Direct Insertion Polymerization of Ionic Monomers: Rapid Production of Anion Exchange Membranes

Hsu, Jesse H.; Peltier, Cheyenne R.; Treichel, Megan; Gaitor, Jamie C.; Li, Qihao; Girbau, Renee; Macbeth, Alexandra J.; Abruña, Héctor D.; Noonan, Kevin J. T.; Coates, Geoffrey W.; Fors, Brett P.

doi:10.1002/ange.202304778

Title: Direct Insertion Polymerization of Ionic Monomers: Rapid Production of Anion Exchange Membranes

Journal Article · 14 June 2023 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202304778 · OSTI ID:1984912

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Department of Chemistry and Chemical Biology Cornell University Ithaca NY 14853 USA
Department of Chemistry Carnegie Mellon University Pittsburgh PA 15213 USA

Abstract The limited number of methods to directly polymerize ionic monomers currently hinders rapid diversification and production of ionic polymeric materials, namely anion exchange membranes (AEMs) which are essential components in emerging alkaline fuel cell and electrolyzer technologies. Herein, we report a direct coordination‐insertion polymerization of cationic monomers, providing the first direct synthesis of aliphatic polymers with high ion incorporations and allowing facile access to a broad range of materials. We demonstrate the utility of this method by rapidly generating a library of solution processable ionic polymers for use as AEMs. We investigate these materials to study the influence of cation identity on hydroxide conductivity and stability. We found that AEMs with piperidinium cations exhibited the highest performance, with high alkaline stability, hydroxide conductivity of 87 mS cm ⁻¹ at 80 °C, and a peak power density of 730 mW cm ⁻² when integrated into a fuel cell device.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0019445

OSTI ID:: 1984912

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 30 Vol. 135; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (61)

