Improving cyclability of Li metal batteries at elevated temperatures and its origin revealed by cryo-electron microscopy

Abstract

Operations of lithium-ion batteries have long been limited to a narrow temperature range close to room temperature. At elevated temperatures, cycling degradation speeds up due to enhanced side reactions, especially when high-reactivity lithium metal is used as the anode. Here, we demonstrate enhanced performance in lithium metal batteries operated at elevated temperatures. In an ether-based electrolyte at 60 °C, an average Coulombic efficiency of 99.3% is obtained and more than 300 stable cycles are realized, but, at 20 °C, the Coulombic efficiency drops dramatically within 75 cycles, corresponding to an average Coulombic efficiency of 90.2%. Cryo-electron microscopy reveals a drastically different solid electrolyte interface nanostructure emerging at 60 °C, which maintains mechanical stability, inhibits continuous side reactions and guarantees good cycling stability and low electrochemical impedance. Furthermore, larger lithium particles grown at the elevated temperature reduce the electrolyte/electrode interfacial area, which decreases the per-cycle lithium loss and enables higher Coulombic efficiencies.

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Fig. 1: The conventional wisdom about the operating temperature of battery performance.
Fig. 2: Enhanced performance at elevated temperature demonstrated by Cu/Li cells.
Fig. 3: Cryo-EM reveals an emergent SEI nanostructure formed at elevated temperature.
Fig. 4: Elevated temperature nucleates larger Li particles and optimizes the electrode/electrolyte contact area.
Fig. 5: Elevated temperature results in small and stable impedance during cycling.
Fig. 6: Enhanced performance at elevated temperature demonstrated by LiFePO4/Li cells.

Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

Y.C. acknowledges support from the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies, Battery Materials Research (BMR) Program and Battery 500 Consortium of the US Department of Energy, Stanford Global Climate and Energy Projects (GCEP), the Office of Naval Research, the Joint Center for Energy Storage Research (JCESR) and a KAUST Investigator Award. A.P. acknowledges support from the National Defense Science and Engineering Graduate Fellowship and the Stanford Graduate Fellowship. Part of this work was performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under award ECCS-1542152.

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J.W., A.P. and Y.C. conceived and designed the experiments. J.W. and A.P. performed the experiments. W.H. and Y.L. conducted TEM characterization. J.W., A.P., W.H. and Y.C. co-wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Yi Cui.

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Wang, J., Huang, W., Pei, A. et al. Improving cyclability of Li metal batteries at elevated temperatures and its origin revealed by cryo-electron microscopy. Nat Energy 4, 664–670 (2019). https://doi.org/10.1038/s41560-019-0413-3

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