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Tuning the Performance of Poly(quaterphenyl piperidinium) Anion-Exchange Membranes by Monomer Configuration

Mansouri Bakvand, Pegah LU ; Pan, Dong LU ; Allushi, Andrit LU and Jannasch, Patric LU orcid (2025) In Advanced Energy Materials 15(25).
Abstract
Poly(arylene piperidinium)s are attractive anion exchange membranes (AEMs) for alkaline membrane fuel cells and water electrolyzers because of their high chemical stability and hydroxide conductivity. Here, ether- and fluorine-free hydroxide conducting poly(quaterphenyl piperidinium) membranes with very similar ion exchange capacity (IEC), but different ratios of meta to para connectivity in the quaterphenyl units, are synthesized and explored. Ionic clustering, water uptake, and the hydroxide conductivity of the AEMs increase gradually with increasing backbone flexibility, i.e., the fraction of meta connectivity. At 80 °C, the AEMs with para,para- and meta,meta-quaterphenyl units,... (More)
Poly(arylene piperidinium)s are attractive anion exchange membranes (AEMs) for alkaline membrane fuel cells and water electrolyzers because of their high chemical stability and hydroxide conductivity. Here, ether- and fluorine-free hydroxide conducting poly(quaterphenyl piperidinium) membranes with very similar ion exchange capacity (IEC), but different ratios of meta to para connectivity in the quaterphenyl units, are synthesized and explored. Ionic clustering, water uptake, and the hydroxide conductivity of the AEMs increase gradually with increasing backbone flexibility, i.e., the fraction of meta connectivity. At 80 °C, the AEMs with para,para- and meta,meta-quaterphenyl units, respectively, reach a conductivity of 96 and 178 mS cm−1, respectively, at a water uptake of 37 and 209%, respectively. Alkaline stability evaluations reveal high alkaline stability, increasing with backbone flexibility. Under very harsh conditions, the cationic loss increases with chain stiffness and occurs mainly through Hofmann β-elimination, but also increasingly via nucleophilic methyl substitution. Copolymerization of quaterphenyls provides properties in between the corresponding homopolymers. In conclusion, it is demonstrated that the configuration of the quaterphenyl monomer can be efficiently tailored to manipulate the chain flexibility of highly alkali-stable AEMs for control over the water uptake and ionic conductivity in a wide range without changing the ionic content of the membranes.
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author
; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Advanced Energy Materials
volume
15
issue
25
article number
2402869
pages
13 pages
publisher
Wiley-Blackwell
external identifiers
  • scopus:85205419228
ISSN
1614-6840
DOI
10.1002/aenm.202402869
language
English
LU publication?
yes
additional info
Euromat 2023 - special collection, guest-edited by Vito Di Noto and Dirk Lehmhus
id
6aac0de2-b5c8-4441-ba0b-8cfce1ba5ad0
date added to LUP
2024-07-02 13:46:33
date last changed
2025-07-02 09:32:25
@article{6aac0de2-b5c8-4441-ba0b-8cfce1ba5ad0,
  abstract     = {{Poly(arylene piperidinium)s are attractive anion exchange membranes (AEMs) for alkaline membrane fuel cells and water electrolyzers because of their high chemical stability and hydroxide conductivity. Here, ether- and fluorine-free hydroxide conducting poly(quaterphenyl piperidinium) membranes with very similar ion exchange capacity (IEC), but different ratios of <i>meta </i>to <i>para </i>connectivity in the quaterphenyl units, are synthesized and explored. Ionic clustering, water uptake, and the hydroxide conductivity of the AEMs increase gradually with increasing backbone flexibility, i.e., the fraction of <i>meta </i>connectivity. At 80 °C, the AEMs with <i>para</i>,<i>para</i>- and <i>meta</i>,<i>meta</i>-quaterphenyl units, respectively, reach a conductivity of 96 and 178 mS cm<sup>−1</sup>, respectively, at a water uptake of 37 and 209%, respectively. Alkaline stability evaluations reveal high alkaline stability, increasing with backbone flexibility. Under very harsh conditions, the cationic loss increases with chain stiffness and occurs mainly through Hofmann <i>β</i>-elimination, but also increasingly via nucleophilic methyl substitution. Copolymerization of quaterphenyls provides properties in between the corresponding homopolymers. In conclusion, it is demonstrated that the configuration of the quaterphenyl monomer can be efficiently tailored to manipulate the chain flexibility of highly alkali-stable AEMs for control over the water uptake and ionic conductivity in a wide range without changing the ionic content of the membranes.<br/>}},
  author       = {{Mansouri Bakvand, Pegah and Pan, Dong and Allushi, Andrit and Jannasch, Patric}},
  issn         = {{1614-6840}},
  language     = {{eng}},
  number       = {{25}},
  publisher    = {{Wiley-Blackwell}},
  series       = {{Advanced Energy Materials}},
  title        = {{Tuning the Performance of Poly(quaterphenyl piperidinium) Anion-Exchange Membranes by Monomer Configuration}},
  url          = {{http://dx.doi.org/10.1002/aenm.202402869}},
  doi          = {{10.1002/aenm.202402869}},
  volume       = {{15}},
  year         = {{2025}},
}