Achieving High‐Performance and 2000 h Stability in Anion Exchange Membrane Fuel Cells by Manipulating Ionomer Properties and Electrode Optimization Ul Hassan, Noor; Mandal, Mrinmay; Huang, Garrett Advanced Energy Materials, Vol. 10, Issue 40 https://doi.org/10.1002/aenm.202001986	journal	September 2020
Cationic Metallo-Polyelectrolytes for Robust Alkaline Anion-Exchange Membranes Zhu, Tianyu; Xu, Shichao; Rahman, Anisur Angewandte Chemie International Edition, Vol. 57, Issue 9 https://doi.org/10.1002/anie.201712387	journal	January 2018
Alkaline Stability of Quaternary Ammonium Cations for Alkaline Fuel Cell Membranes and Ionic Liquids Marino, M. G.; Kreuer, K. D. ChemSusChem, Vol. 8, Issue 3 https://doi.org/10.1002/cssc.201403022	journal	November 2014
Prospects for Alkaline Anion-Exchange Membranes in Low Temperature Fuel Cells Varcoe, J.; Slade, R. Fuel Cells, Vol. 5, Issue 2, p. 187-200 https://doi.org/10.1002/fuce.200400045	journal	October 2004
Endo/Exo Reactivity Ratios in Living Vinyl Addition Polymerization of Substituted Norbornenes Tsai, Steven D.; Register, Richard A. Macromolecular Chemistry and Physics, Vol. 219, Issue 11 https://doi.org/10.1002/macp.201800059	journal	April 2018
Direct Synthesis of Imidazolium-Functional Polyethylene by Insertion Copolymerization Jian, Zhongbao; Leicht, Hannes; Mecking, Stefan Macromolecular Rapid Communications, Vol. 37, Issue 11 https://doi.org/10.1002/marc.201600073	journal	April 2016
A green hydrogen economy for a renewable energy society Oliveira, Alexandra M.; Beswick, Rebecca R.; Yan, Yushan Current Opinion in Chemical Engineering, Vol. 33 https://doi.org/10.1016/j.coche.2021.100701	journal	September 2021
Developmental toxicity of Nafion byproduct 2 (NBP2) in the Sprague-Dawley rat with comparisons to hexafluoropropylene oxide-dimer acid (HFPO-DA or GenX) and perfluorooctane sulfonate (PFOS) Conley, Justin M.; Lambright, Christy S.; Evans, Nicola Environment International, Vol. 160 https://doi.org/10.1016/j.envint.2021.107056	journal	February 2022
Novel quaternary ammonium microblock poly (p-phenylene-co-aryl ether ketone)s as anion exchange membranes for alkaline fuel cells Dong, Xue; Xue, Boxin; Qian, Huidong Journal of Power Sources, Vol. 342 https://doi.org/10.1016/j.jpowsour.2016.12.114	journal	February 2017
Review of cell performance in anion exchange membrane fuel cells Dekel, Dario R. Journal of Power Sources, Vol. 375 https://doi.org/10.1016/j.jpowsour.2017.07.117	journal	January 2018
Anion exchange membrane fuel cells: Current status and remaining challenges Gottesfeld, Shimshon; Dekel, Dario R.; Page, Miles Journal of Power Sources, Vol. 375 https://doi.org/10.1016/j.jpowsour.2017.08.010	journal	January 2018
Alkaline polymer electrolyte fuel cells stably working at 80 °C Peng, Hanqing; Li, Qihao; Hu, Meixue Journal of Power Sources, Vol. 390 https://doi.org/10.1016/j.jpowsour.2018.04.047	journal	June 2018
On the origin of permanent performance loss of anion exchange membrane fuel cells: Electrochemical oxidation of phenyl group Maurya, Sandip; Lee, Albert S.; Li, Dongguo Journal of Power Sources, Vol. 436 https://doi.org/10.1016/j.jpowsour.2019.226866	journal	October 2019
Anion exchange membranes for alkaline fuel cells: A review Merle, Géraldine; Wessling, Matthias; Nijmeijer, Kitty Journal of Membrane Science, Vol. 377, Issue 1-2, p. 1-35 https://doi.org/10.1016/j.memsci.2011.04.043	journal	July 2011
Anionic multiblock copolymer membrane based on vinyl addition polymerization of norbornenes: Applications in anion-exchange membrane fuel cells Mandal, Mrinmay; Huang, Garrett; Kohl, Paul A. Journal of Membrane Science, Vol. 570-571 https://doi.org/10.1016/j.memsci.2018.10.041	journal	January 2019
Alkaline-stable anion exchange membranes: A review of synthetic approaches You, Wei; Noonan, Kevin J. T.; Coates, Geoffrey W. Progress in Polymer Science, Vol. 100 https://doi.org/10.1016/j.progpolymsci.2019.101177	journal	January 2020
