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Diversity-oriented synthesis of polymer membranes with ion solvation cages

Nature volume 592, pages 225–231 (2021)Cite this article

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Abstract

Microporous polymers feature shape-persistent free volume elements (FVEs), which are permeated by small molecules and ions when used as membranes for chemical separations, water purification, fuel cells and batteries1,2,3. Identifying FVEs that have analyte specificity remains a challenge, owing to difficulties in generating polymers with sufficient diversity to enable screening of their properties. Here we describe a diversity-oriented synthetic strategy for microporous polymer membranes to identify candidates featuring FVEs that serve as solvation cages for lithium ions (Li+). This strategy includes diversification of bis(catechol) monomers by Mannich reactions to introduce Li+-coordinating functionality within FVEs, topology-enforcing polymerizations for networking FVEs into different pore architectures, and several on-polymer reactions for diversifying pore geometries and dielectric properties. The most promising candidate membranes featuring ion solvation cages exhibited both higher ionic conductivity and higher cation transference number than control membranes, in which FVEs were aspecific, indicating that conventional bounds for membrane permeability and selectivity for ion transport can be overcome4. These advantages are associated with enhanced Li+ partitioning from the electrolyte when cages are present, higher diffusion barriers for anions within pores, and network-enforced restrictions on Li+ coordination number compared to the bulk electrolyte, which reduces the effective mass of the working ion. Such membranes show promise as anode-stabilizing interlayers in high-voltage lithium metal batteries.

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Fig. 1: DOS of PIMs with ion solvation cages.
Fig. 2: Structure–transport relationships within the DOS PIM library.
Fig. 3: Molecular structure of Li+ solvation cages in PIMs and free-energy analysis of cage-to-cage Li+ transport.
Fig. 4: Electrochemical and structural characterization of Li metal cells.

Data availability

The data supporting the findings of this study are available within the paper and its Supplementary Information and Supplementary Data, and also from the authors upon reasonable request. Crystallographic data for compounds 3–7, 9 and 10 are available free of charge from the Cambridge Crystallographic Data Centre (www.ccdc.cam.ac.uk) under reference numbers 2061993–2061197, 2061199 and 2061198, respectively. Source data are provided with this paper.

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Acknowledgements

This work was supported by the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences. Portions of this work, including polymer synthesis and characterization, were carried out as a user project at the Molecular Foundry, which is supported by the Office of Science, Office of Basic Energy Sciences of the US DOE under contract number DE-AC02-05CH11231. S.M.M. and M.E.C. acknowledge support from the Center for Gas Separations Relevant to Clean Energy Technologies, an Energy Frontier Research Center funded by the US DOE, Office of Science, Basic Energy Sciences under award number DE-SC0001015 to carry out principal component analysis, gas sorption and GIWAXS measurements. GIWAXS and single-crystal measurements were carried out at the Advanced Light Source, which is a DOE Office of Science User Facility under contract number DE-AC02-05CH11231. Computation was carried out at the National Energy Research Scientific Computing Center (NERSC), a US DOE Office of Science User Facility operated under the same contract. PFG-NMR measurements were performed at the Environmental Molecular Sciences Laboratory (EMSL), a national user facility sponsored by the DOE’s Office of Biological and Environmental Research and located in the Pacific Northwest National Laboratory. J.S. and C.F. acknowledge support from the Advanced Research Projects Agency-Energy Integration and Optimization of Novel Ion Conducting Solids (IONICS) programme under grant number DE-AR0000774 to carry out Li–NMC622 cell cycling. The cathodes were produced by B. Polzin, S. Trask and A. Jansen at the US DOE CAMP (Cell Analysis, Modeling and Prototyping) Facility, Argonne National Laboratory. The CAMP Facility is fully supported by the DOE Vehicle Technologies Office.

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Authors and Affiliations

  1. Joint Center for Energy Storage Research, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Miranda J. Baran, Swagat Sahu, Artem Baskin, David Prendergast & Brett A. Helms

  2. Department of Chemistry, University of California, Berkeley, CA, USA

    Miranda J. Baran, Michael A. Baird & Stephen M. Meckler

  3. The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Mark E. Carrington, Junhua Song, Chengyin Fu, David Prendergast & Brett A. Helms

  4. Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, WA, USA

    Kee Sung Han & Karl T. Mueller

  5. Joint Center for Energy Storage Research, Pacific Northwest National Laboratory, Richland, WA, USA

    Kee Sung Han & Karl T. Mueller

  6. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Simon J. Teat

  7. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Brett A. Helms

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Contributions

B.A.H. designed and directed the study. M.J.B., M.E.C., S.S., M.A.B. and S.M.M. synthesized and characterized the monomers and polymers. S.J.T. conducted single-crystal X-ray crystallography and analysed the results. M.E.C. carried out the principal component analysis. M.J.B., M.A.B. and C.F. carried out ion transport experiments. K.S.H. and K.T.M. conducted PFG-NMR experiments. J.S. conducted full-cell cycling experiments. D.P. designed and directed the theoretical study. A.B. conducted the simulations. B.A.H. wrote the paper with contributions from all co-authors.

Corresponding author

Correspondence to Brett A. Helms.

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Competing interests

B.A.H., M.J.B., M.E.C., S.S. and S.M.M. are named as inventors in US provisional patent application 62/719,498 submitted by Lawrence Berkeley National Laboratory, which covers the DOS PIM library, as well as aspects of its use.

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Peer review information Nature thanks Elie Paillard and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

This file contains Supplementary Methods, Supplementary Tables 1–10, and Supplementary Figures 1–62.

Supplementary Data

This zipped file contains 7 .cif files with the crystal structures for compounds 3, 4, 5, 6, 7, 9 and 10.

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Baran, M.J., Carrington, M.E., Sahu, S. et al. Diversity-oriented synthesis of polymer membranes with ion solvation cages. Nature 592, 225–231 (2021). https://doi.org/10.1038/s41586-021-03377-7

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