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7Li MRI of Li batteries reveals location of microstructural lithium

Abstract

There is an ever-increasing need for advanced batteries for portable electronics, to power electric vehicles and to facilitate the distribution and storage of energy derived from renewable energy sources1,2. The increasing demands on batteries and other electrochemical devices have spurred research into the development of new electrode materials that could lead to better performance and lower cost (increased capacity, stability and cycle life, and safety)1,2,3. These developments have, in turn, given rise to a vigorous search for the development of robust and reliable diagnostic tools to monitor and analyse battery performance, where possible, in situ4,5,6,7,8,9. Yet, a proven, convenient and non-invasive technology, with an ability to image in three dimensions the chemical changes that occur inside a full battery as it cycles, has yet to emerge. Here we demonstrate techniques based on magnetic resonance imaging, which enable a completely non-invasive visualization and characterization of the changes that occur on battery electrodes and in the electrolyte. The current application focuses on lithium-metal batteries and the observation of electrode microstructure build-up as a result of charging. The methods developed here will be highly valuable in the quest for enhanced battery performance and in the evaluation of other electrochemical devices.

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Figure 1: Schematic representations of a bag-cell battery and one-dimensional 7Li NMR spectra in the pristine and charged states.
Figure 2: 7Li magnetic resonance and SEM images of Li microstructure formation in Li bag cells.
Figure 3: Three-dimensional MRI images of the Li-metal bag cells.
Figure 4: 7Li chemical-shift images of the Li-metal bag cell.

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References

  1. Goodenough, J. B. & Kim, Y. Challenges for rechargeable Li batteries. Chem Mater. 22, 587–603 (2010).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  3. Whittingham, M. S. Lithium batteries and cathode materials. Chem. Rev. 104, 4271–4301 (2004).

    Article  CAS  Google Scholar 

  4. Grey, C. P. & Dupre, N. NMR studies of cathode materials for lithium-ion rechargeable batteries. Chem. Rev. 104, 4493–4512 (2004).

    Article  CAS  Google Scholar 

  5. 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 

  6. 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 

  7. Bhattacharyya, R. et al. In situ NMR observation of the formation of metallic lithium microstructures in lithium batteries. Nature Mater. 9, 504–510 (2010).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  9. Amalraj, S. F. & Aurbach, D. The use of in situ techniques in R&D of Li and Mg rechargeable batteries. J. Solid State Electrochem. 15, 877–890 (2011).

    Article  CAS  Google Scholar 

  10. López, C. M., Vaughey, J. T. & Dees, D. W. Morphological transitions on lithium metal anodes. J. Electrochem. Soc. 156, A726–A729 (2009).

    Article  Google Scholar 

  11. Westbrook, C., Roth, C. K. & Talbot, J. MRI in Practice (John Wiley, 2011).

    Google Scholar 

  12. Callaghan, P. T. Principles of Nuclear Magnetic Resonance Microscopy (Oxford Univ. Press, 2003).

    Google Scholar 

  13. Gladden, L. F., Mantle, M. D. & Sederman, A. J. in Advances in Catalysis Vol. 50 (eds Gates, B. C. & Knozinger, H.) 1–75 (Elsevier Academic, 2006).

    Google Scholar 

  14. Bajaj, V. S., Paulsen, J., Harel, E. & Pines, A. Zooming in on microscopic flow by remotely detected MRI. Science 330, 1078–1081 (2010).

    Article  CAS  Google Scholar 

  15. Blümich, B. NMR Imaging of Materials (Oxford Univ. Press, 2003).

    Book  Google Scholar 

  16. Casanova, F., Perlo, J. & Blümich, B. Single-Sided NMR (Springer, 2011).

    Book  Google Scholar 

  17. Zhang, Z. & Balcom, B. J. in PEM Fuel Cell Diagnostic Tools (eds Wang, H., Yuan, X. & Li, H.) 229–254 (Taylor and Francis, 2011).

