How the Hydrophobic Interface between a Perfluorosulfonic Acid Polymer and Water Vapor Controls Membrane Hydration

Soniat, Marielle; Houle, Frances A.

doi:10.1021/acsapm.1c01805

How the Hydrophobic Interface between a Perfluorosulfonic Acid Polymer and Water Vapor Controls Membrane Hydration

Journal Article · Thu Apr 07 00:00:00 EDT 2022 · ACS Applied Polymer Materials

DOI:https://doi.org/10.1021/acsapm.1c01805· OSTI ID:1879823

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Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Stable hydration in perfluorinated polyelectrolyte membranes such as Nafion is essential to maintain good ion conductivity and manage permeation, especially in vapor-fed devices where water content depends on relative humidity in a gas stream. Extensive studies in the literature have shown that Nafion hydration in water vapor is controlled by its interfacial transport resistance. Nafion forms a fluorine-rich layer at the polymer-gas interface, and it has been proposed that this layer blocks water transport due to its hydrophobicity. To develop a molecular-level description of the physics underlying transport resistance in this system, we have performed a computational reaction-diffusion kinetics study of water evaporation from Nafion. Two distinct models are examined, one mimicking the blocking function proposed in the literature and the other assuming that there is no blocking, treating instead water evaporation as a dynamic balance between uptake from the gas and desorption from the polymer surface. Simulation results are compared to time-dependent infrared data over a range of 100-0% relative humidity from the literature. Only the dynamic model successfully reproduces experimental observations. This indicates that the physical nature of interfacial transport resistance is not slow diffusion across an interfacial layer; rather, it is due to the competition between dehydration and rehydration. The simulation data provide details on the accompanying water distributions throughout the membrane and on interfacial kinetics, showing that they are characterized by strong fluctuations.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231; SC0004993

OSTI ID:: 1879823

Journal Information:: ACS Applied Polymer Materials, Journal Name: ACS Applied Polymer Materials Journal Issue: 5 Vol. 4; ISSN 2637-6105

Publisher:: ACS PublicationsCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
dehydration
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simulations
water vapor

How the Hydrophobic Interface between a Perfluorosulfonic Acid Polymer and Water Vapor Controls Membrane Hydration

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