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High-performance spiro-branched polymeric membranes for sustainability applications

Nature Sustainability volume 7, pages 910–919 (2024)Cite this article

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Abstract

Ion exchange membranes are semi-permeable thin films allowing for selective transport of either anions or cations and have wide applications in desalination, wastewater treatment and energy conversion and storage. Poly(aryl piperidinium) polymers are promising materials for a new generation of anion exchange membranes with high chemical stability, although their ionic conductivity remains to be further improved. Here we report a design of branched microporous poly(aryl piperidinium) membranes that combine ultra-high Cl− conductivity (120 mS cm−1 at 80 °C), excellent mechanical and chemical stability and solution processability. At the heart of our rational design is the use of stereo-contorted spirobifluorene monomers to control the topology and orientations of branched chains, achieving balanced rigidity and flexibility. The loose chain packing structure reduces the energy barrier for ion dissociation and diffusion within the polymer networks, which can be processed into large-area membranes aided by a colloidal method. When applied to redox flow batteries, our microporous membranes deliver record-breaking performance at a high current density of 400 mA cm−2. Our work suggests a feasible strategy for the development of high-performance membranes that will find more applications critical to sustainability.

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Fig. 1: Comparison of varied ion channels and design strategy of proposed spiral branched membranes.
Fig. 2: Characterizations and simulations of spiral branched membranes.
Fig. 3: Ion conduction and ion transport mechanism.
Fig. 4: Performances of neutral AORFBs assembled with AMV, QPBPip and QPSPBPip membranes.
Fig. 5: Performances of VRFBs assembled with Nafion 212, QPBPip and QPSPBPip membranes.

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Data availability

All data that support the findings in the current study are available within the Article and its Supplementary Information. The relevant raw data for each figure are provided as source or supplementary data files. Source data are provided with this paper.

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Acknowledgements

This research was supported by the National Key R&D Program of China (number 2021YFB4000300 (Z.Y.)), the National Natural Science Foundation of China (number U20A20127 (T.X.), 22322811 (X.G.), 22278388 (X.G.), 12275270 (Hongjun Zhang)), the Strategic Priority Research Program of the Chinese Academy of Sciences (number XDB0450401 (T.X.)) and the Anhui Province major industrial innovation plan (AHZDCYCX-LSDT2023-08 (T.X.)).

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Authors and Affiliations

  1. Key Laboratory of Precision and Intelligent Chemistry, Collaborative Innovation Centre of Chemistry for Energy Materials, School of Chemistry and Material Science, University of Science and Technology of China, Hefei, People’s Republic of China

    Huaqing Zhang, Wanjie Song, Kang Peng, Lixuan Sun, Cui Yang, Xin Zhang, Xian Liang, Zhengjin Yang, Liang Wu, Xiaolin Ge & Tongwen Xu

  2. State Key Laboratory of Particle Detection and Electronics, University of Science and Technology of China, Hefei, People’s Republic of China

    Wei Xu, Hongjun Zhang & Bangjiao Ye

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  1. Huaqing Zhang
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Contributions

Huaqing Zhang designed the experiments, fabricated the membranes, performed the membrane characterizations, conduced corresponding tests and wrote the manuscript. W.X., Hongjun Zhang and B.Y. measured the PALS of the membranes. K.P. helped with neutral AORFB testing. X.G. and T.X, supervised and guided the work and revised the manuscript. Z.Y., L.W. and X.L. helped to revise the manuscript. W.S., L.S., C.Y. and X.Z. contributed to the data analysis.

Corresponding authors

Correspondence to Xiaolin Ge or Tongwen Xu.

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Nature Sustainability thanks Antoni Forner-Cuenca, Rémy R. Jacquemond, Qilei Song and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Zhang, H., Xu, W., Song, W. et al. High-performance spiro-branched polymeric membranes for sustainability applications. Nat Sustain 7, 910–919 (2024). https://doi.org/10.1038/s41893-024-01364-0

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