Diversity-oriented synthesis of polymer membranes with ion solvation cages

Baran, Miranda J.; Carrington, Mark E.; Sahu, Swagat; Baskin, Artem; Song, Junhua; Baird, Michael A.; Han, Kee Sung; Mueller, Karl T.; Teat, Simon J.; Meckler, Stephen M.; Fu, Chengyin; Prendergast, David; Helms, Brett A.

doi:10.1038/s41586-021-03377-7

Diversity-oriented synthesis of polymer membranes with ion solvation cages

Journal Article · Wed Apr 07 00:00:00 EDT 2021 · Nature (London)

DOI:https://doi.org/10.1038/s41586-021-03377-7· OSTI ID:1788026

Baran, Miranda J. ^[1]; Carrington, Mark E. ^[2]; Sahu, Swagat ^[3]; ^[3]; Song, Junhua ^[2]; Baird, Michael A. ^[4]; ^[5]; ^[5]; ^[6]; ^[4]; Fu, Chengyin ^[2]; ^[7]; ^[7]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Energy Storage Research (JCESR); Univ. of California, Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Energy Storage Research (JCESR)
Univ. of California, Berkeley, CA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Joint Center for Energy Storage Research (JCESR)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Energy Storage Research (JCESR); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry

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 batteries. It remains a significant challenge to identify FVEs with analyte specificity, due to difficulties in generating microporous polymer libraries with sufficient diversity for screening their properties. Here, we describe a diversity-oriented synthetic (DOS) strategy for microporous polymer membranes from which we identified those whose FVEs serve as solid solvation cages for lithium ions (Li⁺). Furthermore, key elements of our strategy included diversification of bis(catechol)-type monomers via multi-component Mannich reactions to introduce Li+-coordinating functionality within individual FVEs, topology-enforcing polymerizations for generating macromolecular skeletal diversity for networking FVEs into different pore architectures, and several classes of on-polymer reactions for diversifying pore geometries and dielectric properties. Lead candidate polymer membranes featuring explicit ion solvation cages exhibited both higher ionic conductivity and higher cation transference number than control membranes where FVEs were aspecific, which indicates conventional bounds for membrane permeability and selectivity for ion transport can be overcome.4 These advantages are tied to enhanced Li⁺ partitioning from the electrolyte when the cages are present, higher diffusion barriers for anions within the pores, and network-enforced restrictions on the number of solvent molecules bound to Li+ by comparison 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 for electric mobility.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Advanced Research Projects Agency - Energy (ARPA-E); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-76RL01830; AC02-05CH11231; SC0001015; AR0000774

OSTI ID:: 1788026

Report Number(s):: PNNL-SA--159809

Journal Information:: Nature (London), Journal Name: Nature (London) Journal Issue: 7853 Vol. 592; ISSN 0028-0836

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Diversity-oriented synthesis of polymer membranes with ion solvation cages

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