skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Abstract

Here, 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 exposuremore » 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) (SC-22)
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. doi: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. doi: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 = {Here, 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 Φv, 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 Φv = 0.29; a crossover from lamellar to bicontinuous morphology is obtained at the same value of Φv. 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 Φv.},
doi = {10.1063/1.5029452},
journal = {Journal of Chemical Physics},
number = 16,
volume = 149,
place = {United States},
year = {2018},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Figures / Tables:

Table I Table I: Membranes used in this work.

Save / Share:

Works referenced in this record:

Sulfonated hydrocarbon membranes for medium-temperature and low-humidity proton exchange membrane fuel cells (PEMFCs)
journal, November 2011


Main-chain, statistically sulfonated proton exchange membranes: the relationships of acid concentration and proton mobility to water content and their effect upon proton conductivity
journal, January 2007

  • Peckham, Timothy J.; Schmeisser, Jennifer; Rodgers, Marianne
  • Journal of Materials Chemistry, Vol. 17, Issue 30
  • DOI: 10.1039/b702339a

Self‐consistent theory of block copolymer blends: Neutral solvent
journal, August 1990

  • Whitmore, M. D.; Noolandi, J.
  • The Journal of Chemical Physics, Vol. 93, Issue 4
  • DOI: 10.1063/1.458879

Water Uptake by and Transport Through Nafion® 117 Membranes
journal, January 1993

  • Zawodzinski, Thomas A.
  • Journal of The Electrochemical Society, Vol. 140, Issue 4
  • DOI: 10.1149/1.2056194

High Performance Vanadium Redox Flow Batteries with Optimized Electrode Configuration and Membrane Selection
journal, January 2012

  • Liu, Q. H.; Grim, G. M.; Papandrew, A. B.
  • Journal of The Electrochemical Society, Vol. 159, Issue 8
  • DOI: 10.1149/2.051208jes

Increased Water Retention in Polymer Electrolyte Membranes at Elevated Temperatures Assisted by Capillary Condensation
journal, November 2007

  • Park, Moon Jeong; Downing, Kenneth H.; Jackson, Andrew
  • Nano Letters, Vol. 7, Issue 11
  • DOI: 10.1021/nl072617l

Ordering Transition of Block Copolymer Films
journal, April 2005

  • Arceo, Abraham; Green, Peter F.
  • The Journal of Physical Chemistry B, Vol. 109, Issue 15
  • DOI: 10.1021/jp050636i

Phase Behavior of a Block Copolymer in Solvents of Varying Selectivity
journal, August 2000

  • Hanley, Kenneth J.; Lodge, Timothy P.; Huang, Ching-I
  • Macromolecules, Vol. 33, Issue 16
  • DOI: 10.1021/ma000318b

Conductivity and water uptake in block copolymers containing protonated polystyrene sulfonate and their imidazolium salts
journal, January 2011

  • Wang, Xin; Beers, Keith M.; Kerr, John B.
  • Soft Matter, Vol. 7, Issue 9
  • DOI: 10.1039/c0sm01520b

Water Uptake and Proton Conductivity in Porous Block Copolymer Electrolyte Membranes
journal, August 2015


Humidity-Induced Phase Transitions in Ion-Containing Block Copolymer Membranes
journal, March 2008

  • Park, Moon Jeong; Nedoma, Alisyn J.; Geissler, Phillip L.
  • Macromolecules, Vol. 41, Issue 6
  • DOI: 10.1021/ma702320t

Block Copolymer Membranes for Efficient Capture of a Chemotherapy Drug
journal, July 2016


Swelling study of perfluorosulphonated ionomer membranes
journal, January 1993


Effect of Crystallization on Proton Transport in Model Polymer Electrolyte Membranes
journal, June 2014

  • Beers, Keith M.; Wong, David T.; Jackson, Andrew J.
  • Macromolecules, Vol. 47, Issue 13
  • DOI: 10.1021/ma500298w

The water content dependence of electro-osmotic drag in proton-conducting polymer electrolytes
journal, February 1995


Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries
journal, March 2013

  • Bouchet, Renaud; Maria, Sébastien; Meziane, Rachid
  • Nature Materials, Vol. 12, Issue 5
  • DOI: 10.1038/nmat3602

Ion-containing polymers: new energy & clean water
journal, May 2010


Transport Properties of Sulfonated Poly(styrene- b -isobutylene- b -styrene) Triblock Copolymers at High Ion-Exchange Capacities
journal, January 2006

  • Elabd, Yossef A.; Napadensky, Eugene; Walker, Charles W.
  • Macromolecules, Vol. 39, Issue 1
  • DOI: 10.1021/ma051958n

Ionic Conductivity of Low Molecular Weight Block Copolymer Electrolytes
journal, January 2013

  • Yuan, Rodger; Teran, Alexander A.; Gurevitch, Inna
  • Macromolecules, Vol. 46, Issue 3
  • DOI: 10.1021/ma3024552

Effect of Morphology of Nanoscale Hydrated Channels on Proton Conductivity in Block Copolymer Electrolyte Membranes
journal, June 2014

  • Chen, X. Chelsea; Wong, David T.; Yakovlev, Sergey
  • Nano Letters, Vol. 14, Issue 7
  • DOI: 10.1021/nl501537p

Diffusion in microstructured block copolymer solutions
journal, May 1991

  • Balsara, N. P.; Eastman, C. E.; Foster, M. D.
  • Makromolekulare Chemie. Macromolecular Symposia, Vol. 45, Issue 1
  • DOI: 10.1002/masy.19910450124

Block Copolymers for Fuel Cells
journal, January 2011

  • Elabd, Yossef A.; Hickner, Michael A.
  • Macromolecules, Vol. 44, Issue 1
  • DOI: 10.1021/ma101247c

Phase Behavior of Symmetric Sulfonated Block Copolymers
journal, May 2008

  • Park, Moon Jeong; Balsara, Nitash P.
  • Macromolecules, Vol. 41, Issue 10
  • DOI: 10.1021/ma702733f

Phase Behavior of Polystyrene- block -poly(2-vinylpyridine) Copolymers in a Selective Ionic Liquid Solvent
journal, July 2009

  • Virgili, Justin M.; Hexemer, Alexander; Pople, John A.
  • Macromolecules, Vol. 42, Issue 13
  • DOI: 10.1021/ma900483n

Morphology and Conductivity in Ionic Liquid Incorporated Sulfonated Block Copolymers
journal, July 2011

  • Kim, Sung Yeon; Yoon, Eunjin; Joo, Taiha
  • Macromolecules, Vol. 44, Issue 13
  • DOI: 10.1021/ma200278c

Self-Assembly and Transport Limitations in Confined Nafion Films
journal, January 2013

  • Modestino, Miguel A.; Paul, Devproshad K.; Dishari, Shudipto
  • Macromolecules, Vol. 46, Issue 3, p. 867-873
  • DOI: 10.1021/ma301999a

Triblock copolymer ionomer membranes
journal, March 2004

  • Elabd, Yossef A.; Walker, Charles W.; Beyer, Frederick L.
  • Journal of Membrane Science, Vol. 231, Issue 1-2
  • DOI: 10.1016/j.memsci.2003.11.019

Determination of water diffusion coefficients in perfluorosulfonate ionomeric membranes
journal, July 1991

  • Zawodzinski, Thomas A.; Neeman, Michal; Sillerud, Laurel O.
  • The Journal of Physical Chemistry, Vol. 95, Issue 15
  • DOI: 10.1021/j100168a060

Enhanced proton transport in nanostructured polymer electrolyte/ionic liquid membranes under water-free conditions
journal, October 2010

  • Kim, Sung Yeon; Kim, Suhan; Park, Moon Jeong
  • Nature Communications, Vol. 1, Issue 1
  • DOI: 10.1038/ncomms1086

Design of Cluster-free Polymer Electrolyte Membranes and Implications on Proton Conductivity
journal, September 2012

  • Beers, Keith M.; Balsara, Nitash P.
  • ACS Macro Letters, Vol. 1, Issue 10
  • DOI: 10.1021/mz300389f