Anion exchange polyelectrolytes for membranes and ionomers Chen, Nanjun; Lee, Young Moo Progress in Polymer Science, Vol. 113 https://doi.org/10.1016/j.progpolymsci.2020.101345	journal	February 2021
Toxicity of Balb-c mice exposed to recently identified 1,1,2,2-tetrafluoro-2-[1,1,1,2,3,3-hexafluoro-3-(1,1,2,2-tetrafluoroethoxy)propan-2-yl]oxyethane-1-sulfonic acid (PFESA-BP2) Lang, Johnsie R.; Strynar, Mark J.; Lindstrom, Andrew B. Toxicology, Vol. 441 https://doi.org/10.1016/j.tox.2020.152529	journal	August 2020
Adsorption of Polyaromatic Backbone Impacts the Performance of Anion Exchange Membrane Fuel Cells Matanovic, Ivana; Maurya, Sandip; Park, Eun Joo Chemistry of Materials, Vol. 31, Issue 11 https://doi.org/10.1021/acs.chemmater.9b01092	journal	May 2019
Electrocatalysis in Alkaline Media and Alkaline Membrane-Based Energy Technologies Yang, Yao; Peltier, Cheyenne R.; Zeng, Rui Chemical Reviews, Vol. 122, Issue 6 https://doi.org/10.1021/acs.chemrev.1c00331	journal	February 2022
Anion-Exchange Membrane Water Electrolyzers Du, Naiying; Roy, Claudie; Peach, Retha Chemical Reviews, Vol. 122, Issue 13 https://doi.org/10.1021/acs.chemrev.1c00854	journal	April 2022
Degradation of Organic Cations under Alkaline Conditions You, Wei; Hugar, Kristina M.; Selhorst, Ryan C. The Journal of Organic Chemistry, Vol. 86, Issue 1 https://doi.org/10.1021/acs.joc.0c02051	journal	November 2020
Exploring the Effects of Bulky Cations Tethered to Semicrystalline Polymers: The Case of Tetraaminophosphoniums with Ring-Opened Polynorbornenes Treichel, Megan; Tyler Womble, C.; Selhorst, Ryan Macromolecules, Vol. 53, Issue 19 https://doi.org/10.1021/acs.macromol.0c00422	journal	September 2020
Systematic Alkaline Stability Study of Polymer Backbones for Anion Exchange Membrane Applications Mohanty, Angela D.; Tignor, Steven E.; Krause, Jessica A. Macromolecules, Vol. 49, Issue 9 https://doi.org/10.1021/acs.macromol.5b02550	journal	April 2016
Synthesis of Alkaline Anion Exchange Membranes with Chemically Stable Imidazolium Cations: Unexpected Cross-Linked Macrocycles from Ring-Fused ROMP Monomers You, Wei; Hugar, Kristina M.; Coates, Geoffrey W. Macromolecules, Vol. 51, Issue 8 https://doi.org/10.1021/acs.macromol.8b00209	journal	April 2018
Multiblock Copolymer Anion-Exchange Membranes Derived from Vinyl Addition Polynorbornenes Selhorst, Ryan; Gaitor, Jamie; Lee, Minjung ACS Applied Energy Materials, Vol. 4, Issue 9 https://doi.org/10.1021/acsaem.1c02094	journal	September 2021
Anion Exchange Membranes’ Evolution toward High Hydroxide Ion Conductivity and Alkaline Resiliency Arges, Christopher G.; Zhang, Le ACS Applied Energy Materials, Vol. 1, Issue 7 https://doi.org/10.1021/acsaem.8b00387	journal	June 2018
Highly Conductive Anion-Exchange Membranes Based on Cross-Linked Poly(norbornene): Vinyl Addition Polymerization Mandal, Mrinmay; Huang, Garrett; Kohl, Paul A. ACS Applied Energy Materials, Vol. 2, Issue 4 https://doi.org/10.1021/acsaem.8b02051	journal	March 2019
Highly Conducting Anion-Exchange Membranes Based on Cross-Linked Poly(norbornene): Ring Opening Metathesis Polymerization Chen, Wanting; Mandal, Mrinmay; Huang, Garrett ACS Applied Energy Materials, Vol. 2, Issue 4 https://doi.org/10.1021/acsaem.8b02052	journal	February 2019
Phenyl Oxidation Impacts the Durability of Alkaline Membrane Water Electrolyzer Li, Dongguo; Matanovic, Ivana; Lee, Albert S. ACS Applied Materials & Interfaces, Vol. 11, Issue 10 https://doi.org/10.1021/acsami.9b00711	journal	February 2019
Suppressing Crossover in Nonaqueous Redox Flow Batteries with Polyethylene-Based Anion-Exchange Membranes Peltier, Cheyenne R.; Rhodes, Zayn; Macbeth, Alexandra J. ACS Energy Letters, Vol. 7, Issue 11 https://doi.org/10.1021/acsenergylett.2c01551	journal	October 2022
