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.
Subscribe to Journal
Get full journal access for 1 year
only $4.92 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
All relevant data are included in the paper and its Supplementary Information. Source data are provided with this paper.
Armand, M. & Tarascon, J. M. Building better batteries. Nature 451, 652–657 (2008).
Chu, S. & Majumdar, A. Opportunities and challenges for a sustainable energy future. Nature 488, 294–303 (2012).
Lin, D., Liu, Y. & Cui, Y. Reviving the lithium metal anode for high-energy batteries. Nat. Nanotechnol. 12, 194–206 (2017).
Liu, J. et al. Pathways for practical high-energy long-cycling lithium metal batteries. Nat. Energy 4, 180–186 (2019).
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).
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).
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).
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).
Chen, S. et al. Critical parameters for evaluating coin cells and pouch cells of rechargeable Li-metal batteries. Joule 3, 1094–1105 (2019).
Sun, Y. et al. High-capacity battery cathode prelithiation to offset initial lithium loss. Nat. Energy 1, 15008 (2016).
Cheng, Q. et al. Graphene-like-graphite as fast-chargeable and high-capacity anode materials for lithium ion batteries. Sci. Rep. 7, 14782 (2017).
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).
Xiao, J. et al. Understanding and applying coulombic efficiency in lithium metal batteries. Nat. Energy 5, 561–568 (2020).
Yu, Z. et al. Molecular design for electrolyte solvents enabling energy-dense and long-cycling lithium metal batteries. Nat. Energy 5, 526–533 (2020).
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).
Shi, P. et al. Electrochemical diagram of an ultrathin lithium metal anode in pouch cells. Adv. Mater. 31, 1902785 (2019).
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).
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).
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).
Liu, Y. et al. Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode. Nat. Commun. 7, 10992 (2016).
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).
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).
Huang, G. et al. Lithiophilic 3D nanoporous nitrogen-doped graphene for dendrite-free and ultrahigh-rate lithium-metal anodes. Adv. Mater. 31, 1805334 (2019).
Wang, Y. & Cheng, Y.-T. A nanoindentation study of the viscoplastic behavior of pure lithium. Scr. Mater. 130, 191–195 (2017).
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).
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).
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).
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).
Jang, J. et al. Chemically prelithiated graphene for anodes of Li-ion batteries. Energy Fuels 34, 13048–13055 (2020).
Yao, C. et al. An efficient prelithiation of graphene oxide nanoribbons wrapping silicon nanoparticles for stable Li+ storage. Carbon 168, 392–403 (2020).
Tomaszewska, A. et al. Lithium-ion battery fast charging: a review. eTransportation 1, 100011 (2019).
Wu, H. & Cui, Y. Designing nanostructured Si anodes for high energy lithium ion batteries. Nano Today 7, 414–429 (2012).
Sun, Y., Liu, N. & Cui, Y. Promises and challenges of nanomaterials for lithium-based rechargeable batteries. Nat. Energy 1, 16071 (2016).
Niu, C. et al. High-energy lithium metal pouch cells with limited anode swelling and long stable cycles. Nat. Energy 4, 551–559 (2019).
Zhang, Y.-j et al. Integrated reduced graphene oxide multilayer/Li composite anode for rechargeable lithium metal batteries. RSC Adv. 6, 11657–11664 (2016).
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).
Shi, F. et al. Lithium metal stripping beneath the solid electrolyte interphase. Proc. Natl Acad. Sci. USA 115, 8529–8534 (2018).
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).
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.
The authors declare no competing interests.
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 Figs. 1–18, Table 1, Note 1 and refs. 1–3.
Flexibility test of ultrathin GO film.
USER reaction on GO film.
Controllable calendaring on porous eGF film.
Edge-contact molten Li infusion into eGF host.
Flexibility test of ultrathin Li@eGF foil.
About this article
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 (2021). https://doi.org/10.1038/s41560-021-00833-6