skip to main content

DOE PAGESDOE PAGES

Title: Impact of Nano- and Mesoscales on Macroscopic Cation Conductivity in Perfluorinated-Sulfonic-Acid Membranes

A mean-field local-density theory is outlined for ion transport in perfluorinated-sulfonic-acid (PFSA) membranes. A theory of molecular-level interactions predict nanodomain and macroscale conductivity. The effects of solvation, dielectric saturation, dispersion forces, image charge, finite size, and confinement are included in a physically consistent 3D-model domain geometry. Probability-distribution profiles of aqueous cation concentration at the domain-scale are in agreement with atomistic simulations using no explicit fitting parameters. Measured conductivities of lithium-, sodium-, and proton-form membranes with equivalent weights of 1100, 1000, and 825 g/mol(SO3) validate the macroscale predictions using a single-value mesoscopic fitting parameter. Cation electrostatic interactions with pendant sulfonate groups are the largest source of migration resistance at the domain-scale. Tortuosity of ionically conductive domains is the largest source of migration resistance at the macroscale. In conclusion, our proposed transport model is consistent across multiple length scales. We provide a compelling methodology to guide material design and optimize performance in energy-conversion applications of PFSA membranes.
Authors:
ORCiD logo [1] ;  [2] ; ORCiD logo [3]
  1. Univ. of California, Berkeley, CA (United States). Chemical and Biomolecular Engineering Dept.; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Conversion Group
  2. Univ. of California, Berkeley, CA (United States). Chemical and Biomolecular Engineering Dept.; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Earth Sciences Division
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Conversion Group
Publication Date:
Grant/Contract Number:
AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 51; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1460302

Crothers, Andrew R., Radke, Clayton J., and Weber, Adam Z.. Impact of Nano- and Mesoscales on Macroscopic Cation Conductivity in Perfluorinated-Sulfonic-Acid Membranes. United States: N. p., Web. doi:10.1021/acs.jpcc.7b07360.
Crothers, Andrew R., Radke, Clayton J., & Weber, Adam Z.. Impact of Nano- and Mesoscales on Macroscopic Cation Conductivity in Perfluorinated-Sulfonic-Acid Membranes. United States. doi:10.1021/acs.jpcc.7b07360.
Crothers, Andrew R., Radke, Clayton J., and Weber, Adam Z.. 2017. "Impact of Nano- and Mesoscales on Macroscopic Cation Conductivity in Perfluorinated-Sulfonic-Acid Membranes". United States. doi:10.1021/acs.jpcc.7b07360. https://www.osti.gov/servlets/purl/1460302.
@article{osti_1460302,
title = {Impact of Nano- and Mesoscales on Macroscopic Cation Conductivity in Perfluorinated-Sulfonic-Acid Membranes},
author = {Crothers, Andrew R. and Radke, Clayton J. and Weber, Adam Z.},
abstractNote = {A mean-field local-density theory is outlined for ion transport in perfluorinated-sulfonic-acid (PFSA) membranes. A theory of molecular-level interactions predict nanodomain and macroscale conductivity. The effects of solvation, dielectric saturation, dispersion forces, image charge, finite size, and confinement are included in a physically consistent 3D-model domain geometry. Probability-distribution profiles of aqueous cation concentration at the domain-scale are in agreement with atomistic simulations using no explicit fitting parameters. Measured conductivities of lithium-, sodium-, and proton-form membranes with equivalent weights of 1100, 1000, and 825 g/mol(SO3) validate the macroscale predictions using a single-value mesoscopic fitting parameter. Cation electrostatic interactions with pendant sulfonate groups are the largest source of migration resistance at the domain-scale. Tortuosity of ionically conductive domains is the largest source of migration resistance at the macroscale. In conclusion, our proposed transport model is consistent across multiple length scales. We provide a compelling methodology to guide material design and optimize performance in energy-conversion applications of PFSA membranes.},
doi = {10.1021/acs.jpcc.7b07360},
journal = {Journal of Physical Chemistry. C},
number = 51,
volume = 121,
place = {United States},
year = {2017},
month = {11}
}