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Lithium anode interlayer design for all-solid-state lithium-metal batteries

Nature Energy volume 9, pages 251–262 (2024)Cite this article

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Abstract

All-solid-state lithium-metal batteries (ASSLBs) have attracted intense interest due to their high energy density and high safety. However, Li dendrite growth and high interface resistance remain challenging due to insufficient understanding of the mechanism. Here we develop two types of porous lithiophobic interlayer (Li7N2I–carbon nanotube and Li7N2I–Mg) to enable Li to plate at the Li/interlayer interface and reversibly penetrate into the porous interlayer. The experimental and simulation results reveal that a balance of lithiophobicity, electronic and ionic conductivities and interlayer’s porosity are the key enablers for stable Li plating/stripping at a high capacity. A fine-tuned Li7N2I–carbon nanotube interlayer enables Li/LNI/Li symmetric cell to achieve a high critical current density of 4.0 mA cm−2 at 4.0 mAh cm−2 at 25 °C; the Li7N2I–Mg interlayer enables a Li4SiO4@LiNi0.8Mn0.1Co0.1O2/Li6PS5Cl/20 µm-Li full cell to achieve an areal capacity of 2.2 mAh cm−2, maintaining 82.4% capacity retention after 350 cycles at 60 °C at a rate of 0.5 C. The interlayer design principle opens opportunities to develop safe and high energy ASSLBs.

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Fig. 1: The evolution of Li/interlayer interface after cells assemble, Li nucleation, Li growth and Li stripping.
Fig. 2: Li stripping/plating behaviours in ionic conductive, mixed conductive and electronic conductive interlayers.
Fig. 3: Li dendrite suppression capability of mixed conductive LNI–CNT interlayers.
Fig. 4: Proposed design principle for Li dendrite suppression.
Fig. 5: Optimization of mixed conductive interlayer and full cell performance with a 20 µm lithium-metal anode.

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Data availability

The data supporting the findings of this study are available within the article and its Supplementary Information files.

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Acknowledgements

This work was supported by the US Department of Energy (DOE) under award number DEEE0008856 (received by C.W.) and award number DE-AC05-76RL01830.

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Authors and Affiliations

  1. Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, MD, USA

    Zeyi Wang, Jiale Xia, Xiao Ji, Yijie Liu, Jiaxun Zhang, Xinzi He, Hongli Wan & Chunsheng Wang

  2. Department of Materials Science and Engineering, University of Maryland, College Park, MD, USA

    Weiran Zhang

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Contributions

Z.W. designed and conducted the experiments, performed the calculations and analysed the data. J.X, X.J. and H.W. conducted the electrochemical experiments. J.X., J.Z. X.H. and W.Z. performed XRD, Raman, SEM and ToF-SIMS characterizations. Y.L. synthesized the LLZO. Z.W. wrote the draft manuscript. All authors revised the manuscript. C.W. conceived and supervised the project. All authors contributed to the interpretation of the results.

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Correspondence to Hongli Wan or Chunsheng Wang.

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Nature Energy thanks Nagaphani Aetukuri, Nicolas Delaporte and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–40, Tables 1–6 and Notes 1–13.

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Wang, Z., Xia, J., Ji, X. et al. Lithium anode interlayer design for all-solid-state lithium-metal batteries. Nat Energy 9, 251–262 (2024). https://doi.org/10.1038/s41560-023-01426-1

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