skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Highly conductive and chemically stable alkaline anion exchange membranes via ROMP of trans -cyclooctene derivatives

Abstract

Alkaline anion exchange membranes (AAEMs) are an important component of alkaline exchange membrane fuel cells (AEMFCs), which facilitate the efficient conversion of fuels to electricity using nonplatinum electrode catalysts. However, low hydroxide conductivity and poor long-term alkaline stability of AAEMs are the major limitations for the widespread application of AEMFCs. In this paper, we report the synthesis of highly conductive and chemically stable AAEMs from the living polymerization of trans -cyclooctenes. A trans -cyclooctene–fused imidazolium monomer was designed and synthesized on gram scale. Using these highly ring-strained monomers, we produced a range of block and random copolymers. Surprisingly, AAEMs made from the random copolymer exhibited much higher conductivities than their block copolymer analogs. Investigation by transmission electron microscopy showed that the block copolymers had a disordered microphase segregation which likely impeded ion conduction. A cross-linked random copolymer demonstrated a high level of hydroxide conductivity (134 mS/cm at 80 °C). More importantly, the membranes exhibited excellent chemical stability due to the incorporation of highly alkaline-stable multisubstituted imidazolium cations. No chemical degradation was detected by 1 H NMR spectroscopy when the polymers were treated with 2 M KOH in CD 3 OH at 80 °C for 30 d.

Authors:
; ; ; ; ORCiD logo
Publication Date:
Research Org.:
Cornell Univ., Ithaca, NY (United States). Energy Frontier Research Center (EFRC) Center for Alkaline-Based Energy+B11:C29 Solutions (CABES)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1509916
Alternate Identifier(s):
OSTI ID: 1566669
Grant/Contract Number:  
SC0019445
Resource Type:
Journal Article: Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; alkaline anion exchange membrane; trans-cyclooctene; block and random copolymer; cross-linked polymer; transmission electron microscopy

Citation Formats

You, Wei, Padgett, Elliot, MacMillan, Samantha N., Muller, David A., and Coates, Geoffrey W. Highly conductive and chemically stable alkaline anion exchange membranes via ROMP of trans -cyclooctene derivatives. United States: N. p., 2019. Web. doi:10.1073/pnas.1900988116.
You, Wei, Padgett, Elliot, MacMillan, Samantha N., Muller, David A., & Coates, Geoffrey W. Highly conductive and chemically stable alkaline anion exchange membranes via ROMP of trans -cyclooctene derivatives. United States. doi:10.1073/pnas.1900988116.
You, Wei, Padgett, Elliot, MacMillan, Samantha N., Muller, David A., and Coates, Geoffrey W. Mon . "Highly conductive and chemically stable alkaline anion exchange membranes via ROMP of trans -cyclooctene derivatives". United States. doi:10.1073/pnas.1900988116.
@article{osti_1509916,
title = {Highly conductive and chemically stable alkaline anion exchange membranes via ROMP of trans -cyclooctene derivatives},
author = {You, Wei and Padgett, Elliot and MacMillan, Samantha N. and Muller, David A. and Coates, Geoffrey W.},
abstractNote = {Alkaline anion exchange membranes (AAEMs) are an important component of alkaline exchange membrane fuel cells (AEMFCs), which facilitate the efficient conversion of fuels to electricity using nonplatinum electrode catalysts. However, low hydroxide conductivity and poor long-term alkaline stability of AAEMs are the major limitations for the widespread application of AEMFCs. In this paper, we report the synthesis of highly conductive and chemically stable AAEMs from the living polymerization of trans -cyclooctenes. A trans -cyclooctene–fused imidazolium monomer was designed and synthesized on gram scale. Using these highly ring-strained monomers, we produced a range of block and random copolymers. Surprisingly, AAEMs made from the random copolymer exhibited much higher conductivities than their block copolymer analogs. Investigation by transmission electron microscopy showed that the block copolymers had a disordered microphase segregation which likely impeded ion conduction. A cross-linked random copolymer demonstrated a high level of hydroxide conductivity (134 mS/cm at 80 °C). More importantly, the membranes exhibited excellent chemical stability due to the incorporation of highly alkaline-stable multisubstituted imidazolium cations. No chemical degradation was detected by 1 H NMR spectroscopy when the polymers were treated with 2 M KOH in CD 3 OH at 80 °C for 30 d.},
doi = {10.1073/pnas.1900988116},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
issn = {0027-8424},
number = ,
volume = ,
place = {United States},
year = {2019},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1073/pnas.1900988116

Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Prospects for Alkaline Anion-Exchange Membranes in Low Temperature Fuel Cells
journal, October 2004


Influence of strain on chemical reactivity. Relative reactivity of torsionally distorted double bonds in MCPBA epoxidations
journal, April 1992

  • Shea, Kenneth J.; Kim, Jang Seob
  • Journal of the American Chemical Society, Vol. 114, Issue 8
  • DOI: 10.1021/ja00034a042

Review of cell performance in anion exchange membrane fuel cells
journal, January 2018


Robust Hydroxide Ion Conducting Poly(biphenyl alkylene)s for Alkaline Fuel Cell Membranes
journal, July 2015


A Photochemical Synthesis of Functionalized trans -Cyclooctenes Driven by Metal Complexation
journal, March 2008

  • Royzen, Maksim; Yap, Glenn P. A.; Fox, Joseph M.
  • Journal of the American Chemical Society, Vol. 130, Issue 12
  • DOI: 10.1021/ja8001919

Cationic Polyelectrolytes, Stable in 10 M KOH aq at 100 °C
journal, September 2017


Tuning the properties of poly(2,6-dimethyl-1,4-phenylene oxide) anion exchange membranes and their performance in H 2 /O 2 fuel cells
journal, January 2018

  • Liu, Lei; Chu, Xiaomeng; Liao, Jiayou
  • Energy & Environmental Science, Vol. 11, Issue 2
  • DOI: 10.1039/C7EE02468A

Alkaline Stability of Quaternary Ammonium Cations for Alkaline Fuel Cell Membranes and Ionic Liquids
journal, November 2014


Permethyl Cobaltocenium (Cp*2Co+) as an Ultra-Stable Cation for Polymer Hydroxide-Exchange Membranes
journal, June 2015

  • Gu, Shuang; Wang, Junhua; Kaspar, Robert B.
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep11668

Imidazolium Cations with Exceptional Alkaline Stability: A Systematic Study of Structure–Stability Relationships
journal, July 2015

  • Hugar, Kristina M.; Kostalik, Henry A.; Coates, Geoffrey W.
  • Journal of the American Chemical Society, Vol. 137, Issue 27
  • DOI: 10.1021/jacs.5b02879

Rapid Analysis of Tetrakis(dialkylamino)phosphonium Stability in Alkaline Media
journal, October 2017


Interconnected ionic domains enhance conductivity in microphase separated block copolymer electrolytes
journal, January 2017

  • Arges, Christopher G.; Kambe, Yu; Dolejsi, Moshe
  • Journal of Materials Chemistry A, Vol. 5, Issue 11
  • DOI: 10.1039/C6TA10838E

Phosphonium-Functionalized Polyethylene: A New Class of Base-Stable Alkaline Anion Exchange Membranes
journal, October 2012

  • Noonan, Kevin J. T.; Hugar, Kristina M.; Kostalik, Henry A.
  • Journal of the American Chemical Society, Vol. 134, Issue 44
  • DOI: 10.1021/ja307466s

Multication Side Chain Anion Exchange Membranes
journal, January 2016


Oxygen reduction at the silver/hydroxide-exchange membrane interface
journal, January 2008

  • Sleightholme, Alice E. S.; Varcoe, John R.; Kucernak, Anthony R.
  • Electrochemistry Communications, Vol. 10, Issue 1
  • DOI: 10.1016/j.elecom.2007.11.008

Cationic Metallo-Polyelectrolytes for Robust Alkaline Anion-Exchange Membranes
journal, January 2018

  • Zhu, Tianyu; Xu, Shichao; Rahman, Anisur
  • Angewandte Chemie International Edition, Vol. 57, Issue 9
  • DOI: 10.1002/anie.201712387

Anion conducting multiblock copolymers with multiple head-groups
journal, January 2018

  • Liu, Lisha; Huang, Garrett; Kohl, Paul A.
  • Journal of Materials Chemistry A, Vol. 6, Issue 19
  • DOI: 10.1039/C8TA00753E

Metal-Cation-Based Anion Exchange Membranes
journal, March 2012

  • Zha, Yongping; Disabb-Miller, Melanie L.; Johnson, Zachary D.
  • Journal of the American Chemical Society, Vol. 134, Issue 10
  • DOI: 10.1021/ja211365r

Transport Properties of Sulfonated Poly(styrene- b -isobutylene- b -styrene) Triblock Copolymers at High Ion-Exchange Capacities
journal, January 2006

  • Elabd, Yossef A.; Napadensky, Eugene; Walker, Charles W.
  • Macromolecules, Vol. 39, Issue 1
  • DOI: 10.1021/ma051958n

