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Low-temperature and high-rate-charging lithium metal batteries enabled by an electrochemically active monolayer-regulated interface

Nature Energy volume 5, pages 534–542 (2020)Cite this article

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Abstract

Stable operation of rechargeable lithium-based batteries at low temperatures is important for cold-climate applications, but is plagued by dendritic Li plating and unstable solid–electrolyte interphase (SEI). Here, we report on high-performance Li metal batteries under low-temperature and high-rate-charging conditions. The high performance is achieved by using a self-assembled monolayer of electrochemically active molecules on current collectors that regulates the nanostructure and composition of the SEI and deposition morphology of Li metal anodes. A multilayer SEI that contains a lithium fluoride-rich inner phase and amorphous outer layer effectively seals the Li surface, in contrast to the conventional SEI, which is non-passive at low temperatures. Consequently, galvanic Li corrosion and self-discharge are suppressed, stable Li deposition is achieved from −60 °C to 45 °C, and a Li | LiCoO2 cell with a capacity of 2.0 mAh cm−2 displays a 200-cycle life at −15 °C with a recharge time of 45 min.

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Fig. 1: A stable low-temperature SEI regulated by an EAM on Cu.
Fig. 2: In situ decomposition of the EAM during SEI formation.
Fig. 3: Li nucleation and growth regulated by the EAM Cu.
Fig. 4: SEI nanostructure regulated by the EAM.
Fig. 5: EAM decomposition at the interface by nanoscale depth-profiling XPS.
Fig. 6: Composition of Li metal anode SEI formed at 25° and −15 °C.
Fig. 7: Battery performance under low-temperature conditions.
Fig. 8: Low-temperature SEI chemistry studied by modelling and quantitative NMR.

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Acknowledgements

This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy, through the Advanced Battery Materials Research (BMR) Program (Battery500 Consortium) award no. DE-EE0008198. T.R. and A.T.N. acknowledge the provision of computing resources on Bebop, a high-performance computing cluster operated by the Laboratory Computing Resource Center at Argonne National Laboratory. We thank S. Zheng for discussion on the performance of batteries at low temperatures.

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Authors and Affiliations

  1. Department of Mechanical Engineering, The Pennsylvania State University, University Park, PA, USA

    Yue Gao, Shuai Liu, Daiwei Wang, Tianhang Chen & Donghai Wang

  2. Materials Science Division, Argonne National Laboratory, Lemont, IL, USA

    Tomas Rojas & Anh T. Ngo

  3. Nanoscale and Quantum Phenomena Institute and the Department of Physics and Astronomy, Ohio University, Athens, OH, USA

    Tomas Rojas

  4. Materials Research Institute, The Pennsylvania State University, University Park, PA, USA

    Ke Wang & Haiying Wang

  5. Department of Chemical Engineering, University of Illinois at Chicago, Chicago, IL, USA

    Anh T. Ngo

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Contributions

Y.G. and Donghai Wang conceived and designed the experiments. Y.G., T.C., and S.L. prepared the materials and electrodes. T.R. and A.T.N. designed and conducted the electrochemical simulation of the low-temperature SEI. K.W. and H.W. performed the TEM experiments. Y.G. and Daiwei Wang conducted the electrochemical tests. All authors discussed and analysed the data. Y.G. and Donghai Wang prepared the manuscript with input from all co-authors.

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Correspondence to Donghai Wang.

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Supplementary Figs. 1–51, discussion, Tables 1–9 and refs. 1–7.

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Gao, Y., Rojas, T., Wang, K. et al. Low-temperature and high-rate-charging lithium metal batteries enabled by an electrochemically active monolayer-regulated interface. Nat Energy 5, 534–542 (2020). https://doi.org/10.1038/s41560-020-0640-7

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