Quaternary Ammonium-Functionalized Polyethylene-Based Anion Exchange Membranes: Balancing Performance and Stability Peltier, Cheyenne R.; You, Wei; Fackovic Volcanjk, Dea ACS Energy Letters, Vol. 8, Issue 5 https://doi.org/10.1021/acsenergylett.3c00319	journal	April 2023
Protocol for the Quantitative Assessment of Organic Cation Stability for Polymer Electrolytes Hugar, Kristina M.; You, Wei; Coates, Geoffrey W. ACS Energy Letters, Vol. 4, Issue 7 https://doi.org/10.1021/acsenergylett.9b00908	journal	June 2019
Living Vinyl Addition Polymerization of Substituted Norbornenes by a t -Bu ₃ P-Ligated Methylpalladium Complex Kim, Dong-Gyun; Bell, Andrew; Register, Richard A. ACS Macro Letters, Vol. 4, Issue 3 https://doi.org/10.1021/acsmacrolett.5b00079	journal	February 2015
Tetrakis(dialkylamino)phosphonium Polyelectrolytes Prepared by Reversible Addition–Fragmentation Chain Transfer Polymerization Womble, C. Tyler; Coates, Geoffrey W.; Matyjaszewski, Krzysztof ACS Macro Letters, Vol. 5, Issue 2 https://doi.org/10.1021/acsmacrolett.5b00910	journal	January 2016
The search for larger and more weakly coordinating anions Strauss, Steven H. Chemical Reviews, Vol. 93, Issue 3 https://doi.org/10.1021/cr00019a005	journal	May 1993
Phosphonium-Functionalized Polyethylene: A New Class of Base-Stable Alkaline Anion Exchange Membranes Noonan, Kevin J. T.; Hugar, Kristina M.; Kostalik, Henry A. Journal of the American Chemical Society, Vol. 134, Issue 44 https://doi.org/10.1021/ja307466s	journal	October 2012
A Ring-Opening Metathesis Polymerization Route to Alkaline Anion Exchange Membranes: Development of Hydroxide-Conducting Thin Films from an Ammonium-Functionalized Monomer Clark, Timothy J.; Robertson, Nicholas J.; Kostalik IV, Henry A. Journal of the American Chemical Society, Vol. 131, Issue 36 https://doi.org/10.1021/ja905242r	journal	September 2009
Tunable High Performance Cross-Linked Alkaline Anion Exchange Membranes for Fuel Cell Applications Robertson, Nicholas J.; Kostalik, Henry A.; Clark, Timothy J. Journal of the American Chemical Society, Vol. 132, Issue 10 https://doi.org/10.1021/ja908638d	journal	March 2010
Imidazolium Cations with Exceptional Alkaline Stability: A Systematic Study of Structure–Stability Relationships Hugar, Kristina M.; Kostalik, Henry A.; Coates, Geoffrey W. Journal of the American Chemical Society, Vol. 137, Issue 27 https://doi.org/10.1021/jacs.5b02879	journal	July 2015
Rational Synthesis of Metallo-Cations Toward Redox- and Alkaline-Stable Metallo-Polyelectrolytes Zhu, Tianyu; Sha, Ye; Firouzjaie, Horie Adabi Journal of the American Chemical Society, Vol. 142, Issue 2 https://doi.org/10.1021/jacs.9b12051	journal	December 2019
Solvent Processable Tetraalkylammonium-Functionalized Polyethylene for Use as an Alkaline Anion Exchange Membrane Kostalik, Henry A.; Clark, Timothy J.; Robertson, Nicholas J. Macromolecules, Vol. 43, Issue 17 https://doi.org/10.1021/ma101172a	journal	September 2010
(η³-Allyl)palladium(II) and Palladium(II) Nitrile Catalysts for the Addition Polymerization of Norbornene Derivatives with Functional Groups Mathew, Joice P.; Reinmuth, Annette; Melia, Jennifer Macromolecules, Vol. 29, Issue 8 https://doi.org/10.1021/ma9515285	journal	January 1996
Addition Polymerization of Functionalized Norbornenes: The Effect of Size, Stereochemistry, and Coordinating Ability of the Substituent Funk, Jeffrey K.; Andes, Cecily E.; Sen, Ayusman Organometallics, Vol. 23, Issue 8 https://doi.org/10.1021/om049943l	journal	March 2004
Syntheses and Structures of Bulky Monophosphine-Ligated Methylpalladium Complexes: Application to Homo- and Copolymerization of Norbornene and/or Methoxycarbonylnorbornene Yamashita, Makoto; Takamiya, Ikuko; Jin, Koichiro Organometallics, Vol. 25, Issue 19 https://doi.org/10.1021/om060347w	journal	September 2006
Poly(aryl piperidinium) membranes and ionomers for hydroxide exchange membrane fuel cells Wang, Junhua; Zhao, Yun; Setzler, Brian P. Nature Energy, Vol. 4, Issue 5 https://doi.org/10.1038/s41560-019-0372-8	journal	April 2019
