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

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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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.

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

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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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