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:

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

Nature Energy volume 6, pages 790–798 (2021)Cite this article

Subjects

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.

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

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.

Similar content being viewed by others

Data availability

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

References

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

    Article  Google Scholar 

  2. Chu, S. & Majumdar, A. Opportunities and challenges for a sustainable energy future. Nature 488, 294–303 (2012).

    Article  Google Scholar 

  3. Lin, D., Liu, Y. & Cui, Y. Reviving the lithium metal anode for high-energy batteries. Nat. Nanotechnol. 12, 194–206 (2017).

    Article  Google Scholar 

  4. Liu, J. et al. Pathways for practical high-energy long-cycling lithium metal batteries. Nat. Energy 4, 180–186 (2019).

    Article  Google Scholar 

  5. Cheng, X.-B., Zhang, R., Zhao, C.-Z. & Zhang, Q. Toward safe lithium metal anode in rechargeable batteries: a review. Chem. Rev. 117, 10403–10473 (2017).

    Article  Google Scholar 

  6. Lin, D. et al. Layered reduced graphene oxide with nanoscale interlayer gaps as a stable host for lithium metal anodes. Nat. Nanotechnol. 11, 626–632 (2016).

    Article  Google Scholar 

  7. Tikekar, M. D., Choudhury, S., Tu, Z. & Archer, L. A. Design principles for electrolytes and interfaces for stable lithium-metal batteries. Nat. Energy 1, 16114 (2016).

    Article  Google Scholar 

  8. Albertus, P., Babinec, S., Litzelman, S. & Newman, A. Status and challenges in enabling the lithium metal electrode for high-energy and low-cost rechargeable batteries. Nat. Energy 3, 16–21 (2018).

    Article  Google Scholar 

  9. Chen, S. et al. Critical parameters for evaluating coin cells and pouch cells of rechargeable Li-metal batteries. Joule 3, 1094–1105 (2019).

    Article  Google Scholar 

  10. Sun, Y. et al. High-capacity battery cathode prelithiation to offset initial lithium loss. Nat. Energy 1, 15008 (2016).

    Article  Google Scholar 

  11. Cheng, Q. et al. Graphene-like-graphite as fast-chargeable and high-capacity anode materials for lithium ion batteries. Sci. Rep. 7, 14782 (2017).

    Article  Google Scholar 

  12. Weber, R. et al. Long cycle life and dendrite-free lithium morphology in anode-free lithium pouch cells enabled by a dual-salt liquid electrolyte. Nat. Energy 4, 683–689 (2019).

    Article  Google Scholar 

  13. Xiao, J. et al. Understanding and applying coulombic efficiency in lithium metal batteries. Nat. Energy 5, 561–568 (2020).

    Article  Google Scholar 

  14. Yu, Z. et al. Molecular design for electrolyte solvents enabling energy-dense and long-cycling lithium metal batteries. Nat. Energy 5, 526–533 (2020).

    Article  Google Scholar 

  15. Schmuch, R., Wagner, R., Hörpel, G., Placke, T. & Winter, M. Performance and cost of materials for lithium-based rechargeable automotive batteries. Nat. Energy 3, 267–278 (2018).

    Article  Google Scholar 

  16. Shi, P. et al. Electrochemical diagram of an ultrathin lithium metal anode in pouch cells. Adv. Mater. 31, 1902785 (2019).

    Article  Google Scholar 

  17. Mashtalir, O., Nguyen, M., Bodoin, E., Swonger, L. & O’Brien, S. P. High-purity lithium metal films from aqueous mineral solutions. ACS Omega 3, 181–187 (2018).

    Article  Google Scholar 

  18. Kato, A., Hayashi, A. & Tatsumisago, M. Enhancing utilization of lithium metal electrodes in all-solid-state batteries by interface modification with gold thin films. J. Power Sources 309, 27–32 (2016).

    Article  Google Scholar 

  19. Chen, H. et al. Electrode design with integration of high tortuosity and sulfur-philicity for high-performance lithium-sulfur battery. Matter 2, 1605–1620 (2020).

    Article  Google Scholar 

  20. Liu, Y. et al. Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode. Nat. Commun. 7, 10992 (2016).

    Article  Google Scholar 

  21. Liang, Z. et al. Composite lithium metal anode by melt infusion of lithium into a 3D conducting scaffold with lithiophilic coating. Proc. Natl Acad. Sci. USA 113, 2862–2867 (2016).

    Article  Google Scholar 

  22. Chi, S.-S., Liu, Y., Song, W.-L., Fan, L.-Z. & Zhang, Q. Prestoring lithium into stable 3D nickel foam host as dendrite-free lithium metal anode. Adv. Funct. Mater. 27, 1700348 (2017).

    Article  Google Scholar 

  23. Huang, G. et al. Lithiophilic 3D nanoporous nitrogen-doped graphene for dendrite-free and ultrahigh-rate lithium-metal anodes. Adv. Mater. 31, 1805334 (2019).

