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Reversible epitaxial electrodeposition of metals in battery anodes

Jingxu Zheng https://orcid.org/0000-0002-0673-0560, Qing Zhao https://orcid.org/0000-0003-0625-9892, Tian Tang https://orcid.org/0000-0002-2233-4912, Jiefu Yin, Calvin D. Quilty https://orcid.org/0000-0002-0294-6815, Genesis D. Renderos https://orcid.org/0000-0002-6237-3625, Xiaotun Liu https://orcid.org/0000-0002-9968-6545, Yue Deng https://orcid.org/0000-0002-1683-5884, Lei Wang https://orcid.org/0000-0002-6348-8344, David C. Bock https://orcid.org/0000-0002-2387-7791, Cherno Jaye https://orcid.org/0000-0001-6158-6373, Duhan Zhang https://orcid.org/0000-0001-9428-956X, Esther S. Takeuchi, Kenneth J. Takeuchi, Amy C. Marschilok https://orcid.org/0000-0001-9174-0474, and Lynden A. Archer https://orcid.org/0000-0001-9032-2772 [email protected]
Science • 1 Nov 2019 • Vol 366, Issue 6465 • pp. 645-648 • DOI: 10.1126/science.aax6873
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Controlling electrode growth

Batteries with metal anodes can grow dendrites during cycling, which can cause short circuits in a battery or subsequently reduce the charge capacity. Zheng et al. developed a process to electrodeposit zinc on a graphene-coated stainless-steel electrode, such that the zinc forms plates with preferential orientation parallel to the electrode. This is achieved by depositing a graphene layer on stainless steel designed to epitaxially match the basal (002) plane of metallic zinc, minimizing lattice strain. During cycling, the zinc will redeposit in plate form rather than as a dendrite such that the batteries show excellent reversibility over thousands of cycles.
Science, this issue p. 645

Abstract

The propensity of metals to form irregular and nonplanar electrodeposits at liquid-solid interfaces has emerged as a fundamental barrier to high-energy, rechargeable batteries that use metal anodes. We report an epitaxial mechanism to regulate nucleation, growth, and reversibility of metal anodes. The crystallographic, surface texturing, and electrochemical criteria for reversible epitaxial electrodeposition of metals are defined and their effectiveness demonstrated by using zinc (Zn), a safe, low-cost, and energy-dense battery anode material. Graphene, with a low lattice mismatch for Zn, is shown to be effective in driving deposition of Zn with a locked crystallographic orientation relation. The resultant epitaxial Zn anodes achieve exceptional reversibility over thousands of cycles at moderate and high rates. Reversible electrochemical epitaxy of metals provides a general pathway toward energy-dense batteries with high reversibility.
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Supplementary Materials

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Materials and Methods
Figs. S1 to S31
Tables S1 to S4
References (35–38)
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Science
Volume 366 | Issue 6465
1 November 2019

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Copyright © 2019 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.
This is an article distributed under the terms of the Science Journals Default License.

Submission history

Received: 13 April 2019
Accepted: 8 October 2019
Published in print: 1 November 2019

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Acknowledgments

The authors express their gratitude to X. Zheng, L. Li, L. Luo, R. Luo, M. Pfeifer, and X. Ren for valuable discussions. Funding: This work was supported as part of the Center for Mesoscale Transport Properties, an Energy Frontier Research Center supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under award DE-SC0012673. NEXAFS experiments were carried out at the 7-ID SST-1 beamline in the National Synchrotron Light Source II at Brookhaven National Laboratory, which is supported by the U.S. Department of Energy under contracts DE-AC02-98CH10886 and DE-SC-00112704. G.D.R. acknowledges the Graduate Assistance in Areas of National Need Fellowship (GAANN). L.A.A. acknowledges the James A. Friend Family Distinguished Professorship in Engineering. E.S.T. acknowledges the William and Jane Knapp Chair in Energy and the Environment. This work made use of the Cornell Center for Materials Research Shared Facilities, which are supported through the NSF Materials Research Science and Engineering Center program (DMR-1719875). The work also used CESI Shared Facilities partly sponsored by the NSF MRI DMR-1338010 and Kavli Institute at Cornell University (KIC). Certain commercial names are mentioned in this manuscript and the supplementary materials for the purpose of example and do not constitute an endorsement by the National Institute of Standards and Technology. This research used Beamline 7-ID-1 of the National Synchrotron Light Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under contract DE-SC0012704. Author contributions: L.A.A. directed the research. J.Z., Q.Z., T.T., and L.A.A. conceived and designed this work. J.Z., Q.Z., and T.T. performed the electrodeposition, electrochemical measurements, and structure characterizations. J.Y. carried out the AFM investigation. L.A.A., J.Z., X.L., Q.Z., Y.D., and D.Z. conducted rheology measurements. C.D.Q., G.D.R., J.Z., E.S.T., K.J.T. and A.C.M. performed the XRD characterization. L.W., D.C.B., C.J., E.S.T., K.J.T., and A.C.M. performed the NEXAFS characterizations. J.Z., L.A.A., Q.Z., and T.T. wrote the article with edits and approval from all the authors. Competing interests: L.A.A. is a founder and member of the board of directors of NOHMs Technologies. This company develops and commercializes electrolytes for Li-ion and Li-sulfur battery technology. The authors declare no other competing interests. Data and materials availability: All data needed to evaluate the conclusions in the paper are present in the paper or the supplementary materials.