Anion-exchange membranes in electrochemical energy systems Varcoe, John R.; Atanassov, Plamen; Dekel, Dario R. Energy & Environmental Science, Vol. 7, Issue 10, p. 3135-3191 https://doi.org/10.1039/C4EE01303D	journal	January 2014
A review on recent developments of anion exchange membranes for fuel cells and redox flow batteries Maurya, Sandip; Shin, Sung-Hee; Kim, Yekyung RSC Advances, Vol. 5, Issue 47 https://doi.org/10.1039/C5RA04741B	journal	January 2015
A comparative study of anion-exchange membranes tethered with different hetero-cycloaliphatic quaternary ammonium hydroxides Dang, Hai-Son; Jannasch, Patric J. Mater. Chem. A, Vol. 5, Issue 41 https://doi.org/10.1039/C7TA06029G	journal	January 2017
A high conductivity ultrathin anion-exchange membrane with 500+ h alkali stability for use in alkaline membrane fuel cells that can achieve 2 W cm ⁻² at 80 °C Wang, Lianqin; Bellini, Marco; Miller, Hamish A. Journal of Materials Chemistry A, Vol. 6, Issue 31 https://doi.org/10.1039/C8TA04783A	journal	January 2018
Durability of anion exchange membrane water electrolyzers Li, Dongguo; Motz, Andrew R.; Bae, Chulsung Energy & Environmental Science, Vol. 14, Issue 6 https://doi.org/10.1039/D0EE04086J	journal	January 2021
A comprehensive review of the structures and properties of ionic polymeric materials Potaufeux, Jean-Emile; Odent, Jérémy; Notta-Cuvier, Delphine Polymer Chemistry, Vol. 11, Issue 37 https://doi.org/10.1039/D0PY00770F	journal	January 2020
Expeditious synthesis of aromatic-free piperidinium-functionalized polyethylene as alkaline anion exchange membranes You, Wei; Ganley, Jacob M.; Ernst, Brian G. Chemical Science, Vol. 12, Issue 11 https://doi.org/10.1039/D0SC05789D	journal	January 2021
Poly(norbornene) anion conductive membranes: homopolymer, block copolymer and random copolymer properties and performance Mandal, Mrinmay; Huang, Garrett; Hassan, Noor Ul Journal of Materials Chemistry A, Vol. 8, Issue 34 https://doi.org/10.1039/D0TA04756B	journal	January 2020
Cationic polymers and their therapeutic potential Samal, Sangram Keshari; Dash, Mamoni; Van Vlierberghe, Sandra Chemical Society Reviews, Vol. 41, Issue 21 https://doi.org/10.1039/c2cs35094g	journal	January 2012
Alkaline polymer electrolyte fuel cells completely free from noble metal catalysts Lu, S.; Pan, J.; Huang, A. Proceedings of the National Academy of Sciences, Vol. 105, Issue 52, p. 20611-20614 https://doi.org/10.1073/pnas.0810041106	journal	December 2008
Highly conductive and chemically stable alkaline anion exchange membranes via ROMP of trans -cyclooctene derivatives You, Wei; Padgett, Elliot; MacMillan, Samantha N. Proceedings of the National Academy of Sciences, Vol. 116, Issue 20 https://doi.org/10.1073/pnas.1900988116	journal	April 2019
A completely precious metal–free alkaline fuel cell with enhanced performance using a carbon-coated nickel anode Gao, Yunfei; Yang, Yao; Schimmenti, Roberto Proceedings of the National Academy of Sciences, Vol. 119, Issue 13 https://doi.org/10.1073/pnas.2119883119	journal	March 2022
A Review of Ionic Polymeric Soft Actuators and Sensors Bahramzadeh, Yousef; Shahinpoor, Mohsen Soft Robotics, Vol. 1, Issue 1 https://doi.org/10.1089/soro.2013.0006	journal	March 2014
The Importance of Water Transport in High Conductivity and High-Power Alkaline Fuel Cells Mandal, Mrinmay; Huang, Garrett; Hassan, Noor Ul Journal of The Electrochemical Society, Vol. 167, Issue 5 https://doi.org/10.1149/2.0022005JES	journal	October 2019
Composite Poly(norbornene) Anion Conducting Membranes for Achieving Durability, Water Management and High Power (3.4 W/cm ² ) in Hydrogen/Oxygen Alkaline Fuel Cells Huang, Garrett; Mandal, Mrinmay; Peng, Xiong Journal of The Electrochemical Society, Vol. 166, Issue 10 https://doi.org/10.1149/2.1301910jes	journal	January 2019

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