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.

  • Article
  • Published:

In situ NMR observation of the formation of metallic lithium microstructures in lithium batteries

Nature Materials volume 9, pages 504–510 (2010)Cite this article

Subjects

Abstract

Lithium metal has the highest volumetric and gravimetric energy density of all negative-electrode materials when used as an electrode material in a lithium rechargeable battery. However, the formation of lithium dendrites and/or ‘moss’ on the metal electrode surface can lead to short circuits following several electrochemical charge–discharge cycles, particularly at high rates, rendering this class of batteries potentially unsafe and unusable owing to the risk of fire and explosion. Many recent investigations have focused on the development of methods to prevent moss/dendrite formation. In parallel, it is important to quantify Li-moss formation, to identify the conditions under which it forms. Although optical and electron microscopy can visually monitor the morphology of the lithium-electrode surface and hence the moss formation, such methods are not well suited for quantitative studies. Here we report the use of in situ NMR spectroscopy, to provide time-resolved, quantitative information about the nature of the metallic lithium deposited on lithium-metal electrodes.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

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

Figure 1: Schematic showing the radiofrequency penetration in a block of lithium metal and in the whisker-like dendritic structures.
Figure 2: NMR signal intensities of multiple lithium strips of length and width 11 mm×4.5 mm (normalized with respect to the thinnest strip).
Figure 3: 7Li NMR spectra of a LiCoO2–Li cell obtained during one charge–discharge electrochemical cycle.
Figure 4: The effect of multiple (>28) charge–discharge cycles on the 7Li NMR spectra of a metallic lithium symmetric cell containing an ionic–liquid electrolyte (C2mim BF4+LiBF4) and a VC additive.
Figure 5: 7Li NMR spectra of a metallic lithium symmetric cell containing the second ionic–liquid electrolyte C4mpyr TFSI + LiTFSI, during electrochemical cycling with different applied currents.
Figure 6: 7Li NMR spectra of a lithium electrode of a pristine symmetric cell (composed of two rectangular strips of size 4 mm × 8 mm × 0.38 mm with a 1 mm separator between them) at different orientations with respect to the magnetic field.

Similar content being viewed by others

References

  1. Armand, M. & Tarascon, J. M. Building better batteries. Nature 451, 652–657 (2008).

    Article  CAS  Google Scholar 

  2. Tarascon, J. M. & Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 414, 359–367 (2001).

    Article  CAS  Google Scholar 

  3. Epelboin, I., Froment, M., Garreau, M., Thevenin, J. & Warin, D. Behavior of secondary lithium and aluminum–lithium electrodes in propylene carbonate. Proc.-Electrochem. Soc. 80-4, 417–429 (1980).

    CAS  Google Scholar 

  4. Sannier, L. et al. Room temperature lithium metal batteries based on a new gel polymer electrolyte membrane. J. Power Sources 144, 231–237 (2005).

    Article  CAS  Google Scholar 

  5. Wang, C., Wang, D. L. & Dai, C. S. High-rate capability and enhanced cyclability of rechargeable lithium batteries using foam lithium anode. J. Electrochem. Soc. 155, A390–A394 (2008).

    Article  CAS  Google Scholar 

  6. Xu, J. Q., Yang, J., NuLi, Y., Wang, J. L. & Zhang, Z. S. Additive-containing ionic liquid electrolytes for secondary lithium battery. J. Power Sources 160, 621–626 (2006).

    Article  CAS  Google Scholar 

  7. Orsini, F. et al. In situ scanning electron microscopy (SEM) observation of interfaces within plastic lithium batteries. J. Power Sources 76, 19–29 (1998).

    Article  CAS  Google Scholar 

  8. Saint, J. et al. Compatibility of LixTiyMn1−yO2 (y=0, 0.11) electrode materials with pyrrolidinium-based ionic liquid electrolyte systems. J. Electrochem. Soc. 155, A172–A180 (2008).

    Article  CAS  Google Scholar 

  9. Howlett, P. C., MacFarlane, D. R. & Hollenkamp, A. F. High lithium metal cycling efficiency in a room-temperature ionic liquid. Electrochem. Solid State Lett. 7, A97–A101 (2004).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  11. Monroe, C. & Newman, J. Dendrite growth in lithium/polymer systems—a propagation model for liquid electrolytes under galvanostatic conditions. J. Electrochem. Soc. 150, A1377–A1384 (2003).

    Article  CAS  Google Scholar 

  12. Chazalviel, J. N. Electrochemical aspects of the generation of ramified metallic electrodeposits. Phys. Rev. A 42, 7355–7367 (1990).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  14. Chevallier, F. et al. In situ 7Li-nuclear magnetic resonance observation of reversible lithium insertion into disordered carbons. Electrochem. Solid State Lett. 6, A225–A228 (2003).

    Article  CAS  Google Scholar 

  15. Letellier, M., Chevallier, F. & Morcrette, M. In situ 7Li nuclear magnetic resonance observation of the electrochemical intercalation of lithium in graphite; 1st cycle. Carbon 45, 1025–1034 (2007).

