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Ultrafast lithium diffusion in bilayer graphene

Abstract

Solids that simultaneously conduct electrons and ions are key elements for the mass transfer and storage required in battery electrodes. Single-phase materials with a high electronic and high ionic conductivity at room temperature are hard to come by, and therefore multiphase systems with separate ion and electron channels have been put forward instead. Here we report on bilayer graphene as a single-phase mixed conductor that demonstrates Li diffusion faster than in graphite and even surpassing the diffusion of sodium chloride in liquid water. To measure Li diffusion, we have developed an on-chip electrochemical cell architecture in which the redox reaction that forces Li intercalation is localized only at a protrusion of the device so that the graphene bilayer remains unperturbed from the electrolyte during operation. We performed time-dependent Hall measurements across spatially displaced Hall probes to monitor the in-plane Li diffusion kinetics within the graphene bilayer and measured a diffusion coefficient as high as 7×10–5 cm2 s–1.

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Figure 1: Electrochemical device set-up.
Figure 2: Weak localization in bilayer graphene devices at different states of lithiation.
Figure 3: Revealing Li intercalation in between graphene sheets only.
Figure 4: Direct measurement of Li diffusion.

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Acknowledgements

We acknowledge financial support from the Baden-Württemberg Stiftung as well as the European Union graphene flagship and the Deutsche Forschungsgemeinschaft graphene priority programme (SPP 1459). The authors thank K. v. Klitzing for discussions and support, U. Starke and T. Acartürk for the TOF-SIMS analysis and D. Samuelis for initial discussions.

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Contributions

M.K., F.P. and J.H.S. conceived the experiments. M.K. and F.P. fabricated the devices. M.K. performed the experiments. J.P. characterized the electrolyte. J.P. and J.M. contributed to the electrochemical design of the experiments. P.M.O. contributed the theoretical interpretation of the transport experiments. All the authors discussed the results. M.K. and J.H.S. wrote the manuscript and all the authors contributed to it.

Corresponding author

Correspondence to Jurgen H. Smet.

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The authors declare no competing financial interests.

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Kühne, M., Paolucci, F., Popovic, J. et al. Ultrafast lithium diffusion in bilayer graphene. Nature Nanotech 12, 895–900 (2017). https://doi.org/10.1038/nnano.2017.108

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