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Tailoring electrolyte solvation for Li metal batteries cycled at ultra-low temperature

Nature Energy volume 6, pages 303–313 (2021)Cite this article

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Abstract

Lithium metal batteries hold promise for pushing cell-level energy densities beyond 300 Wh kg−1 while operating at ultra-low temperatures (below −30 °C). Batteries capable of both charging and discharging at these temperature extremes are highly desirable due to their inherent reduction in the need for external warming. Here we demonstrate that the local solvation structure of the electrolyte defines the charge-transfer behaviour at ultra-low temperature, which is crucial for achieving high Li metal Coulombic efficiency and avoiding dendritic growth. These insights were applied to Li metal full-cells, where a high-loading 3.5 mAh cm−2 sulfurized polyacrylonitrile (SPAN) cathode was paired with a onefold excess Li metal anode. The cell retained 84% and 76% of its room temperature capacity when cycled at −40 and −60 °C, respectively, which presented stable performance over 50 cycles. This work provides design criteria for ultra-low-temperature lithium metal battery electrolytes, and represents a defining step for the performance of low-temperature batteries.

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Fig. 1: Operational schemes of low-temperature LMBs and the significance of their electrolyte structure for ultra-low Li plating.
Fig. 2: Li metal performance and characterization at benign and ultra-low temperatures.
Fig. 3: Lithium SEI and ionic conductivity study of electrolytes.
Fig. 4: Theoretical and experimental analysis of electrolyte structure.
Fig. 5: Proposed relationship between electrolyte structure and desolvation.
Fig. 6: 1× Li||SPAN full-cell performance at benign and ultra-low temperature.
Fig. 7: The historical context of this work.

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All relevant data are included in the paper and its Supplementary Information.

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Acknowledgements

This work was supported by a NASA Space Technology Graduate Research Opportunity. This work was also partially supported by the Office of Vehicle Technologies of the US Department of Energy through the Advanced Battery Materials Research (BMR) Program (Battery500 Consortium) under contract no. DE-EE0007764 to P.L. This work was also partially supported by an Early Career Faculty grant from NASA’s Space Technology Research Grants Program (ECF 80NSSC18K1512) to Z.C. Part of the work used the UCSD-MTI Battery Fabrication Facility and the UCSD-Arbin Battery Testing Facility. Electron microscopic characterization was performed at the San Diego Nanotechnology Infrastructure (SDNI) of UCSD, a member of the National Nanotechnology Coordinated Infrastructure, which is supported by the National Science Foundation (grant ECCS-1542148). Computational support for this work was provided by the National Energy Research Scientific Computing Center (NERSC), a US Department of Energy Office of Science User Facility operated under contract no. DE-AC02-05CH11231. This work also used the Extreme Science and Engineering Discovery Environment (XSEDE)53 on the Comet supercomputer at the San Diego Supercomputing Center, which is supported by National Science Foundation grant no. ACI-1548562.

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Authors and Affiliations

  1. Department of NanoEngineering, University of California, San Diego, La Jolla, CA, USA

    John Holoubek, Haodong Liu, Guorui Cai, Hongyao Zhou, Tod A. Pascal, Zheng Chen & Ping Liu

  2. Program of Materials Science, University of California, San Diego, La Jolla, CA, USA

    Yijie Yin, Xing Xing, Sicen Yu, Tod A. Pascal, Zheng Chen & Ping Liu

  3. Program of Chemical Engineering, University of California, San Diego, La Jolla, CA, USA

    Zhaohui Wu, Tod A. Pascal, Zheng Chen & Ping Liu

  4. Sustainable Power and Energy Center, University of California, San Diego, La Jolla, CA, USA

    Tod A. Pascal, Zheng Chen & Ping Liu

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Contributions

J.H. conceived the original idea. P.L. and Z.C. directed the project. J.H., H.L. and Z.W. carried out the experiments. Z.W., X.X., S.Y., G.C. and Y.Y. assisted with characterization. T.A.P. directed the computational experiments. J.H., H.L., Z.C. and P.L. wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Tod A. Pascal, Zheng Chen or Ping Liu.

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Peer review information Nature Energy thanks Kevin Leung and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–23, Discussion 1–5, Tables 1–3 and references.

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Holoubek, J., Liu, H., Wu, Z. et al. Tailoring electrolyte solvation for Li metal batteries cycled at ultra-low temperature. Nat Energy 6, 303–313 (2021). https://doi.org/10.1038/s41560-021-00783-z

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