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.
This is a preview of subscription content, access via your institution
Open Access articles citing this article.
Suppressing electrolyte-lithium metal reactivity via Li+-desolvation in uniform nano-porous separator
Nature Communications Open Access 10 January 2022
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 per month
cancel any time
Subscribe to this journal
Receive 51 print issues and online access
$199.00 per year
only $3.90 per issue
Rent or buy this article
Get just this article for as long as you need it
Prices may be subject to local taxes which are calculated during checkout
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.
Slater, A. G. & Cooper, A. I. Function-led design of new porous materials. Science 348, aaa8075 (2015).
Koros, W. J. & Zhang, C. Materials for next-generation molecularly selective synthetic membranes. Nat. Mater. 16, 289–297 (2017).
Li, C. et al. Engineered transport in microporous materials and membranes for clean energy technologies. Adv. Mater. 30, 1704953 (2018).
Park, H. B., Kamcev, J., Robeson, L. M., Elimelech, M. & Freeman, B. D. Maximizing the right stuff: the trade-off between membrane permeability and selectivity. Science 356, eaab0530 (2017).
Schreiber, S. L. Target-oriented and diversity-oriented organic synthesis in drug discovery. Science 287, 1964–1969 (2000).
Burke, M. D., Berger, E. M. & Schreiber, S. L. Generating diverse skeletons of small molecules combinatorially. Science 302, 613–618 (2003).
Burke, M. D. & Schreiber, S. L. A planning strategy for diversity-oriented synthesis. Angew. Chem. Int. Ed. 43, 46–58 (2004).
Tan, D. S. Diversity-oriented synthesis: exploring the intersections between chemistry and biology. Nat. Chem. Biol. 1, 74–84 (2005).
Schreiber, S. L. Molecular diversity by design. Nature 457, 153–154 (2009).
Nielsen, T. E. & Schreiber, S. L. Towards the optimal screening collection: a synthesis strategy. Angew. Chem. Int. Ed. 47, 48–56 (2008).
Galloway, W. R. J. D. et al. Diversity-oriented synthesis as a tool for the discovery of novel biologically active small molecules. Nat. Commun. 1, 80 (2010).
Haggarty, S. J. The principle of complementarity: chemical versus biological space. Curr. Opin. Chem. Biol. 9, 296–303 (2005).
Furukawa, H., Cordova, K. E., O’Keeffe, M. & Yaghi, O. M. The chemistry and applications of metal–organic frameworks. Science 341, 1230444 (2013).
Tranchemontagne, D. J., Ni, Z., O’Keeffe, M. & Yaghi, O. M. Reticular chemistry of metal–organic polyhedra. Angew. Chem. Int. Ed. 47, 5136–5147 (2008).
Holst, J. R., Trewin, A. & Cooper, A. I. Porous organic molecules. Nat. Chem. 2, 915–920 (2010).
Diercks, C. S. & Yaghi, O. M. The atom, the molecule, and the covalent organic framework. Science 355, eaal1585 (2017).
Bisbey, R. P. & Dichtel, W. R. Covalent organic frameworks as a platform for multidimensional polymerization. ACS Cent. Sci. 3, 533–543 (2017).
Cooper, A. I. Porous molecular solids and liquids. ACS Cent. Sci. 3, 544–553 (2017).
Mannich, C. & Krösche, W. Ueber ein Kondensationsprodukt aus Formaldehyd, Ammoniak und Antipyrin. Arch. Pharm. 250, 647–667 (1912).
Arend, M., Westermann, B. & Risch, N. Modern variants of the Mannich reaction. Angew. Chem. Int. Ed. 37, 1044–1070 (1998).
McKeown, N. B. & Budd, P. M. Polymers of intrinsic microporosity (PIMs): organic materials for membrane separations, heterogeneous catalysis and hydrogen storage. Chem. Soc. Rev. 35, 675–683 (2006).
Patel, H. A. & Yavuz, C. T. Noninvasive functionalization of polymers of intrinsic microporosity for enhanced CO2 capture. Chem. Commun. 48, 9989–9991 (2012).
Baran, M. J. et al. Design rules for membranes from polymers of intrinsic microporosity for crossover-free aqueous electrochemical devices. Joule 3, 2968–2985 (2019).
Tan, R. et al. Hydrophilic microporous membranes for selective ion separation and flow-battery energy storage. Nat. Mater. 19, 195–202 (2020); author correction 19, 251 (2020).
Eloy, F. & Lenaers, R. The chemistry of amidoximes and related compounds. Chem. Rev. 62, 155–183 (1962).
Bartoli, G. et al. Unusual and unexpected reactivity of t-butyl dicarbonate (Boc2O) with alcohols in the presence of magnesium perchlorate. A new and general route to t-butyl ethers. Org. Lett. 7, 427–430 (2005).
Bruce, P. G. & Vincent, C. A. Steady state current flow in solid binary electrolyte cells. J. Electroanal. Chem. Interf. Electrochem. 225, 1–17 (1987).
