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In situ p-block protective layer plating in carbonate-based electrolytes enables stable cell cycling in anode-free lithium batteries

Nature Materials volume 23, pages 1686–1694 (2024)Cite this article

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Abstract

‘Anode-free’ Li metal batteries offer the highest possible energy density but face low Li coulombic efficiency when operated in carbonate electrolytes. Here we report a performance improvement of anode-free Li metal batteries using p-block tin octoate additive in the carbonate electrolyte. We show that the preferential adsorption of the octoate moiety on the Cu substrate induces the construction of a carbonate-less protective layer, which inhibits the side reactions and contributes to the uniform Li plating. In the mean time, the reduction of Sn2+ at the initial charging process builds a stable lithophilic layer of Cu6Sn5 alloy and Sn, improving the affinity between the Li and the Cu substrate. Notably, anode-free Li metal pouch cells with tin octoate additive demonstrate good cycling stability with a high coulombic efficiency of ~99.1%. Furthermore, this in situ p-block layer plating strategy is also demonstrated with other types of p-block metal octoate, as well as a Na metal battery system, demonstrating the high level of universality.

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Fig. 1: Electrochemical stability of metal anode with and without additive.
Fig. 2: Regulation of Li plating/stripping by Sn(Oct)2 additive.
Fig. 3: Li plating/stripping behaviour and characterization of plated Li.
Fig. 4: Electrochemical performance of Li || NCM coin cells and Cu || NCM pouch cells, cells visualization and Li+ solvation analysis.
Fig. 5: Mechanism of Sn(Oct)2 additive on Li plating process.

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Data availability

All of the data that support the findings of this study are available in the Article. Atomic configurations of the computational models constructed in this study are available via figshare at https://doi.org/10.6084/m9.figshare.26340670.v1 (ref. 57). Source data are provided with this paper.

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Acknowledgements

The work leading to these results received funding from the National Natural Science Foundation of China (22179098, to J.M.) and the Fundamental Research Funds for the Central Universities. L.Q. acknowledges support from the National Natural Science Foundation of China (52272203). Y.H. acknowledges support from the National Natural Science Foundation of China (52027816). M.T. acknowledges support from the National Natural Science Foundation of China (22090043). M.Y. acknowledges support from the National Natural Science Foundation of China (52302302). P.S. and T.K. acknowledge support from the German Research Foundation (STR 596/13−1).

Author information

Author notes

  1. These authors contributed equally: Jie Shi, Toshinari Koketsu, Zhenglu Zhu, Menghao Yang.

Authors and Affiliations

  1. Shanghai Key Laboratory for R&D and Application of Metallic Functional Materials, Institute of New Energy for Vehicles, School of Materials Science and Engineering, Tongji University, Shanghai, China

    Jie Shi, Toshinari Koketsu, Zhenglu Zhu, Menghao Yang, Lijun Sui & Jiwei Ma

  2. Department of Chemistry, Technical University Berlin, Berlin, Germany

    Toshinari Koketsu & Peter Strasser

  3. Center for High Pressure Science & Technology Advanced Research, Beijing, China

    Jie Liu & Mingxue Tang

  4. State Key Laboratory of Material Processing and Die & Mold Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan, China

    Zhe Deng, Mengyi Liao, Jingwei Xiang, Yue Shen, Long Qie & Yunhui Huang

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Contributions

J.M. conceived and coordinated the project. J.S., T.K., Z.Z., L.S., J.L., M.T., Z.D., M.L., J.X., Y.S., L.Q., Y.H., P.S. and J.M. carried out experimental work and data analysis. M.Y. performed theoretical calculations. All authors discussed the results. J.S., T.K., Z.Z., M.Y., L.Q., Y.H., P.S. and J.M. wrote the paper with the contributions of all co-authors.

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Correspondence to Long Qie, Yunhui Huang, Peter Strasser or Jiwei Ma.

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Supplementary Information

Supplementary Figs. 1–28 and Tables 1 and 2.

Source data

Source Data Fig. 1

Electrochemical stability of metal anode with and without additive.

Source Data Fig. 2

Regulation of Sn(Oct)2 additive on the Li plating/stripping.

Source Data Fig. 3

Li plating/stripping behaviour and the characterization of plated Li.

Source Data Fig. 4

Electrochemical performance of Li || NCM coin cells and Cu || NCM pouch cells, cell visualization and Li+ solvation analysis.

Source Data Fig. 5

Mechanism of Sn(Oct)2 additive on Li plating process.

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Shi, J., Koketsu, T., Zhu, Z. et al. In situ p-block protective layer plating in carbonate-based electrolytes enables stable cell cycling in anode-free lithium batteries. Nat. Mater. 23, 1686–1694 (2024). https://doi.org/10.1038/s41563-024-01997-8

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