    Article  Google Scholar 

  24. Wang, Y. & Cheng, Y.-T. A nanoindentation study of the viscoplastic behavior of pure lithium. Scr. Mater. 130, 191–195 (2017).

    Article  Google Scholar 

  25. Tariq, S. et al. Li material testing - Fermilab Antiproton Source lithium collection lens. In Proceedings of the 2003 Particle Accelerator Conference 1452–1454 (IEEE Xplore, 2003).

  26. de Vasconcelos, L. S., Xu, R. & Zhao, K. Operando nanoindentation: a new platform to measure the mechanical properties of electrodes during electrochemical reactions. J. Electrochem. Soc. 164, A3840–A3847 (2017).

    Article  Google Scholar 

  27. Holtstiege, F., Bärmann, P., Nölle, R., Winter, M. & Placke, T. Pre-lithiation strategies for rechargeable energy storage technologies: concepts, promises and challenges. Batteries 4, 4 (2018).

    Article  Google Scholar 

  28. Ren, J. J. et al. Pre-lithiated graphene nanosheets as negative electrode materials for Li-ion capacitors with high power and energy density. J. Power Sources 264, 108–113 (2014).

    Article  Google Scholar 

  29. Jang, J. et al. Chemically prelithiated graphene for anodes of Li-ion batteries. Energy Fuels 34, 13048–13055 (2020).

    Article  Google Scholar 

  30. Yao, C. et al. An efficient prelithiation of graphene oxide nanoribbons wrapping silicon nanoparticles for stable Li+ storage. Carbon 168, 392–403 (2020).

    Article  Google Scholar 

  31. Tomaszewska, A. et al. Lithium-ion battery fast charging: a review. eTransportation 1, 100011 (2019).

    Article  Google Scholar 

  32. Wu, H. & Cui, Y. Designing nanostructured Si anodes for high energy lithium ion batteries. Nano Today 7, 414–429 (2012).

    Article  Google Scholar 

  33. Sun, Y., Liu, N. & Cui, Y. Promises and challenges of nanomaterials for lithium-based rechargeable batteries. Nat. Energy 1, 16071 (2016).

    Article  Google Scholar 

  34. Niu, C. et al. High-energy lithium metal pouch cells with limited anode swelling and long stable cycles. Nat. Energy 4, 551–559 (2019).

    Article  Google Scholar 

  35. Zhang, Y.-j et al. Integrated reduced graphene oxide multilayer/Li composite anode for rechargeable lithium metal batteries. RSC Adv. 6, 11657–11664 (2016).

    Article  Google Scholar 

  36. Moorthy, B. et al. Ice-templated free-standing reduced graphene oxide for dendrite-free lithium metal batteries. ACS Appl. Energy Mater. 3, 11053–11060 (2020).

    Article  Google Scholar 

  37. Shi, F. et al. Lithium metal stripping beneath the solid electrolyte interphase. Proc. Natl Acad. Sci. USA 115, 8529–8534 (2018).

    Article  Google Scholar 

  38. LePage, W. S. et al. Lithium mechanics: roles of strain rate and temperature and implications for lithium metal batteries. J. Electrochem. Soc. 166, A89–A97 (2019).

    Article  Google Scholar 

Download references

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.

Author information

Author notes

  1. These authors contributed equally: Hao Chen, Yufei Yang.

Authors and Affiliations

  1. Department of Materials Science and Engineering, Stanford University, Stanford, CA, USA

    Hao Chen, Yufei Yang, You Kyeong Jeong, Rong Xu, Zhuojun Huang, Hansen Wang, Hongxia Wang, Wenxiao Huang, Huiqiao Li, Jiangyan Wang, Hanke Gu & Yi Cui

  2. Department of Chemistry, Stanford University, Stanford, CA, USA

    David T. Boyle

  3. School of Mechanical Engineering, Purdue University, West Lafayette, IN, USA

    Luize Scalco de Vasconcelos & Kejie Zhao

  4. Murata Manufacturing, Nagaokakyo-shi, Japan

    Ryuhei Matsumoto, Kazunari Motohashi & Yuri Nakayama

  5. Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, CA, USA

    Yi Cui

Authors
  1. Hao Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yufei Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. David T. Boyle
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. You Kyeong Jeong
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Rong Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Luize Scalco de Vasconcelos
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Zhuojun Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Hansen Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Hongxia Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Wenxiao Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Huiqiao Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Jiangyan Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Hanke Gu
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Ryuhei Matsumoto
    View author publications

    You can also search for this author in PubMed Google Scholar

  15. Kazunari Motohashi
    View author publications

    You can also search for this author in PubMed Google Scholar

  16. Yuri Nakayama
    View author publications

    You can also search for this author in PubMed Google Scholar

  17. Kejie Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  18. Yi Cui
    View author publications

    You can also search for this author in PubMed Google Scholar

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.

Ethics declarations

Competing interests

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.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

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

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41560-021-00833-6

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