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Title: Theory of Multicomponent Phenomena in Cation-Exchange Membranes: Part I. Thermodynamic Model and Validation

Abstract

We present and validate a mathematical model for multicomponent thermodynamic activity in phase-separated cation-exchange membranes (e.g., perfluorinated sulfonic-acid ionomers). The model consists of an expression for the free energy of the membrane and of the surrounding electrolyte solution. A modified Stokes-Robinson ionic solvation framework treats the solution-like non-idealities resulting from hydration, electrostatics, ion association, and physical interactions in bulk solution and in ionomer hydrophilic domains. Inside the membrane, a mechanics-based composite approach accounts for the swelling of the hydrophobic matrix. Treating the membrane microstructure as a disordered system of domains calculates steric exclusion of ions. Electroneutrality guarantees that the charge of mobile ions in the membrane is equal to the charge on polymer groups. Osmotic coefficients for electrolytes from literature parameterize solution-like interactions while mechanical and X-ray scattering characterization gives most membrane-specific parameters. Model predictions compare favorably to measured membrane thermodynamics (i.e., water and ion uptake) in dilute and concentrated binary and ternary salt electrolytes and in water vapor. Interactions between ions in the membrane are similar to those present in bulk electrolytes. Our results reveal that water and ion uptake is dictated by a balance between solution-like energetics and membrane swelling.

Authors:
; ; ; ;
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Advanced Research Projects Agency - Energy (ARPA-E); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES); US Army Research Office (ARO)
OSTI Identifier:
1598405
Alternate Identifier(s):
OSTI ID: 1619154
Grant/Contract Number:  
AC02-05CH11231; AC02-06CH11357; AR0000149; AWD00004008
Resource Type:
Published Article
Journal Name:
Journal of the Electrochemical Society (Online)
Additional Journal Information:
Journal Name: Journal of the Electrochemical Society (Online) Journal Volume: 167 Journal Issue: 1; Journal ID: ISSN 1945-7111
Publisher:
IOP Publishing
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Crothers, Andrew R., Darling, Robert M., Kusoglu, Ahmet, Radke, Clayton J., and Weber, Adam Z. Theory of Multicomponent Phenomena in Cation-Exchange Membranes: Part I. Thermodynamic Model and Validation. United States: N. p., 2020. Web. doi:10.1149/1945-7111/ab6723.
Crothers, Andrew R., Darling, Robert M., Kusoglu, Ahmet, Radke, Clayton J., & Weber, Adam Z. Theory of Multicomponent Phenomena in Cation-Exchange Membranes: Part I. Thermodynamic Model and Validation. United States. doi:10.1149/1945-7111/ab6723.
Crothers, Andrew R., Darling, Robert M., Kusoglu, Ahmet, Radke, Clayton J., and Weber, Adam Z. Fri . "Theory of Multicomponent Phenomena in Cation-Exchange Membranes: Part I. Thermodynamic Model and Validation". United States. doi:10.1149/1945-7111/ab6723.
@article{osti_1598405,
title = {Theory of Multicomponent Phenomena in Cation-Exchange Membranes: Part I. Thermodynamic Model and Validation},
author = {Crothers, Andrew R. and Darling, Robert M. and Kusoglu, Ahmet and Radke, Clayton J. and Weber, Adam Z.},
abstractNote = {We present and validate a mathematical model for multicomponent thermodynamic activity in phase-separated cation-exchange membranes (e.g., perfluorinated sulfonic-acid ionomers). The model consists of an expression for the free energy of the membrane and of the surrounding electrolyte solution. A modified Stokes-Robinson ionic solvation framework treats the solution-like non-idealities resulting from hydration, electrostatics, ion association, and physical interactions in bulk solution and in ionomer hydrophilic domains. Inside the membrane, a mechanics-based composite approach accounts for the swelling of the hydrophobic matrix. Treating the membrane microstructure as a disordered system of domains calculates steric exclusion of ions. Electroneutrality guarantees that the charge of mobile ions in the membrane is equal to the charge on polymer groups. Osmotic coefficients for electrolytes from literature parameterize solution-like interactions while mechanical and X-ray scattering characterization gives most membrane-specific parameters. Model predictions compare favorably to measured membrane thermodynamics (i.e., water and ion uptake) in dilute and concentrated binary and ternary salt electrolytes and in water vapor. Interactions between ions in the membrane are similar to those present in bulk electrolytes. Our results reveal that water and ion uptake is dictated by a balance between solution-like energetics and membrane swelling.},
doi = {10.1149/1945-7111/ab6723},
journal = {Journal of the Electrochemical Society (Online)},
number = 1,
volume = 167,
place = {United States},
year = {2020},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.1149/1945-7111/ab6723

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Cited by: 3 works
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