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Self-Assembly and Transport Limitations in Confined Nafion Films

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Download Hi-Res ImageDownload to MS-PowerPointCite This:Macromolecules 2013, 46, 3, 867-873
    Article

    Self-Assembly and Transport Limitations in Confined Nafion Films
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    † Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720, United States, and Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
    ‡ Department of Chemical Engineering, Queen’s University, Kingston, Ontario K7L 3N6, Canada
    § Department of Materials Science and Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802, United States
    ∥ National Center for Electron Microscopy, Lawrence Berkeley National Laboratory, and Department of Materials Science and Engineering, University of California, Berkeley, California 94720, United States
    ⊥ Environmental Energy Technologies Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
    *E-mail [email protected]
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    Macromolecules

    Cite this: Macromolecules 2013, 46, 3, 867–873
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    https://doi.org/10.1021/ma301999a
    Published January 23, 2013
    Copyright © 2013 American Chemical Society
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    Abstract

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    Ion-conducting polymers are important materials for a variety of electrochemical applications. Perfluorinated ionomers, such as Nafion, are the benchmark materials for proton conduction and are widely used in fuel cells and other electrochemical devices including solar-fuel generators, chlor-alkali cells, and redox flow batteries. While the behavior of Nafion in bulk membranes (10 to 100s μm thick) has been studied extensively, understanding its properties under thin-film confinement is limited. Elucidating the behavior of thin Nafion films is particularly important for the optimization of fuel-cell catalyst layers or vapor-operated solar-fuel generators, where a thin film of ionomer is responsible for the transport of ions to and from the active electrocatalytic centers. Using a combination of transport-property measurements and structural characterization, this work demonstrates that confinement of Nafion in thin films induced thickness-dependent proton conductivity and ionic-domain structure. Confining Nafion films to thicknesses below 50 nm on a silicon substrate results in a loss of microphase separation of the hydrophilic and hydrophobic domains, which drastically increases the material’s water uptake while in turn decreasing its ionic conductivity.

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    Substrate preparation procedures, sample impedance spectra, ionic conductivity data, QCM mass-uptake data, TEM chemical maps, and characterization of films cast from water diluted solutions. This material is available free of charge via the Internet at http://pubs.acs.org.

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    This article is cited by 194 publications.

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    Cite this: Macromolecules 2013, 46, 3, 867–873
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    Published January 23, 2013
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