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Rejuvenating dead lithium supply in lithium metal anodes by iodine redox

Abstract

Inactive lithium (more frequently called dead lithium) in the forms of solid–electrolyte interphase and electrically isolated metallic lithium is principally responsible for the performance decay commonly observed in lithium metal batteries. A fundamental solution of recovering dead lithium is urgently needed to stabilize lithium metal batteries. Here we quantify the solid–electrolyte interphase components, and determine their relation with the formation of electrically isolated dead lithium metal. We present a lithium restoration method based on a series of iodine redox reactions mainly involving I3/I. Using a biochar capsule host for iodine, we show that the I3/I redox takes place spontaneously, effectively rejuvenating dead lithium to compensate the lithium loss. Through this design, a full-cell using a very limited lithium metal anode exhibits an excellent lifespan of 1,000 cycles with a high Coulombic efficiency of 99.9%. We also demonstrate the design with a commercial cathode in pouch cells.

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Fig. 1: Li restoration based on iodine redox shuttling.
Fig. 2: Microstructures and components of different SEIs.
Fig. 3: The underlying functions of iodine species.
Fig. 4: The inhibition of the electrolyte exhaustion by iodine species.
Fig. 5: Fabrication and characterization of ICPC.
Fig. 6: Electrochemical performance in the half-cells.
Fig. 7: Electrochemical performance in the full-cells.

Data availability

All data supporting the findings of this study are available in the article and its Supplementary Information.

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Acknowledgements

We acknowledge financial support by the National Natural Science Foundation of China (grant nos 51722210, 51972285, U1802254, 21902144 and 52071295), the Natural Science Foundation of Zhejiang Province (grant nos LY17E020010 and LD18E020003) and the Foundation of Zhejiang Institute of Advanced Materials for Science and Innovation (KYY-HX-20190265), and high-performance computational resources (TianHe-2) provided by LvLiang Cloud Computing Center of China. This work was also supported by the US Department of Energy, Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office under the US–China Clean Energy Research Centre (CERC-CVC2) programme. Argonne National Laboratory is operated for the US Department of Energy, Office of Science by UChicago Argonne, LLC, under contract number DE-AC02-06CH11357. We thank S. Song for assistance with the gas chromatography experiments.

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Contributions

C.J., Tiefeng Liu, J.L. and X.T. conceived the concept and designed the experiments. C.J. and M.L. performed the material synthesis and electrochemical measurements. O.S., C.J., Tongchao Liu, Y.Y. and Z.J. participated in material characterization. C.J., X.T., Y.L, Z.L. and W.Z. interpreted the results. Y.W. performed the density functional theory calculations. C.J., Tiefeng Liu, J.N., J.L. and X.T. cowrote the paper. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Jun Lu or Xinyong Tao.

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Supplementary Figs. 1–30 and Table 1.

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Jin, C., Liu, T., Sheng, O. et al. Rejuvenating dead lithium supply in lithium metal anodes by iodine redox. Nat Energy 6, 378–387 (2021). https://doi.org/10.1038/s41560-021-00789-7

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