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Alkali-stable and highly anion conducting poly(phenylene oxide)s carrying quaternary piperidinium cations

Dang, Hai-Son LU and Jannasch, Patric LU (2016) In Journal of Materials Chemistry A 4(30). p.11924-11938
Abstract
New durable and hydroxide ion conducting anion-exchange membranes (AEMs) are currently required in order to develop alkaline fuel cells into efficient and clean energy conversion devices. In the present work we have attached quaternary piperidinium (QPi) groups to poly(2,6-dimethyl-1,4-phenylene oxide)s (PPOs) via flexible alkyl spacer chains with the aim to prepare AEMs. The bromine atoms of bromoalkylated PPOs were displaced in Menshutkin reactions to attach one or two QPi groups, respectively, via heptyl spacers. The cationic polymers have excellent solubility in, e.g., methanol, dimethylsulfoxide and N-methyl-2-pyrrolidone at room temperature, and form tough and transparent membranes. AEMs with bis-QPi side chains efficiently form... (More)
New durable and hydroxide ion conducting anion-exchange membranes (AEMs) are currently required in order to develop alkaline fuel cells into efficient and clean energy conversion devices. In the present work we have attached quaternary piperidinium (QPi) groups to poly(2,6-dimethyl-1,4-phenylene oxide)s (PPOs) via flexible alkyl spacer chains with the aim to prepare AEMs. The bromine atoms of bromoalkylated PPOs were displaced in Menshutkin reactions to attach one or two QPi groups, respectively, via heptyl spacers. The cationic polymers have excellent solubility in, e.g., methanol, dimethylsulfoxide and N-methyl-2-pyrrolidone at room temperature, and form tough and transparent membranes. AEMs with bis-QPi side chains efficiently form ionic clusters and show very high hydroxide ion conductivities, up to 69 and 186 mS cm-1 at 20 and 80 °C, respectively. The AEMs further have excellent alkaline stability, and 1H NMR analysis show no degradation of the AEMs after storage in 1 M NaOH at 90 °C during 8 days. Thermogravimetry indicate decomposition only above 225 °C. The AEM properties were further tuned by controlled formation of bis-QPi crosslinks through an efficient reaction between bromoalkylated PPO and 4,4′-trimethylenebis(1-methylpiperidine) during a reactive membrane casting process. In conclusion, alkali-stable and highly conductive AEMs for alkaline fuel cells can be prepared by placing cycloaliphatic quaternary ammonium cations on flexible side chains and crosslinks. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Materials Chemistry A
volume
4
issue
30
pages
11924 - 11938
publisher
Royal Society of Chemistry
external identifiers
  • Scopus:84979753591
ISSN
2050-7488
DOI
10.1039/C6TA01905F
language
English
LU publication?
yes
id
a2159034-9cb0-4f50-95dc-66b0ea69bd54
date added to LUP
2016-07-02 01:07:21
date last changed
2016-11-20 04:34:33
@misc{a2159034-9cb0-4f50-95dc-66b0ea69bd54,
  abstract     = {New durable and hydroxide ion conducting anion-exchange membranes (AEMs) are currently required in order to develop alkaline fuel cells into efficient and clean energy conversion devices. In the present work we have attached quaternary piperidinium (QPi) groups to poly(2,6-dimethyl-1,4-phenylene oxide)s (PPOs) via flexible alkyl spacer chains with the aim to prepare AEMs. The bromine atoms of bromoalkylated PPOs were displaced in Menshutkin reactions to attach one or two QPi groups, respectively, via heptyl spacers. The cationic polymers have excellent solubility in, e.g., methanol, dimethylsulfoxide and N-methyl-2-pyrrolidone at room temperature, and form tough and transparent membranes. AEMs with bis-QPi side chains efficiently form ionic clusters and show very high hydroxide ion conductivities, up to 69 and 186 mS cm<sup>-1</sup> at 20 and 80 °C, respectively. The AEMs further have excellent alkaline stability, and 1H NMR analysis show no degradation of the AEMs after storage in 1 M NaOH at 90 °C during 8 days. Thermogravimetry indicate decomposition only above 225 °C. The AEM properties were further tuned by controlled formation of bis-QPi crosslinks through an efficient reaction between bromoalkylated PPO and 4,4′-trimethylenebis(1-methylpiperidine) during a reactive membrane casting process. In conclusion, alkali-stable and highly conductive AEMs for alkaline fuel cells can be prepared by placing cycloaliphatic quaternary ammonium cations on flexible side chains and crosslinks.},
  author       = {Dang, Hai-Son and Jannasch, Patric},
  issn         = {2050-7488},
  language     = {eng},
  number       = {30},
  pages        = {11924--11938},
  publisher    = {ARRAY(0x949b0b0)},
  series       = {Journal of Materials Chemistry A},
  title        = {Alkali-stable and highly anion conducting poly(phenylene oxide)s carrying quaternary piperidinium cations},
  url          = {http://dx.doi.org/10.1039/C6TA01905F},
  volume       = {4},
  year         = {2016},
}