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Visualizing the growth process of sodium microstructures in sodium batteries by in-situ 23Na MRI and NMR spectroscopy

Nature Nanotechnology volume 15, pages 883–890 (2020)Cite this article

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Abstract

The growth of sodium dendrites and the associated solid electrolyte interface (SEI) layer is a critical and fundamental issue influencing the safety and cycling lifespan of sodium batteries. In this work, we use in-situ 23Na magnetic resonance imaging (MRI) and nuclear magnetic resonance (NMR) techniques, along with an innovative analytical approach, to provide space-resolved and quantitative insights into the formation and evolution of sodium metal microstructures (SMSs; that is, dendritic and mossy Na metal) during the deposition and stripping processes. Our results reveal that the growing SMSs give rise to a linear increase in the overpotential until a transition voltage of 0.15 V is reached, at which point violent electrochemical decomposition of the electrolyte is triggered, leading to the formation of mossy-type SMSs and rapid battery failure. In addition, we determined the existence of NaH in the SEI on sodium metal with ex-situ NMR results. The poor electronic conductivity of NaH is beneficial for the growth of a stable SEI on sodium metal.

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Fig. 1: Electrochemical performances and morphologies of Na metals cycled with different electrolytes.
Fig. 2: In-situ 23Na metal MRI images of the Na || Cu batteries during the first cycle in F0 and F2 electrolytes.
Fig. 3: In-situ 23Na metal MRI images of the Na || Cu batteries.
Fig. 4: The growth of SMSs observed by operando NMR.
Fig. 5: The correlation between the SMSs and overpotential.
Fig. 6: Ex-situ NMR characterization of SEI species.
Fig. 7: The correlation between overpotential and SMSs with two contrasting SEI features derived from F0 and F2 electrolytes, and the corresponding morphological evolution schematics.

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The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

This research is financially supported by National Key Research and Development Program of China (grant nos. 2018YFB0905400 and 2016YFB0901500) and National Natural Science Foundation of China (grant nos. 21935009, 21761132030 and 21603231). R.F. acknowledges support from the National High Magnetic Field Laboratory, which is supported by NSF Cooperative Agreement DMR-1644779 and the State of Florida. We acknowledge R. Liu and J. Dahn for helpful discussion.

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Authors and Affiliations

  1. State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China

    Yuxuan Xiang, Guorui Zheng, Ziteng Liang, Xiangsi Liu, Shijian Chen, Ke Zhou, Jianping Zhu, Min Lin, Huajin He, Jiajia Wan, Shenshui Yu & Yong Yang

  2. Department of Chemistry, University of Cambridge, Cambridge, UK

    Yanting Jin

  3. Xiamen Institute of Rare Earth Materials, and Fujian Institute of Research on the Structure of Matter, Haixi Institutes, Chinese Academy of Sciences, Xiamen, China

    Guiming Zhong

  4. National High Magnetic Field Laboratory, Tallahassee, FL, USA

    Riqiang Fu

  5. 4135 Belle Meade Circle, Belmont, NC, USA

    Yangxing Li

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  1. Yuxuan Xiang
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Contributions

Y.Y., Y.X. and G. Zhong proposed and planned the project. Y.Y. and G. Zhong supervised the project. Y.X., X.L., S.Y. and Z.L. carried out the NMR measurements. Y.X. and G. Zheng prepared the in-situ cells. S.C. and H.H. performed the SEM measurements and K.Z. and J.Z. performed and analysed XPS experiments. M.L. conducted the theoretical calculations. R.F. and J.W. assisted in data analysis. Y.X. and G. Zhong wrote the manuscript. Y.J. and Y.L. contributed to the discussion and revision of the manuscript.

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Correspondence to Guiming Zhong or Yong Yang.

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Supplementary Information

Supplementary Figs. 1–14, Tables 1 and 2, discussion and refs. 1–3.

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Xiang, Y., Zheng, G., Liang, Z. et al. Visualizing the growth process of sodium microstructures in sodium batteries by in-situ 23Na MRI and NMR spectroscopy. Nat. Nanotechnol. 15, 883–890 (2020). https://doi.org/10.1038/s41565-020-0749-7

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