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Title: Impact of hygrothermal aging on structure/function relationship of perfluorosulfonic-acid membrane

Abstract

Perfluorosulfonic-acid (PFSA) membranes are widely used as the solid electrolyte in electrochemical devices where their main functionalities are ion (proton) conduction and gas separation in a thermomechanically stable matrix. Due to prolonged operational requirements in these devices, PFSA membranes' properties change with time due to hygrothermal aging. This paper studies the evolution of PFSA structure/property relationship changes during hygrothermal aging, including chemical changes leading to changes in ion-exchange capacity (IEC), nanostructure, water-uptake behavior, conductivity, and mechanical properties. Our findings demonstrate that with hygrothermal aging, the storage modulus increases, while IEC and water content decrease, consistent with the changes in nanostructure, that is, water- and crystalline-domain spacings inferred from small- and wide-angle X-ray scattering (SAXS/WAXS) experiments. In addition, the impact of aging is found to depend on the membrane's thermal prehistory and post-treatments, although universal correlations exist between nanostructural changes and water uptake. The findings have impact on understanding lifetime, durability, and use of these and related polymers in various technologies.

Authors:
 [1];  [2];  [2];  [3];  [3];  [2];  [2]
+ Show Author Affiliations
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Tianjin Univ., Tianjin (China)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1329879
Alternate Identifier(s):
OSTI ID: 1454456
Report Number(s):
LA-UR-15-24975
Journal ID: ISSN 0887-6266
Grant/Contract Number:  
AC52-06NA25396; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Polymer Science. Part B, Polymer Physics
Additional Journal Information:
Journal Volume: 54; Journal Issue: 5; Journal ID: ISSN 0887-6266
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
30 DIRECT ENERGY CONVERSION; energy sciences; fuel cell; PFSA ionomers; ion-exchange capacity; structure/property; SAXS/WAXS; hygrothermal ageing

Citation Formats

Shi, Shouwen, Dursch, Thomas J., Blake, Colin, Mukundan, Rangachary, Borup, Rodney L., Weber, Adam Z., and Kusoglu, Ahmet. Impact of hygrothermal aging on structure/function relationship of perfluorosulfonic-acid membrane. United States: N. p., 2015. Web. doi:10.1002/polb.23946.
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Shi, Shouwen, Dursch, Thomas J., Blake, Colin, Mukundan, Rangachary, Borup, Rodney L., Weber, Adam Z., & Kusoglu, Ahmet. Impact of hygrothermal aging on structure/function relationship of perfluorosulfonic-acid membrane. United States. https://doi.org/10.1002/polb.23946
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Shi, Shouwen, Dursch, Thomas J., Blake, Colin, Mukundan, Rangachary, Borup, Rodney L., Weber, Adam Z., and Kusoglu, Ahmet. Tue . "Impact of hygrothermal aging on structure/function relationship of perfluorosulfonic-acid membrane". United States. https://doi.org/10.1002/polb.23946. https://www.osti.gov/servlets/purl/1329879.
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@article{osti_1329879,
title = {Impact of hygrothermal aging on structure/function relationship of perfluorosulfonic-acid membrane},
author = {Shi, Shouwen and Dursch, Thomas J. and Blake, Colin and Mukundan, Rangachary and Borup, Rodney L. and Weber, Adam Z. and Kusoglu, Ahmet},
abstractNote = {Perfluorosulfonic-acid (PFSA) membranes are widely used as the solid electrolyte in electrochemical devices where their main functionalities are ion (proton) conduction and gas separation in a thermomechanically stable matrix. Due to prolonged operational requirements in these devices, PFSA membranes' properties change with time due to hygrothermal aging. This paper studies the evolution of PFSA structure/property relationship changes during hygrothermal aging, including chemical changes leading to changes in ion-exchange capacity (IEC), nanostructure, water-uptake behavior, conductivity, and mechanical properties. Our findings demonstrate that with hygrothermal aging, the storage modulus increases, while IEC and water content decrease, consistent with the changes in nanostructure, that is, water- and crystalline-domain spacings inferred from small- and wide-angle X-ray scattering (SAXS/WAXS) experiments. In addition, the impact of aging is found to depend on the membrane's thermal prehistory and post-treatments, although universal correlations exist between nanostructural changes and water uptake. The findings have impact on understanding lifetime, durability, and use of these and related polymers in various technologies.},
doi = {10.1002/polb.23946},
journal = {Journal of Polymer Science. Part B, Polymer Physics},
number = 5,
volume = 54,
place = {United States},
year = {Tue Oct 20 00:00:00 EDT 2015},
month = {Tue Oct 20 00:00:00 EDT 2015}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1002/polb.23946
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Cited by: 30 works
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Figures / Tables:

Figure 1 Figure 1: Chemical structure of PFSA and process of anhydride formation through sulfonic-acid group condensation.
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