Journal
ACS APPLIED ENERGY MATERIALS
Volume 4, Issue 10, Pages 11652-11665Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acsaem.1c02389
Keywords
poly(arylene piperidinium) membranes; polyhydroxylalkylations; hydroxide conductivity; water electrolyzers; alkaline fuel cells
Funding
- Swedish Energy Agency [505191, 45057-1, 37806-3]
- Swedish Research Council [45397-1, 2015-04820]
- Swedish Foundation for Strategic Research, SSF [EM16-0060]
- Royal Physiographic Society of Lund
- Swedish Research Council [2015-04820] Funding Source: Swedish Research Council
- Swedish Foundation for Strategic Research (SSF) [EM16-0060] Funding Source: Swedish Foundation for Strategic Research (SSF)
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To develop anion exchange membranes with high chemical stability and hydroxide conductivity, poly(arylene piperidine)s carrying mono- or dicationic side chains were synthesized. Series 1 AEMs showed excellent alkaline stability and high hydroxide conductivity, suitable for harsh alkaline conditions, while series 2 AEMs exhibited higher conductivity under moderate water uptake but were more vulnerable to hydroxide attack.
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. Sub-sequently, 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 degrees C during 30 days. In addition, these AEMs reached a hydroxide conductivity up to 131 mS cm(-1) at 80 degrees 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 degrees 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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