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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 oftrans-cyclooctenes. Atrans-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 1H NMR spectroscopy when the polymers were treated with 2 M KOH in CD 3OH at 80 °C for 30 d.

Authors:
; ; ; ; ORCiD logo
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Alkaline-Based Energy+B11:C29 Solutions (CABES); Cornell Univ., Ithaca, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1566669
DOE Contract Number:  
SC0019445
Resource Type:
Journal Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 116; Journal Issue: 20; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
catalysis (heterogeneous), electrocatalysis, hydrogen and fuel cells, charge transport, membranes, water, materials and chemistry by design, synthesis (novel materials)

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_1566669,
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 oftrans-cyclooctenes. Atrans-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 by1H NMR spectroscopy when the polymers were treated with 2 M KOH in CD3OH 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 = 20,
volume = 116,
place = {United States},
year = {2019},
month = {4}
}

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