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Title: Swelling of individual nanodomains in hydrated block copolymer electrolyte membranes

Abstract

In this work, we examine the swelling of nanostructured block copolymer electrolytes immersed in liquid water. A series of sulfonated polystyrene-b-polyethylene-b-polystyrene (S-SES) membranes having the same nominal chemical composition but two different morphologies are prepared by systematic changes in processing. We start with a membrane comprising a mixture of homopolymer polystyrene (hPS) and a polystyrene-b-polyethylene-b-polystyrene (SES) copolymer. hPS is subsequently selectively removed from the membrane and the polystyrene domains are sulfonated to give S-SES membranes. The morphology of the membranes is controlled by controlling Φ v, the volume fraction of hPS in the blended membrane. The morphology of the membranes was studied by small angle X-ray scattering (SAXS), cryogenic scanning transmission electron microscopy (cryo-STEM), and cryogenic electron tomography. The overall domain swelling measured by SAXS decreases slightly at Φ v = 0.29; a crossover from lamellar to bicontinuous morphology is obtained at the same value of Φ v. The bicontinuous morphologies absorb more water than the lamellar morphologies. By contrast, the nanodomain swelling of the bicontinuous membrane (120%) is slightly less than that of the lamellar membrane (150%). Quantitative analysis of the STEM images and electron tomography was used to determine the swelling on the hydrophilic and hydrophobic domains duemore » to exposure to water. The hydrophilic sulfonated polystyrene-rich domain spacing increases while the hydrophobic polyethylene domain spacing decreases when the membranes are hydrated. The extent of increase and decrease is not a strong function of Φ v.« less

Authors:
ORCiD logo [1];  [1];  [2]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division and Energy Technologies Area; Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; National Institutes of Health (NIH); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Contributing Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
OSTI Identifier:
1471824
Alternate Identifier(s):
OSTI ID: 1461038; OSTI ID: 1580332
Grant/Contract Number:  
AC05-00OR22725; AC02-05-CH11231; GM051487; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 149; Journal Issue: 16; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; electrolytes; polymers; nanodomains; scanning electron microscopy; x-ray scattering; fuel cells; tomography

Citation Formats

Chen, X. Chelsea, Jiang, Xi, and Balsara, Nitash P. Swelling of individual nanodomains in hydrated block copolymer electrolyte membranes. United States: N. p., 2018. Web. doi:10.1063/1.5029452.
Chen, X. Chelsea, Jiang, Xi, & Balsara, Nitash P. Swelling of individual nanodomains in hydrated block copolymer electrolyte membranes. United States. https://doi.org/10.1063/1.5029452
Chen, X. Chelsea, Jiang, Xi, and Balsara, Nitash P. Fri . "Swelling of individual nanodomains in hydrated block copolymer electrolyte membranes". United States. https://doi.org/10.1063/1.5029452. https://www.osti.gov/servlets/purl/1471824.
@article{osti_1471824,
title = {Swelling of individual nanodomains in hydrated block copolymer electrolyte membranes},
author = {Chen, X. Chelsea and Jiang, Xi and Balsara, Nitash P.},
abstractNote = {In this work, we examine the swelling of nanostructured block copolymer electrolytes immersed in liquid water. A series of sulfonated polystyrene-b-polyethylene-b-polystyrene (S-SES) membranes having the same nominal chemical composition but two different morphologies are prepared by systematic changes in processing. We start with a membrane comprising a mixture of homopolymer polystyrene (hPS) and a polystyrene-b-polyethylene-b-polystyrene (SES) copolymer. hPS is subsequently selectively removed from the membrane and the polystyrene domains are sulfonated to give S-SES membranes. The morphology of the membranes is controlled by controlling Φ v, the volume fraction of hPS in the blended membrane. The morphology of the membranes was studied by small angle X-ray scattering (SAXS), cryogenic scanning transmission electron microscopy (cryo-STEM), and cryogenic electron tomography. The overall domain swelling measured by SAXS decreases slightly at Φ v = 0.29; a crossover from lamellar to bicontinuous morphology is obtained at the same value of Φ v. The bicontinuous morphologies absorb more water than the lamellar morphologies. By contrast, the nanodomain swelling of the bicontinuous membrane (120%) is slightly less than that of the lamellar membrane (150%). Quantitative analysis of the STEM images and electron tomography was used to determine the swelling on the hydrophilic and hydrophobic domains due to exposure to water. The hydrophilic sulfonated polystyrene-rich domain spacing increases while the hydrophobic polyethylene domain spacing decreases when the membranes are hydrated. The extent of increase and decrease is not a strong function of Φ v.},
doi = {10.1063/1.5029452},
journal = {Journal of Chemical Physics},
number = 16,
volume = 149,
place = {United States},
year = {2018},
month = {7}
}

Journal Article:
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Figures / Tables:

Table I Table I: Membranes used in this work.

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