A Stable Hydroxide-Conducting Polymer
journal, June 2012

  • Thomas, Owen D.; Soo, Kristen J. W. Y.; Peckham, Timothy J.
  • Journal of the American Chemical Society, Vol. 134, Issue 26
  • DOI: 10.1021/ja303067t

Alkaline direct alcohol fuel cells
journal, June 2010


Anion-exchange membranes in electrochemical energy systems
journal, January 2014

  • Varcoe, John R.; Atanassov, Plamen; Dekel, Dario R.
  • Energy & Environmental Science, Vol. 7, Issue 10, p. 3135-3191
  • DOI: 10.1039/C4EE01303D

A Soluble and Highly Conductive Ionomer for High-Performance Hydroxide Exchange Membrane Fuel Cells
journal, August 2009

  • Gu, Shuang; Cai, Rui; Luo, Ting
  • Angewandte Chemie International Edition, Vol. 48, Issue 35, p. 6499-6502
  • DOI: 10.1002/anie.200806299

Vulcanization of cis- and trans-polyisoprene and their blends: crystallization characteristics and properties
journal, March 2001


The Living ROMP of trans -Cyclooctene
journal, February 2009

  • Walker, Ron; Conrad, Rosemary M.; Grubbs, Robert H.
  • Macromolecules, Vol. 42, Issue 3
  • DOI: 10.1021/ma801693q

Degradation of anion exchange membranes used for hydrogen production by ultrapure water electrolysis
journal, January 2014

  • Parrondo, Javier; Arges, Christopher G.; Niedzwiecki, Mike
  • RSC Advances, Vol. 4, Issue 19, p. 9875-9879
  • DOI: 10.1039/c3ra46630b

Chemically Cross-Linked Polycyclooctene:  Synthesis, Characterization, and Shape Memory Behavior
journal, December 2002

  • Liu, Changdeng; Chun, Seung B.; Mather, Patrick T.
  • Macromolecules, Vol. 35, Issue 27
  • DOI: 10.1021/ma021141j

Highly anion conductive, alkyl-chain-grafted copolymers as anion exchange membranes for operable alkaline H 2 /O 2 fuel cells
journal, January 2017

  • Yang, Cheng; Liu, Lei; Han, Xiaojin
  • Journal of Materials Chemistry A, Vol. 5, Issue 21
  • DOI: 10.1039/C7TA00481H

Highly Conductive Anion-Exchange Membranes from Microporous Tröger's Base Polymers
journal, August 2016

  • Yang, Zhengjin; Guo, Rui; Malpass-Evans, Richard
  • Angewandte Chemie International Edition, Vol. 55, Issue 38
  • DOI: 10.1002/anie.201605916

Branched comb-shaped poly(arylene ether sulfone)s containing flexible alkyl imidazolium side chains as anion exchange membranes
journal, January 2018

  • Liu, Dong; Xu, Muzi; Fang, Mingliang
  • Journal of Materials Chemistry A, Vol. 6, Issue 23
  • DOI: 10.1039/C8TA02115E

N -Alkyl Interstitial Spacers and Terminal Pendants Influence the Alkaline Stability of Tetraalkylammonium Cations for Anion Exchange Membrane Fuel Cells
journal, April 2016


Thermodynamics of Counterion Release Is Critical for Anion Exchange Membrane Conductivity
journal, May 2018

  • Kwasny, Michael T.; Zhu, Liang; Hickner, Michael A.
  • Journal of the American Chemical Society, Vol. 140, Issue 25
  • DOI: 10.1021/jacs.8b03979

Poly(arylene alkylene)s with pendant N -spirocyclic quaternary ammonium cations for anion exchange membranes
journal, January 2018

  • Pham, Thanh Huong; Olsson, Joel S.; Jannasch, Patric
  • Journal of Materials Chemistry A, Vol. 6, Issue 34
  • DOI: 10.1039/C8TA04699A

Polymerized Ionic Liquid Block and Random Copolymers: Effect of Weak Microphase Separation on Ion Transport
journal, August 2012

  • Ye, Yuesheng; Choi, Jae-Hong; Winey, Karen I.
  • Macromolecules, Vol. 45, Issue 17
  • DOI: 10.1021/ma301036b

Water Uptake Study of Anion Exchange Membranes
journal, April 2018


Tunable High Performance Cross-Linked Alkaline Anion Exchange Membranes for Fuel Cell Applications
journal, March 2010