Evans, J., Vincent, C. A. & Bruce, P. G. Electrochemical measurement of transference numbers in polymer electrolytes. Polymer 28, 2324–2328 (1987).
Choo, Y., Halat, D. M., Villaluenga, I., Timachova, K. & Balsara, N. P. Diffusion and migration in polymer electrolytes. Prog. Polym. Sci. 103, 101220 (2020).
Laio, A. & Gervasio, F. L. Metadynamics: a method to stimulate rare events and reconstruct the free energy in biophysics. Rep. Prog. Phys. 71, 126601 (2008).
Barducci, A., Bonomi, M. & Parrinello, M. Metadynamics. WIREs Comput. Mol. Sci. 1, 826–843 (2011).
Li, C. et al. A polysulfide-blocking microporous polymer membrane tailored for hybrid Li–sulfur flow batteries. Nano Lett. 15, 5724–5729 (2015).
Ward, A. L. et al. Materials genomics screens for adaptive ion transport behavior by redox-switchable microporous polymer membranes in lithium–sulfur batteries. ACS Cent. Sci. 3, 399–406 (2017).
Ma, L. et al. Nanoporous polymer films with high cation transference number stabilize lithium metal anodes in light-weight batteries for electrified transportation. Nano Lett. 19, 1387–1394 (2019).
Fu, C. et al. Universal chemomechanical design rules for solid-ion conductors to prevent dendrite formation in lithium metal batteries. Nat. Mater. 19, 758–766 (2020).
Shi, F. et al. Lithium metal stripping beneath the solid electrolyte interphase. Proc. Natl Acad. Sci. USA 115, 8529–8534 (2018).
Albertus, P. et al. Status and challenges in enabling the lithium metal electrode for high-energy and low-cost rechargeable batteries. Nat. Energy 3, 16–21 (2018).
Fredericks, W. L., Sripad, S., Bower, G. C. & Viswanathan, V. Performance metrics required of next-generation batteries to electrify Vertical Takeoff And Landing (VTOL) aircraft. ACS Energy Lett. 3, 2989–2994 (2018).
Liu, J. et al. Pathways for practical high-energy long-cycling lithium metal batteries. Nat. Energy 4, 180–186 (2019).
Viswanathan, V. & Knapp, B. M. Potential for electric aircraft. Nat. Sustain. 2, 88–89 (2019).
Sripad, S. & Viswanathan, V. Quantifying the economic case for electric semi-trucks. ACS Energy Lett. 4, 149–155 (2019).
Bachman, J. E., Smith, Z. P., Li, T., Xu, T. & Long, J. R. Enhanced ethylene separation and plasticization resistance in polymer membranes incorporating metal–organic framework nanocrystals. Nat. Mater. 15, 845–849 (2016).
Wei, X. et al. TEMPO-based catholyte for high-energy density nonaqueous redox flow batteries. Adv. Mater. 26, 7649–7653 (2014).
Yang, Z. et al. Highly conductive anion-exchange membranes from microporous Tröger’s base polymers. Angew. Chem. Int. Ed. 55, 11499 (2016).
Doris, S. E. et al. Macromolecular design strategies for preventing active-material crossover in non-aqueous all-organic redox-flow batteries. Angew. Chem. Int. Ed. 56, 1595–1599 (2017).
Yushkin, A., Vasilensky, V., Khotimskiy, V., Szymczyk, A. & Volkov, A. Evaluation of liquid transport properties of hydrophobic polymers of intrinsic microporosity by electrical resistance measurement. J. Membr. Sci. 554, 346 (2018).
Jain, A. et al. The Materials Project: a materials genome approach to accelerating materials innovation. APL Mater. 1, 011002 (2013).
Gromski, P. S., Henson, A., Granda, J. & Cronin, L. How to explore chemical space using algorithms and automation. Nat. Rev. Chem. 3, 119–128 (2019).
Häse, F., Roch, L. M. & Aspuru-Guzik, A. Next-generation experimentation with self-driving laboratories. Trends Chem. 1, 282–291 (2019).
Burger, B. et al. A mobile robotic chemist. Nature 583, 237–241 (2020).
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.
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.
Peer review information Nature thanks Elie Paillard and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
This file contains Supplementary Methods, Supplementary Tables 1–10, and Supplementary Figures 1–62.
This zipped file contains 7 .cif files with the crystal structures for compounds 3, 4, 5, 6, 7, 9 and 10.
Rights and permissions
About this article
Cite this article
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
This article is cited by
Formation of hierarchically ordered structures in conductive polymers to enhance the performances of lithium-ion batteries
Nature Energy (2023)
Suppressing electrolyte-lithium metal reactivity via Li+-desolvation in uniform nano-porous separator
Nature Communications (2022)
Diversity provides the solution
Nature Reviews Chemistry (2021)
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.