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

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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.

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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.

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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.

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Correspondence to Clare P. Grey.

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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) doi:10.1038/nmat2764

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