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Influence of Mesoscale Interactions on Proton, Water, and Electrokinetic Transport in Solvent-Filled Membranes: Theory and Simulation

  • Andrew R. Crothers
    Andrew R. Crothers
    Department of Chemical and Biomolecular Engineering, University of California, Berkeley, Berkeley, California 94720 United States
    Energy Technologies Area, Lawrence Berkeley National Laboratory, Berkeley, California 94720 United States
  • Ahmet Kusoglu
    Ahmet Kusoglu
    Energy Technologies Area, Lawrence Berkeley National Laboratory, Berkeley, California 94720 United States
  • Clayton J. Radke
    Clayton J. Radke
    Department of Chemical and Biomolecular Engineering, University of California, Berkeley, Berkeley, California 94720 United States
    Earth and Environmental Sciences Area, Lawrence Berkeley National Laboratory, Berkeley, California 94720 United States
  • , and 
  • Adam Z. Weber*
    Adam Z. Weber
    Department of Chemical and Biomolecular Engineering, University of California, Berkeley, Berkeley, California 94720 United States
    Energy Technologies Area, Lawrence Berkeley National Laboratory, Berkeley, California 94720 United States
    *Email: [email protected]
Cite this: Langmuir 2022, 38, 34, 10362–10374
Publication Date (Web):August 15, 2022
https://doi.org/10.1021/acs.langmuir.2c00706
Copyright © 2022 American Chemical Society

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    Abstract

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    Transport of protons and water through water-filled, phase-separated cation-exchange membranes occurs through a network of interconnected nanoscale hydrophilic aqueous domains. This paper uses numerical simulations and theory to explore the role of the mesoscale network on water, proton, and electrokinetic transport in perfluorinated sulfonic acid (PFSA) membranes, pertinent to electrochemical energy-conversion devices. Concentrated-solution theory describes microscale transport. Network simulations model mesoscale effects and ascertain macroscopic properties. An experimentally consistent 3D Voronoi-network topology characterizes the interconnected channels in the membrane. Measured water, proton, and electrokinetic transport properties from literature validate calculations of macroscopic properties from network simulations and from effective-medium theory. The results demonstrate that the hydrophilic domain size affects the various microscale, domain-level transport modes dissimilarly, resulting in different distributions of microscale coefficients for each mode of transport. As a result, the network mediates the transport of species nonuniformly with dissimilar calculated tortuosities for water, proton, and electrokinetic transport coefficients (i.e., 4.7, 3.0, and 6.1, respectively, at a water content of 8 H2O molecules per polymer charge equivalent). The dominant water-transport pathways across the membrane are different than those taken by the proton cation. Finally, the distribution of transport properties across the network induces local electrokinetic flows that couple water and proton transport; specifically, local electrokinetic transport induces water chemical-potential gradients that decrease macroscopic conductivity by up to a factor of 3. Macroscopic proton, water, and electrokinetic transport coefficients depend on the collective microscale transport properties of all modes of transport and their distribution across the hydrophilic domain network.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.langmuir.2c00706.

    • Appendixes with derivations of the pedagogical model; calculation of microscale transport coefficients; algorithm of network generation and solutions; and effective-medium theory (PDF)

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    Cited By

    This article is cited by 1 publications.

    1. Thomas Y. George, Isabelle C. Thomas, Naphtal O. Haya, John P. Deneen, Cliffton Wang, Michael J. Aziz. Membrane–Electrolyte System Approach to Understanding Ionic Conductivity and Crossover in Alkaline Flow Cells. ACS Applied Materials & Interfaces 2023, 15 (49) , 57252-57264. https://doi.org/10.1021/acsami.3c14173

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