    Book  Google Scholar 

  18. Wang, M., Feindel, K. W., Bergens, S. H. & Wasylishen, R. E. In situ quantification of the in-plane water content in the Nafion membrane of an operating polymer-electrolyte membrane fuel cell using 1H micro-magnetic resonance imaging experiments. J. Power Sources 195, 7316–7322 (2010).

    Article  CAS  Google Scholar 

  19. Davenport, A. J., Forsyth, M. & Britton, M. M. Visualisation of chemical processes during corrosion of zinc using magnetic resonance imaging. Electrochem. Commun. 12, 44–47 (2010).

    Article  CAS  Google Scholar 

  20. Kawamura, J. & Iwai, Y. Tohoku Univ Takes MRI Images of Li-ion Battery. http://techon.nikkeibp.co.jp/english/NEWS_EN/20090709/172827/ (2009).

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

    Article  CAS  Google Scholar 

  22. Gireaud, L., Grugeon, S., Laruelle, S., Yrieix, B. & Tarascon, J. M. Lithium metal stripping/plating mechanisms studies: A metallurgical approach. Electrochem. Commun. 8, 1639–1649 (2006).

    Article  CAS  Google Scholar 

  23. Yoshimatsu, I., Hirai, T. & Yamaki, J. Lithium electrode morphology during cycling in lithium cells. J. Electrochem. Soc. 135, 2422–2427 (1988).

    Article  CAS  Google Scholar 

  24. Brissot, C., Rosso, M., Chazalviel, J. N. & Lascaud, S. In situ concentration cartography in the neighborhood of dendrites growing in lithium/polymer-electrolyte/lithium cells. J. Electrochem. Soc. 146, 4393–4400 (1999).

    Article  CAS  Google Scholar 

  25. Aurbach, D., Zinigrad, E., Cohen, Y. & Teller, H. A short review of failure mechanisms of lithium metal and lithiated graphite anodes in liquid electrolyte solutions. Solid State Ionics 148, 405–416 (2002).

    Article  CAS  Google Scholar 

  26. Jackson, J. D. Classical Electrodynamics 3rd edn (John Wiley, 1990).

    Google Scholar 

  27. Zhong, C. J. et al. Nanostructured catalysts in fuel cells. Nanotechnology 21, 062001 (2010).

    Article  Google Scholar 

  28. Holby, E. F., Sheng, W. C., Shao-Horn, Y. & Morgan, D. Pt nanoparticle stability in PEM fuel cells: Influence of particle size distribution and crossover hydrogen. Energy Environ. Sci. 2, 865–871 (2009).

    Article  CAS  Google Scholar 

  29. Hoult, D. I. The principle of reciprocity in signal strength calculations—a mathematical guide. Concepts Magn. Reson. 12, 173–187 (2000).

    Article  CAS  Google Scholar 

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Acknowledgements

We would like to thank R. Bhattacharrya, B. Key and L. Zhou for their help in the initial stages to this project. Research was carried out as part of the NECCES, an Energy Frontier Research Center funded by the US Department of Energy, Office of Basic Energy Sciences, under award DE-SC0001294. We thank the US National Science Foundation (and grant CMI 0957586) for summer salary for A.J.

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Contributions

S.C., N.M.T. and H.J.C. carried out experiments, N.M.T. and H.J.C. prepared samples, S.C. and A.J. carried out data processing, S.C., L-S.D. and H.J.C. prepared figures and S.C., N.M.T., C.P.G. and A.J. wrote the manuscript. All authors analysed and discussed the results.

Corresponding authors

Correspondence to Clare P. Grey or Alexej Jerschow.

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The authors declare no competing financial interests.

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Chandrashekar, S., Trease, N., Chang, H. et al. 7Li MRI of Li batteries reveals location of microstructural lithium. Nature Mater 11, 311–315 (2012). https://doi.org/10.1038/nmat3246

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