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Thermal Transitions in Perfluorosulfonated Ionomer Thin-Films

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    Thermal Transitions in Perfluorosulfonated Ionomer Thin-Films
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    • Meron Tesfaye
      Meron Tesfaye
      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
      More by Meron Tesfaye
    • Douglas I. Kushner
      Douglas I. Kushner
      Energy Technologies Area, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
      More by Douglas I. Kushner
      Orcidhttp://orcid.org/0000-0002-3020-7737
    • Bryan D. McCloskey
      Bryan D. McCloskey
      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
      More by Bryan D. McCloskey
      Orcidhttp://orcid.org/0000-0001-6599-2336
    • Adam Z. Weber
      Adam Z. Weber
      Energy Technologies Area, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
      More by Adam Z. Weber
      Orcidhttp://orcid.org/0000-0002-7749-1624
    • Ahmet Kusoglu*
      Ahmet Kusoglu
      Energy Technologies Area, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
      *E-mail: [email protected]
      More by Ahmet Kusoglu
      Orcidhttp://orcid.org/0000-0002-2761-1050
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    ACS Macro Letters

    Cite this: ACS Macro Lett. 2018, 7, 10, 1237–1242
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    https://doi.org/10.1021/acsmacrolett.8b00628
    Published September 20, 2018
    Copyright © 2018 American Chemical Society
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    Abstract

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    Thin perfluorosulfonated ion-conducting polymers (PFSI ionomers) in energy-conversion devices have limitations in functionality attributed to confinement-driven and surface-dependent interactions. This study highlights the effects of confinement and interface-dependent interactions of PFSI thin-films by exploring thin-film thermal transition temperature (TT). Change in TT in polymers is an indicator for chain relaxation and mobility with implications on properties like gas transport. This work demonstrates an increase in TT with decreasing PFSI film thickness in acid (H+) form (from 70 to 130 °C for 400 to 10 nm, respectively). In metal cation (M+) exchanged PFSI, TT remained constant with thickness. Results point to an interplay between increased chain mobility at the free surface and hindered motion near the rigid substrate interface, which is amplified upon further confinement. This balance is additionally impacted by ionomer intermolecular forces, as strong electrostatic networks within the PFSI–M+ matrix raises TT above the mainly hydrogen-bonded PFSI–H+ ionomer.

    Copyright © 2018 American Chemical Society

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    This article is cited by 28 publications.

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    ACS Macro Letters

    Cite this: ACS Macro Lett. 2018, 7, 10, 1237–1242
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsmacrolett.8b00628
    Published September 20, 2018
    Copyright © 2018 American Chemical Society
    Request reuse permissions

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