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

  15. 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).

  16. 16.

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

  17. 17.

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

  18. 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).

  19. 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).

  20. 20.

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

  21. 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).

  22. 22.

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

  23. 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).

  24. 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).

  25. 25.

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

  26. 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).

  27. 27.

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

  28. 28.

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

  29. 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).

  30. 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).

  31. 31.

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

  32. 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).

  33. 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).

  34. 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).

  35. 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).

  36. 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).

  37. 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).

  38. 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).

  39. 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).

  40. 40.

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

  41. 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).

  42. 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).

  43. 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).

  44. 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).

  45. 45.

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

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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

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.

Correspondence to Wu Xu or Chongmin Wang.

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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.

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

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