Water Dynamics of Superacid Aromatic Proton Exchange Membranes for Fuel Cell Applications

Huang, Zitan; Oh, Sol Mi; Winey, Karen I.; Hickner, Michael A.

doi:10.1021/acs.macromol.4c02925

Water Dynamics of Superacid Aromatic Proton Exchange Membranes for Fuel Cell Applications

Journal Article · Thu Feb 20 00:00:00 EST 2025 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.4c02925· OSTI ID:2530948

^[1]; Oh, Sol Mi ^[2]; ^[2]; ^[3]

Pennsylvania State University, Philadelphia, PA (United States)
University of Pennsylvania, Philadelphia, PA (United States)
Michigan State University, East Lansing, MI (United States)

Proton exchange membranes (PEMs) with high conductivity are of critical importance for the development of fuel cells, electrolyzers, and other electrochemical technologies. In this research, poly(1,1,2,2-tetrafluoro-2-phenoxyethane-1-sulfonic acid) (PTPS) with an aromatic polymer main chain and a perfluorinated superacidic polymer side chain was synthesized. The water dynamics of PTPS were characterized across various length scales using a combination of Fourier-transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR) and compared with Nafion, a standard perfluorinated PEM, and sulfonated poly(ether sulfone) (SPES 40), an aromatic PEM without perfluorinated superacid side chains. The T₁ and T₂ relaxation times of water in the samples probed by NMR increase from SPES 40 to PTPS to Nafion, indicating that the local motion of the water molecules becomes faster. This trend corresponds well with the relative fraction of bulk-like water determined using FTIR. At larger length scales, the diffusion coefficient of water was characterized using pulsed-field gradient NMR (PFG-NMR). At a longer diffusion time (Δ = 100 ms), PTPS has a smaller diffusion coefficient compared with both Nafion and SPES 40, due to restricted diffusion, and this effect is also evident in the proton conductivity of the hydrated membranes. From this comparison, it is apparent that the aromatic backbone and side chain type greatly influence the water dynamics in PEMs at various length scales and the water dynamics significantly impact the bulk proton conductivity. These insights will lead to new designs for aromatic PEMs and help to identify bottlenecks in current materials.

View Accepted Manuscript (DOE)

Research Organization:: Michigan State University, East Lansing, MI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0023386

OSTI ID:: 2530948

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 5 Vol. 58; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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