Prevention of dendrite growth and volume expansion to give high-performance aprotic bimetallic Li-Na alloy–O2 batteries

Nature Chemistry volume 11, pages64–70(2019)Cite this article

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Abstract

Rechargeable aprotic alkali metal (Li or Na)–O2 batteries are the subject of great interest because of their high theoretical specific energy. However, the growth of dendrites and cracks at the Li or Na anode, as well as their corrosive oxidation lead to poor cycling stability and safety issues. Understanding the mechanism and improving Li/Na-ion plating and stripping electrochemistry are therefore essential to realizing their technological potential. Here, we report how the use of a Li-Na alloy anode and an electrolyte additive realizes an aprotic bimetal Li-Na alloy–O2 battery with improved cycling stability. Electrochemical investigations show that stripping and plating of Li and Na and the robust and flexible passivation film formed in situ (by 1,3-dioxolane additive reacting with the Li-Na alloy) suppress dendrite and buffer alloy anode volume expansion and thus prevent cracking, avoiding electrolyte consumption and ensuring high electron transport efficiency and continued electrochemical reactions.

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Fig. 1: Illustration of dendrite and crack suppression.
Fig. 2: Characterization of the Li-Na alloy.
Fig. 3: Oxidation and corrosion resistance as well as metal electrode morphology.
Fig. 4: Electrochemical performance for symmetric batteries.
Fig. 5: Electrochemical characterization for metal–O2 batteries.

Data availability

The authors declare that all the data supporting the findings of this study are available within the paper and its Supplementary Information.

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Acknowledgements

This work was financially supported by the National Key R&D Program of China (grants 2017YFA0206700), the National Natural Science Foundation of China (grants 21725103, 51472232, 51522101, 51471075, 51631004, 21771013 and 51522202), the Strategic Priority Research Program of the Chinese Academy of Sciences (grant XDA09010404), JCKY2016130B010, 111 project (grant B14009), and the Program for the JLU Science and Technology Innovative Research Team (2017TD-09).

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Affiliations

  1. State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China

    Jin-ling Ma, Yue Yu & Xin-bo Zhang

  2. Key Laboratory of Automobile Materials, Ministry of Education, and Department of Materials Science and Engineering, Jilin University, Changchun, Jilin, China

    Jin-ling Ma, Fan-lu Meng, Jun-min Yan & Qing Jiang

  3. University of Chinese Academy of Sciences, Beijing, China

    Jin-ling Ma

  4. University of Science and Technology of China, Hefei, Anhui, China

    Yue Yu

  5. Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology of Ministry of Education School of Chemistry Beihang University Beijing, Beijing, China

    Da-peng Liu & Yu Zhang

  6. International Research Institute for Multidisciplinary Science Beihang University Beijing, Beijing, China

    Yu Zhang

  7. Beijing Advanced Innovation Center for Biomedical Engineering Beihang University Beijing, Beijing, China

    Yu Zhang

Authors
  1. Jin-ling Ma
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  2. Fan-lu Meng
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Contributions

X.B.Z., J.M.Y., Y.Z. and J.L.M. developed the research concept. J.M.Y. designed the Li-Na alloy and catalyst, and J.L.M. then prepared the materials. X.B.Z. designed the electrochemical experiments, which J.L.M and Y.Y. performed. X.B.Z., J.M.Y., Y.Z., J.L.M. and F.L.M. contributed to interpretation of the results and wrote the manuscript, and all authors contributed to the scientific discussion.

Corresponding authors

Correspondence to Jun-min Yan or Yu Zhang or Xin-bo Zhang.

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Supplementary Information

Supplementary Methods, Supplementary Figures 1–27, Supplementary Tables 1–4

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Ma, Jl., Meng, Fl., Yu, Y. et al. Prevention of dendrite growth and volume expansion to give high-performance aprotic bimetallic Li-Na alloy–O2 batteries. Nature Chem 11, 64–70 (2019). https://doi.org/10.1038/s41557-018-0166-9

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