  • Robertson, Nicholas J.; Kostalik, Henry A.; Clark, Timothy J.
  • Journal of the American Chemical Society, Vol. 132, Issue 10
  • DOI: 10.1021/ja908638d

Thermally Cross-Linked Anion Exchange Membranes from Solvent Processable Isoprene Containing Ionomers
journal, January 2015

  • Tsai, Tsung-Han; Ertem, S. Piril; Maes, Ashley M.
  • Macromolecules, Vol. 48, Issue 3
  • DOI: 10.1021/ma502362a

Achieving Continuous Anion Transport Domains Using Block Copolymers Containing Phosphonium Cations
journal, June 2016


Synthesis of Precision Ionic Polyolefins Derived from Ionic Liquids
journal, February 2010

  • Aitken, Brian S.; Lee, Minjae; Hunley, Matthew T.
  • Macromolecules, Vol. 43, Issue 4
  • DOI: 10.1021/ma9024174

A review on recent developments of anion exchange membranes for fuel cells and redox flow batteries
journal, January 2015

  • Maurya, Sandip; Shin, Sung-Hee; Kim, Yekyung
  • RSC Advances, Vol. 5, Issue 47
  • DOI: 10.1039/C5RA04741B

Kinetic Study of Living Ring-Opening Metathesis Polymerization with Third-Generation Grubbs Catalysts
journal, September 2017

  • Walsh, Dylan J.; Lau, Sii Hong; Hyatt, Michael G.
  • Journal of the American Chemical Society, Vol. 139, Issue 39
  • DOI: 10.1021/jacs.7b08010

Anion exchange membranes for alkaline fuel cells: A review
journal, July 2011

  • Merle, Géraldine; Wessling, Matthias; Nijmeijer, Kitty
  • Journal of Membrane Science, Vol. 377, Issue 1-2, p. 1-35
  • DOI: 10.1016/j.memsci.2011.04.043

Expanding metal cation options in polymeric anion exchange membranes
journal, January 2017

  • Kwasny, Michael T.; Tew, Gregory N.
  • Journal of Materials Chemistry A, Vol. 5, Issue 4
  • DOI: 10.1039/C6TA07990C

Anion Conductive Block Poly(arylene ether)s: Synthesis, Properties, and Application in Alkaline Fuel Cells
journal, July 2011

  • Tanaka, Manabu; Fukasawa, Keita; Nishino, Eriko
  • Journal of the American Chemical Society, Vol. 133, Issue 27, p. 10646-10654
  • DOI: 10.1021/ja204166e

Stabilizing the Imidazolium Cation in Hydroxide-Exchange Membranes for Fuel Cells
journal, August 2013


Anion Transport in a Chemically Stable, Sterically Bulky α-C Modified Imidazolium Functionalized Anion Exchange Membrane
journal, July 2014

  • Liu, Ye; Wang, Junhua; Yang, Yuan
  • The Journal of Physical Chemistry C, Vol. 118, Issue 28, p. 15136-15145
  • DOI: 10.1021/jp5027674

Relating alkaline stability to the structure of quaternary phosphonium cations
journal, January 2018

  • Zhang, Bingzi; Long, Hai; Kaspar, Robert B.
  • RSC Advances, Vol. 8, Issue 47
  • DOI: 10.1039/C8RA03440K

Ultrastable and High Ion-Conducting Polyelectrolyte Based on Six-Membered N-Spirocyclic Ammonium for Hydroxide Exchange Membrane Fuel Cell Applications
journal, April 2018

  • Chen, Nanjun; Long, Chuan; Li, Yunxi
  • ACS Applied Materials & Interfaces, Vol. 10, Issue 18
  • DOI: 10.1021/acsami.8b02884

Assessing the influence of different cation chemistries on ionic conductivity and alkaline stability of anion exchange membranes
journal, January 2012

  • Arges, Christopher G.; Parrondo, Javier; Johnson, Graham
  • Journal of Materials Chemistry, Vol. 22, Issue 9
  • DOI: 10.1039/c2jm14898f

Variable Temperature ROMP: Leveraging Low Ring Strain Thermodynamics To Achieve Well-Defined Polypentenamers
journal, June 2017


Anion Exchange Membranes’ Evolution toward High Hydroxide Ion Conductivity and Alkaline Resiliency
journal, June 2018


Hydrocarbon-Based Polymer Electrolyte Membranes: Importance of Morphology on Ion Transport and Membrane Stability
journal, March 2017


Hydroxide-Stable Ionenes
journal, April 2014

  • Wright, Andrew G.; Holdcroft, Steven
  • ACS Macro Letters, Vol. 3, Issue 5
  • DOI: 10.1021/mz500168d