Authors

Affiliations

Jingxu Zheng* https://orcid.org/0000-0002-0673-0560
Department of Materials Science and Engineering, Cornell University, Ithaca, NY 14853, USA.
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Qing Zhao* https://orcid.org/0000-0003-0625-9892
Robert Frederick Smith School of Chemical and Biomolecular Engineering, Cornell University, Ithaca, NY 14853, USA.
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Tian Tang https://orcid.org/0000-0002-2233-4912
Department of Materials Science and Engineering, Cornell University, Ithaca, NY 14853, USA.
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Jiefu Yin
Robert Frederick Smith School of Chemical and Biomolecular Engineering, Cornell University, Ithaca, NY 14853, USA.
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Calvin D. Quilty https://orcid.org/0000-0002-0294-6815
Department of Chemistry, Stony Brook University, Stony Brook, NY 11794, USA.
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Genesis D. Renderos https://orcid.org/0000-0002-6237-3625
Department of Chemistry, Stony Brook University, Stony Brook, NY 11794, USA.
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Xiaotun Liu https://orcid.org/0000-0002-9968-6545
Robert Frederick Smith School of Chemical and Biomolecular Engineering, Cornell University, Ithaca, NY 14853, USA.
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Yue Deng https://orcid.org/0000-0002-1683-5884
Department of Materials Science and Engineering, Cornell University, Ithaca, NY 14853, USA.
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Lei Wang https://orcid.org/0000-0002-6348-8344
Energy Sciences Directorate, Brookhaven National Laboratory, Interdisciplinary Sciences Building, Building 734, Upton, NY 11973, USA.
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David C. Bock https://orcid.org/0000-0002-2387-7791
Energy Sciences Directorate, Brookhaven National Laboratory, Interdisciplinary Sciences Building, Building 734, Upton, NY 11973, USA.
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Cherno Jaye https://orcid.org/0000-0001-6158-6373
Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD 20899, USA.
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Duhan Zhang https://orcid.org/0000-0001-9428-956X
Sibley School of Mechanical and Aerospace Engineering, Cornell University, Ithaca, NY 14853, USA.
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Esther S. Takeuchi
Department of Chemistry, Stony Brook University, Stony Brook, NY 11794, USA.
Energy Sciences Directorate, Brookhaven National Laboratory, Interdisciplinary Sciences Building, Building 734, Upton, NY 11973, USA.
Department of Materials Science and Chemical Engineering, Stony Brook, NY 11794, USA.
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Kenneth J. Takeuchi
Department of Chemistry, Stony Brook University, Stony Brook, NY 11794, USA.
Energy Sciences Directorate, Brookhaven National Laboratory, Interdisciplinary Sciences Building, Building 734, Upton, NY 11973, USA.
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Amy C. Marschilok https://orcid.org/0000-0001-9174-0474
Department of Chemistry, Stony Brook University, Stony Brook, NY 11794, USA.
Energy Sciences Directorate, Brookhaven National Laboratory, Interdisciplinary Sciences Building, Building 734, Upton, NY 11973, USA.
Department of Materials Science and Chemical Engineering, Stony Brook, NY 11794, USA.
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Lynden A. Archer† https://orcid.org/0000-0001-9032-2772 [email protected]
Department of Materials Science and Engineering, Cornell University, Ithaca, NY 14853, USA.
Robert Frederick Smith School of Chemical and Biomolecular Engineering, Cornell University, Ithaca, NY 14853, USA.
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Correction Statement

20 October 2021: Callouts to the supplementary figures have been corrected to reflect a supplementary figure that was added during review. The original version is available here:
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Funding Information

Basic Energy Sciences: DE-SC0012673

Notes

*
These authors contributed equally to this work.
†Corresponding author. Email: [email protected]

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