Poly(arylene piperidine) Anion Exchange Membranes with Tunable N-Alicyclic Quaternary Ammonium Side Chains
Pan, Dong LU ; Pham, Thanh Huong LU and Jannasch, Patric LU
(2021)
In ACS Applied Energy Materials
4(10).
p.11652-11665
- Abstract
- To develop anion exchange membranes (AEMs) that combine high chemical stability and hydroxide conductivity, we have designed and prepared poly(arylene piperidine)s carrying tunable mono- or dicationic side chains. Poly(biphenyl piperidine) and poly(biphenyl N-methylpiperidine), respectively, were first synthesized by superacid-catalyzed polyhydroxylalkylations. Subsequently, the piperidine rings of these polymers were reacted with bromoalkylated N,N-dimethylpiperidinium (DMP) and 6-azonia spiro[5.5]undecane (ASU) cations, respectively. This gave two series of AEMs in which the polymer backbone contained tertiary and quaternary piperidine rings, respectively, resulting in mono- and dicationic side chains in series 1 and... (More)
- To develop anion exchange membranes (AEMs) that combine high chemical stability and hydroxide conductivity, we have designed and prepared poly(arylene piperidine)s carrying tunable mono- or dicationic side chains. Poly(biphenyl piperidine) and poly(biphenyl N-methylpiperidine), respectively, were first synthesized by superacid-catalyzed polyhydroxylalkylations. Subsequently, the piperidine rings of these polymers were reacted with bromoalkylated N,N-dimethylpiperidinium (DMP) and 6-azonia spiro[5.5]undecane (ASU) cations, respectively. This gave two series of AEMs in which the polymer backbone contained tertiary and quaternary piperidine rings, respectively, resulting in mono- and dicationic side chains in series 1 and 2, respectively. In series 1, both the piperidine rings in the backbone and the pendant cations in the side chains showed excellent alkaline stability, resulting in AEMs, which retained more than 92% of the cations after storage in 2 M NaOH at 90 °C during 30 days. In addition, these AEMs reached a hydroxide conductivity up to 131 mS cm–1 at 80 °C. Benefiting from a high local ionic concentration through the dicationic configuration, the AEMs in series 2 reached a higher conductivity, almost 170 mS cm–1 at 80 °C at moderate water uptake and swelling. Still, these AEMs were more vulnerable to hydroxide attack than the ones in series 1 because of the quaternary piperidinium groups placed in the polymer backbone. In conclusion, the AEMs in series 1 can be employed in electrochemical devices that operate under harsh alkaline conditions, while those in series 2 should be preserved for less aggressive alkaline conditions.
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Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/3629478a-4141-4bc7-a1bc-d65e006d041f
- author
- Pan, Dong
LU
; Pham, Thanh Huong
LU
and Jannasch, Patric
LU
- organization
- publishing date
- 2021
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- poly(arylene piperidinium) membranes, polyhydroxylalkylations, hydroxide conductivity, water electrolyzers, alkaline fuel cells
- in
- ACS Applied Energy Materials
- volume
- 4
- issue
- 10
- pages
- 14 pages
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- scopus:85117766187
- ISSN
- 2574-0962
- DOI
- 10.1021/acsaem.1c02389
- language
- English
- LU publication?
- yes
- additional info
- Published online 6 October 2021
- id
- 3629478a-4141-4bc7-a1bc-d65e006d041f
- date added to LUP
- 2021-08-11 10:01:56
- date last changed
- 2025-04-04 14:40:38
@article{3629478a-4141-4bc7-a1bc-d65e006d041f,
abstract = {{To develop anion exchange membranes (AEMs) that combine high chemical stability and hydroxide conductivity, we have designed and prepared poly(arylene piperidine)s carrying tunable mono- or dicationic side chains. Poly(biphenyl piperidine) and poly(biphenyl <i>N</i>-methylpiperidine), respectively, were first synthesized by superacid-catalyzed polyhydroxylalkylations. Subsequently, the piperidine rings of these polymers were reacted with bromoalkylated <i>N</i>,<i>N</i>-dimethylpiperidinium (DMP) and 6-azonia spiro[5.5]undecane (ASU) cations, respectively. This gave two series of AEMs in which the polymer backbone contained tertiary and quaternary piperidine rings, respectively, resulting in mono- and dicationic side chains in series 1 and 2, respectively. In series 1, both the piperidine rings in the backbone and the pendant cations in the side chains showed excellent alkaline stability, resulting in AEMs, which retained more than 92% of the cations after storage in 2 M NaOH at 90 °C during 30 days. In addition, these AEMs reached a hydroxide conductivity up to 131 mS cm<sup>–1</sup> at 80 °C. Benefiting from a high local ionic concentration through the dicationic configuration, the AEMs in series 2 reached a higher conductivity, almost 170 mS cm<sup>–1</sup> at 80 °C at moderate water uptake and swelling. Still, these AEMs were more vulnerable to hydroxide attack than the ones in series 1 because of the quaternary piperidinium groups placed in the polymer backbone. In conclusion, the AEMs in series 1 can be employed in electrochemical devices that operate under harsh alkaline conditions, while those in series 2 should be preserved for less aggressive alkaline conditions.<br/>}},
author = {{Pan, Dong and Pham, Thanh Huong and Jannasch, Patric}},
issn = {{2574-0962}},
keywords = {{poly(arylene piperidinium) membranes; polyhydroxylalkylations; hydroxide conductivity; water electrolyzers; alkaline fuel cells}},
language = {{eng}},
number = {{10}},
pages = {{11652--11665}},
publisher = {{The American Chemical Society (ACS)}},
series = {{ACS Applied Energy Materials}},
title = {{Poly(arylene piperidine) Anion Exchange Membranes with Tunable <i style="box-sizing: border-box; outline: none;">N</i>-Alicyclic Quaternary Ammonium Side Chains}},
url = {{http://dx.doi.org/10.1021/acsaem.1c02389}},
doi = {{10.1021/acsaem.1c02389}},
volume = {{4}},
year = {{2021}},
}