Bicontinuous Alkaline Fuel Cell Membranes from Strongly Self-Segregating Block Copolymers
journal, August 2013

  • Price, Samuel C.; Ren, Xiaoming; Jackson, Aaron C.
  • Macromolecules, Vol. 46, Issue 18
  • DOI: 10.1021/ma400995n

Anion-Exchange Membranes for Alkaline Fuel-Cell Applications: The Effects of Cations
journal, December 2017


Crosslinking of comb-shaped polymer anion exchange membranes via thiol–ene click chemistry
journal, January 2016

  • Zhu, Liang; Zimudzi, Tawanda J.; Li, Nanwen
  • Polymer Chemistry, Vol. 7, Issue 14
  • DOI: 10.1039/C5PY01911G

Helical (5Z, 11E)-Dibenzo[a,e]cyclooctatetrene: A Spring-Loaded Monomer
journal, April 2008

  • Carnes, Matthew; Buccella, Daniela; Decatur, John
  • Angewandte Chemie International Edition, Vol. 47, Issue 16
  • DOI: 10.1002/anie.200704355

Anion exchange membrane fuel cells: Current status and remaining challenges
journal, January 2018


Hexamethyl-p-terphenyl poly(benzimidazolium): a universal hydroxide-conducting polymer for energy conversion devices
journal, January 2016

  • Wright, Andrew G.; Fan, Jiantao; Britton, Benjamin
  • Energy & Environmental Science, Vol. 9, Issue 6
  • DOI: 10.1039/C6EE00656F

Investigations of conductivity in FEP-based radiation-grafted alkaline anion-exchange membranes
journal, February 2005


Optimization of the pendant chain length in partially fluorinated aromatic anion exchange membranes for alkaline fuel cells
journal, January 2018

  • Ahmed Mahmoud, Ahmed Mohamed; Miyatake, Kenji
  • Journal of Materials Chemistry A, Vol. 6, Issue 29
  • DOI: 10.1039/C8TA04310H

Conformationally strained trans-cyclooctene with improved stability and excellent reactivity in tetrazine ligation
journal, January 2014

  • Darko, Ampofo; Wallace, Stephen; Dmitrenko, Olga
  • Chem. Sci., Vol. 5, Issue 10
  • DOI: 10.1039/C4SC01348D

Polyethylene-Based Block Copolymers for Anion Exchange Membranes
journal, September 2015


A benzyltetramethylimidazolium-based membrane with exceptional alkaline stability in fuel cells: role of its structure in alkaline stability
journal, January 2018

  • Zhu, Yuan; He, Yubin; Ge, Xiaolin
  • Journal of Materials Chemistry A, Vol. 6, Issue 2
  • DOI: 10.1039/C7TA09095A

N -Spirocyclic Quaternary Ammonium Ionenes for Anion-Exchange Membranes
journal, February 2017

  • Pham, Thanh Huong; Olsson, Joel S.; Jannasch, Patric
  • Journal of the American Chemical Society, Vol. 139, Issue 8
  • DOI: 10.1021/jacs.6b12944

Alkaline Stable C2-Substituted Imidazolium-Based Anion-Exchange Membranes
journal, April 2013

  • Lin, Bencai; Dong, Huilong; Li, Youyong
  • Chemistry of Materials, Vol. 25, Issue 9, p. 1858-1867
  • DOI: 10.1021/cm400468u

Nanoparticle-Driven Assembly of Highly Conducting Hybrid Block Copolymer Electrolytes
journal, January 2015

  • Villaluenga, Irune; Chen, Xi Chelsea; Devaux, Didier
  • Macromolecules, Vol. 48, Issue 2
  • DOI: 10.1021/ma502234y

Tetrakis(dialkylamino)phosphonium Polyelectrolytes Prepared by Reversible Addition–Fragmentation Chain Transfer Polymerization
journal, January 2016


Alkaline polymer electrolyte fuel cells completely free from noble metal catalysts
journal, December 2008

  • Lu, S.; Pan, J.; Huang, A.
  • Proceedings of the National Academy of Sciences, Vol. 105, Issue 52, p. 20611-20614
  • DOI: 10.1073/pnas.0810041106

Ion transport properties of mechanically stable symmetric ABCBA pentablock copolymers with quaternary ammonium functionalized midblock
journal, February 2017

  • Ertem, S. Piril; Caire, Benjamin R.; Tsai, Tsung-Han
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 55, Issue 7
  • DOI: 10.1002/polb.24310