    Article  CAS  Google Scholar 

  16. Gerald, R. E. et al. 7Li NMR study of intercalated lithium in curved carbon lattices. J. Power Sources 89, 237–243 (2000).

    Article  CAS  Google Scholar 

  17. Kittel, C. Introduction to Solid State Physics 8th edn (John Wiley, 2004).

    Google Scholar 

  18. Lide, D. R. & Frederikse, H. P. R. CRC Handbook of Chemistry and Physics: A Ready-Reference Book of Chemical and Physical Data 78th edn (CRC Press, 1997).

    Google Scholar 

  19. Egashira, M., Kiyabu, T., Watanabe, I., Okada, S. & Yamaki, J. The effect of additives in room temperature molten salt-based lithium battery electrolytes. Electrochemistry 71, 1114–1116 (2003).

    CAS  Google Scholar 

  20. Lane, G. H., Best, A. S., MacFarlane, D. R., Forsyth, M. & Hollenkamp, A. F. On the role of cyclic unsaturated additives on the behaviour of lithium metal electrodes in ionic liquid electrolytes. Electrochim. Acta 55, 2210–2215 (2010).

    Article  CAS  Google Scholar 

  21. Sivakkumar, S. R., MacFarlane, D. R., Forsyth, M. & Kim, D. W. Ionic liquid-based rechargeable lithium metal–polymer cells assembled with polyaniline/carbon nanotube composite cathode. J. Electrochem. Soc. 154, A834–A838 (2007).

    Article  CAS  Google Scholar 

  22. Bhatt, A. I., Best, A. S., Huang, J. H. & Hollenkamp, A. F. Application of the N-propyl-N-methyl-pyrrolidinium bis(fluorosulfonyl)imide RTIL containing lithium bis(fluorosulfonyl)imide in ionic liquid based lithium batteries. J. Electrochem. Soc. 157, A66–A74 (2010).

    Article  CAS  Google Scholar 

  23. Seki, S. et al. Reversibility of lithium secondary batteries using a room-temperature ionic liquid mixture and lithium metal. Electrochem. Solid State Lett. 8, A577–A578 (2005).

    Article  CAS  Google Scholar 

  24. Sakaebe, H. & Matsumoto, H. N-Methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide (PP 13-TFSI) — novel electrolyte base for Li battery. Electrochem. Commun. 5, 594–598 (2003).

    Article  CAS  Google Scholar 

  25. Slichter, C. P. Principles of Magnetic Resonance 3rd edn (Springer, 1990).

    Book  Google Scholar 

  26. Howlett, P. C., MacFarlane, D. R. & Hollenkamp, A. F. A sealed optical cell for the study of lithium-electrode electrolyte interfaces. J. Power Sources 114, 277–284 (2003).

    Article  CAS  Google Scholar 

  27. Kubo, A., Spaniol, T. P. & Terao, T. The effect of bulk magnetic susceptibility on solid state NMR spectra of paramagnetic compounds. J. Magn. Reson. 133, 330–340 (1998).

    Article  CAS  Google Scholar 

  28. Chen, H. & Grey, C. P. Molten salt synthesis and high rate performance of the ‘desert-rose’ form of LiCoO2 . Adv. Mater. 20, 2206–2210 (2008).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of FreedomCAR and Vehicle Technologies of the US DOE, under contract No DE-AC03-76SF00098, through subcontract No 6517749 with the Lawrence Berkeley National Laboratory (for the application of the methodology), by the New York State Foundation for Science, Technology and Innovation through a NYSTAR award (salary for R.B.), and by the NSF through DMR0804737 (development of the methodology). We thank J-M. Tarascon and M. Morcrette for helpful discussions. A.S.B. thanks CSIRO for an OCE Julius Award to conduct the work at Stony Brook University. CPG is a Royal Society-Wolfson Research Merit Award holder.

Author information

Authors and Affiliations

  1. Chemistry Department, Stony Brook University, Stony Brook, New York 11794-3400, USA

    Rangeet Bhattacharyya, Baris Key, Hailong Chen & Clare P. Grey

  2. Division of Energy Technology, Commonwealth Scientific and Industrial Research Organization, Bayview Ave, Clayton, Victoria 3168, Australia

    Adam S. Best & Anthony F. Hollenkamp

  3. Chemistry Department, University of Cambridge, Lensfield Rd, Cambridge CB2 1EW, UK

    Clare P. Grey

Authors
  1. Rangeet Bhattacharyya
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Baris Key
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Hailong Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Adam S. Best
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Anthony F. Hollenkamp
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Clare P. Grey
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Clare P. Grey.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Information (PDF 379 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Bhattacharyya, R., Key, B., Chen, H. et al. In situ NMR observation of the formation of metallic lithium microstructures in lithium batteries. Nature Mater 9, 504–510 (2010). https://doi.org/10.1038/nmat2764

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nmat2764

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing