Polymer electrolyte membranes based on poly(arylene ether sulfone) with pendant perfluorosulfonic acid

Ying Chang, Giuseppe F. Brunello, Jeffrey Fuller, Melanie L. Disabb-Miller, Marilyn E. Hawley, Yu Seung Kim, Michael Anthony Hickner, Seung Soon Jang, Chulsung Bae

Research output: Contribution to journalArticle

43 Citations (Scopus)

Abstract

Poly(arylene ether sulfone)-based ionomers with sulfonate groups of varying acidity (perfluoroalkyl sulfonate, aryl sulfonate and alkyl sulfonate) were synthesized via borylation of aromatic C-H bonds and Suzuki coupling with sulfonated phenyl bromides. Properties of the ionomers, such as thermal stability, water uptake, ion exchange capacity, morphology and proton conductivity, were analyzed with respect to the effect of the sulfonate group. Superacidic fluoroalkyl sulfonated ionomers displayed much higher conductivity at low relative humidity than less acidic aryl and alkyl sulfonated ionomers in spite of their lower ion exchange capacities. The water uptake of the membranes correlated with their IEC, regardless of the acid group identity. The membranes with fluoroalkyl and alkyl sulfonate groups had similar hydration numbers as a function of RH, but the hydration number of the aromatic sulfonate sample was greater than the other polymers. Ionic domain structure analysis by atomic force microscopy, transmission electron microscopy and small-angle X-ray scattering revealed that all of the aromatic ionomers in this study had a small, disorganized phase structure. These results demonstrate that the primary influence on the proton conductivity of these randomly sulfonated copolymers is the acid strength while the nanoscale domain structure plays a secondary role in the low RH proton transport.

Original languageEnglish (US)
Pages (from-to)272-281
Number of pages10
JournalPolymer Chemistry
Volume4
Issue number2
DOIs
StatePublished - Jan 21 2013

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Sulfones
Ionomers
Alkanesulfonates
Ether
Electrolytes
Protons
Ethers
Polymers
Ion Exchange
Membranes
Arylsulfonates
Acids
Proton conductivity
Water
Atomic Force Microscopy
Hydration
Humidity
Ion exchange
Transmission Electron Microscopy
Bromides

All Science Journal Classification (ASJC) codes

  • Bioengineering
  • Biochemistry
  • Polymers and Plastics
  • Organic Chemistry

Cite this

Chang, Y., Brunello, G. F., Fuller, J., Disabb-Miller, M. L., Hawley, M. E., Kim, Y. S., ... Bae, C. (2013). Polymer electrolyte membranes based on poly(arylene ether sulfone) with pendant perfluorosulfonic acid. Polymer Chemistry, 4(2), 272-281. https://doi.org/10.1039/c2py20666h
Chang, Ying ; Brunello, Giuseppe F. ; Fuller, Jeffrey ; Disabb-Miller, Melanie L. ; Hawley, Marilyn E. ; Kim, Yu Seung ; Hickner, Michael Anthony ; Jang, Seung Soon ; Bae, Chulsung. / Polymer electrolyte membranes based on poly(arylene ether sulfone) with pendant perfluorosulfonic acid. In: Polymer Chemistry. 2013 ; Vol. 4, No. 2. pp. 272-281.
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Chang, Y, Brunello, GF, Fuller, J, Disabb-Miller, ML, Hawley, ME, Kim, YS, Hickner, MA, Jang, SS & Bae, C 2013, 'Polymer electrolyte membranes based on poly(arylene ether sulfone) with pendant perfluorosulfonic acid', Polymer Chemistry, vol. 4, no. 2, pp. 272-281. https://doi.org/10.1039/c2py20666h

Polymer electrolyte membranes based on poly(arylene ether sulfone) with pendant perfluorosulfonic acid. / Chang, Ying; Brunello, Giuseppe F.; Fuller, Jeffrey; Disabb-Miller, Melanie L.; Hawley, Marilyn E.; Kim, Yu Seung; Hickner, Michael Anthony; Jang, Seung Soon; Bae, Chulsung.

In: Polymer Chemistry, Vol. 4, No. 2, 21.01.2013, p. 272-281.

Research output: Contribution to journalArticle

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T1 - Polymer electrolyte membranes based on poly(arylene ether sulfone) with pendant perfluorosulfonic acid

AU - Chang, Ying

AU - Brunello, Giuseppe F.

AU - Fuller, Jeffrey

AU - Disabb-Miller, Melanie L.

AU - Hawley, Marilyn E.

AU - Kim, Yu Seung

AU - Hickner, Michael Anthony

AU - Jang, Seung Soon

AU - Bae, Chulsung

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Y1 - 2013/1/21

N2 - Poly(arylene ether sulfone)-based ionomers with sulfonate groups of varying acidity (perfluoroalkyl sulfonate, aryl sulfonate and alkyl sulfonate) were synthesized via borylation of aromatic C-H bonds and Suzuki coupling with sulfonated phenyl bromides. Properties of the ionomers, such as thermal stability, water uptake, ion exchange capacity, morphology and proton conductivity, were analyzed with respect to the effect of the sulfonate group. Superacidic fluoroalkyl sulfonated ionomers displayed much higher conductivity at low relative humidity than less acidic aryl and alkyl sulfonated ionomers in spite of their lower ion exchange capacities. The water uptake of the membranes correlated with their IEC, regardless of the acid group identity. The membranes with fluoroalkyl and alkyl sulfonate groups had similar hydration numbers as a function of RH, but the hydration number of the aromatic sulfonate sample was greater than the other polymers. Ionic domain structure analysis by atomic force microscopy, transmission electron microscopy and small-angle X-ray scattering revealed that all of the aromatic ionomers in this study had a small, disorganized phase structure. These results demonstrate that the primary influence on the proton conductivity of these randomly sulfonated copolymers is the acid strength while the nanoscale domain structure plays a secondary role in the low RH proton transport.

AB - Poly(arylene ether sulfone)-based ionomers with sulfonate groups of varying acidity (perfluoroalkyl sulfonate, aryl sulfonate and alkyl sulfonate) were synthesized via borylation of aromatic C-H bonds and Suzuki coupling with sulfonated phenyl bromides. Properties of the ionomers, such as thermal stability, water uptake, ion exchange capacity, morphology and proton conductivity, were analyzed with respect to the effect of the sulfonate group. Superacidic fluoroalkyl sulfonated ionomers displayed much higher conductivity at low relative humidity than less acidic aryl and alkyl sulfonated ionomers in spite of their lower ion exchange capacities. The water uptake of the membranes correlated with their IEC, regardless of the acid group identity. The membranes with fluoroalkyl and alkyl sulfonate groups had similar hydration numbers as a function of RH, but the hydration number of the aromatic sulfonate sample was greater than the other polymers. Ionic domain structure analysis by atomic force microscopy, transmission electron microscopy and small-angle X-ray scattering revealed that all of the aromatic ionomers in this study had a small, disorganized phase structure. These results demonstrate that the primary influence on the proton conductivity of these randomly sulfonated copolymers is the acid strength while the nanoscale domain structure plays a secondary role in the low RH proton transport.

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Chang Y, Brunello GF, Fuller J, Disabb-Miller ML, Hawley ME, Kim YS et al. Polymer electrolyte membranes based on poly(arylene ether sulfone) with pendant perfluorosulfonic acid. Polymer Chemistry. 2013 Jan 21;4(2):272-281. https://doi.org/10.1039/c2py20666h