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Near-frictionless ion transport within triazine framework membranes

Nature volume 617, pages 299–305 (2023)Cite this article

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Abstract

The enhancement of separation processes and electrochemical technologies such as water electrolysers1,2, fuel cells3,4, redox flow batteries5,6 and ion-capture electrodialysis7 depends on the development of low-resistance and high-selectivity ion-transport membranes. The transport of ions through these membranes depends on the overall energy barriers imposed by the collective interplay of pore architecture and pore–analyte interaction8,9. However, it remains challenging to design efficient, scaleable and low-cost selective ion-transport membranes that provide ion channels for low-energy-barrier transport. Here we pursue a strategy that allows the diffusion limit of ions in water to be approached for large-area, free-standing, synthetic membranes using covalently bonded polymer frameworks with rigidity-confined ion channels. The near-frictionless ion flow is synergistically fulfilled by robust micropore confinement and multi-interaction between ion and membrane, which afford, for instance, a Na+ diffusion coefficient of 1.18 × 10−9 m2 s–1, close to the value in pure water at infinite dilution, and an area-specific membrane resistance as low as 0.17 Ω cm2. We demonstrate highly efficient membranes in rapidly charging aqueous organic redox flow batteries that deliver both high energy efficiency and high-capacity utilization at extremely high current densities (up to 500 mA cm–2), and also that avoid crossover-induced capacity decay. This membrane design concept may be broadly applicable to membranes for a wide range of electrochemical devices and for precise molecular separation.

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Fig. 1: Schematic illustrations showing existing and proposed ion-selective polymer membranes with varying ion channels.
Fig. 2: Characterization of negatively charged CTF membranes (SCTF).
Fig. 3: Ion transport across the SCTF-BP membrane.
Fig. 4: SCTF-BP membrane enables rapid charging of aqueous alkaline quinone flow battery.

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Data availability

The data that support the findings of this study are available in the manuscript and its Supplementary Information, and also from the corresponding authors on reasonable request.

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Acknowledgements

This work was financially supported by the National Key Research and Development Project (nos. 2021YFB4000300 and 2020YFB1505600) and the National Natural Science Foundation of China (nos. 21922510, 21878281, U20A20127 and 52021002). T.L.L. and J.L. acknowledge financial support by the National Science Foundation (career award, grant no. 1847674). N.B.M. and C.Y. thank the Engineering and Physical Science Research Council for funding through programme grant SynHiSel (no. EP/V047078). P.Z. acknowledges financial support by the China Postdoctoral Science Foundation (no. 2021M693066) and Fundamental Research Funds for the Central Universities (no. WK2060000028). The authors thank H. Zhang for help with positron annihilation lifetime spectroscopy experiments. Z.Y. thanks the support of his wife, Q. Fang, and his sons, G.-C. Yang and G.-Q. Yang, during the difficult time of the COVID-19 pandemic.

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Author notes

  1. These authors contributed equally: Peipei Zuo, Chunchun Ye, Zhongren Jiao

Authors and Affiliations

  1. Key Laboratory of Precision and Intelligent Chemistry, Department of Applied Chemistry, School of Chemistry and Material Science, University of Science and Technology of China, Hefei, P. R. China

    Peipei Zuo, Zhongren Jiao, Junkai Fang, Zhengjin Yang & Tongwen Xu

  2. EastCHEM School of Chemistry, University of Edinburgh, Edinburgh, UK

    Chunchun Ye & Neil B. McKeown

  3. Utah State University, Chemistry and Biochemistry, Logan, UT, USA

    Jian Luo & T. Leo Liu

  4. Laboratory of Organic and Macromolecular Chemistry, Friedrich Schiller University Jena, Jena, Germany

    Ulrich S. Schubert

  5. Center for Energy and Environmental Chemistry Jena, Friedrich Schiller University Jena, Jena, Germany

    Ulrich S. Schubert

Authors
  1. Peipei Zuo
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  2. Chunchun Ye
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  4. Jian Luo
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  7. Neil B. McKeown
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  8. T. Leo Liu
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Contributions

Z.Y. and T.X. conceived and directed the project. T.L.L. provided suggestions and guidance during project implementation. P.Z., C.Y. and J.F. conducted experiments. Z.J. performed molecular simulations. P.Z., C.Y., Z.J., J.L., T.L.L., Z.Y. and T.X. analysed and discussed data. P.Z., C.Y., Z.J., Z.Y. and T.X. wrote the manuscript with input from T.L.L., J.L., J.F., U.S.S. and N.B.M. All authors offered constructive feedback on the manuscript.

Corresponding authors

Correspondence to T. Leo Liu, Zhengjin Yang or Tongwen Xu.

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Nature thanks Young Moo Lee and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

This file contains Supplementary Methods, Figs. 1–29, Tables 1–8 and References.

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Zuo, P., Ye, C., Jiao, Z. et al. Near-frictionless ion transport within triazine framework membranes. Nature 617, 299–305 (2023). https://doi.org/10.1038/s41586-023-05888-x

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