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Free-standing ultrathin lithium metal–graphene oxide host foils with controllable thickness for lithium batteries

Abstract

Thin (≤20 μm) and free-standing Li metal foils would enable precise prelithiation of anode materials and high-energy-density Li batteries. Existing Li metal foils are too thick (typically 50 to 750 μm) or too mechanically fragile for these applications. Here, we developed a facile and scalable process for the synthesis of an ultrathin (0.5 to 20 μm), free-standing and mechanically robust Li metal foil within a graphene oxide host. In addition to low areal capacities of ~0.1 to 3.7 mAh cm−2, this Li foil also has a much-improved mechanical strength over conventional pure Li metal foil. Our Li foil can improve the initial Coulombic efficiency of graphite (93%) and silicon (79.4%) anodes to around 100% without generating excessive Li residue, and increases the capacity of Li-ion full cells by 8%. The cycle life of Li metal full cells is prolonged by nine times using this thin Li composite anode.

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Fig. 1: Design and fabrication of micrometre-scale thin host and Li metal film.
Fig. 2: Characterizations of the ultrathin Li@eGF film.
Fig. 3: Ultrathin Li@eGF film enables precise prelithiation and ideal ICE of graphite anode.
Fig. 4: Ultrathin Li@eGF film improved initial ICE and cycling stability of Si anode.
Fig. 5: Ultrathin Li@eGF film improves stability of Li metal || LFP full cell.

Data availability

All relevant data are included in the paper and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

Part of this work was performed at the Stanford Nano Shared Facilities and Stanford Nanofabrication Facility, supported by the National Science Foundation under award ECCS-2026822. Fabrication of the ultrathin Li metal foils and the Li-metal-anode-based full cell applications are funded by Murata Manufacturing. Utilizing the ultrathin Li metal foils to prelithiate the graphite and silicon anode was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy under the Battery Materials Research programme. Y.C. acknowledges the 20-μm-thick pure Li metal foils provided from Hydro-Québec company.

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Authors

Contributions

Y.C. conceived the idea for the project. H.C., Y.Y., Hansen Wang and H.G. designed the experiments and fabricated the electrodes. H.C. conducted the SEM and XPS characterizations. Hongxia Wang conducted the X-ray diffraction characterization and gas chromatograph measurements. Y.K.J. fabricated the nano-Si electrodes. R.X. and L.S.V. conducted the nanoindentation characterizations. Z.H. and Y.Y. conducted the tensile strength characterizations. Y.Y. and J.W. designed the prelithiation process. H.C. and W.H. fabricated the pouch cells. W.H. collected the video for the USER reaction. H.C. and Y.Y. designed and conducted the electrochemical measurements. H.C., Y.Y., D.T.B., R.X., R.M., K.M., Y.N. and Y.C. wrote and revised the manuscript. All authors discussed the results and commented on the manuscript at all stages.

Corresponding author

Correspondence to Yi Cui.

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The authors declare no competing interests.

Additional information

Peer review information Nature Energy thanks Boštjan Genorio, Tianyou Zhai 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. 1–18, Table 1, Note 1 and refs. 1–3.

Supplementary Video 1

Flexibility test of ultrathin GO film.

Supplementary Video 2

USER reaction on GO film.

Supplementary Video 3

Controllable calendaring on porous eGF film.

Supplementary Video 4

Edge-contact molten Li infusion into eGF host.

Supplementary Video 5

Flexibility test of ultrathin Li@eGF foil.

Source data

Source Data Fig. 2

Statistical source data.

Source Data Fig. 3

Statistical source data.

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Chen, H., Yang, Y., Boyle, D.T. et al. Free-standing ultrathin lithium metal–graphene oxide host foils with controllable thickness for lithium batteries. Nat Energy 6, 790–798 (2021). https://doi.org/10.1038/s41560-021-00833-6

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