Fluorine-Free Precise Polymer Electrolyte for Efficient Proton Transport: Experiments and Simulations

Paren, Benjamin A.; Thurston, Bryce A.; Kanthawar, Arjun; Neary, William J.; Kendrick, Aaron; Maréchal, Manuel; Kennemur, Justin G.; Stevens, Mark J.; Frischknecht, Amalie L.; Winey, Karen I.

doi:10.1021/acs.chemmater.1c01443

Title: Fluorine-Free Precise Polymer Electrolyte for Efficient Proton Transport: Experiments and Simulations

Journal Article · Tue Jul 27 00:00:00 EDT 2021 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.1c01443· OSTI ID:1817735

^[1]; Thurston, Bryce A. ^[2]; Kanthawar, Arjun ^[1]; Neary, William J. ^[3]; Kendrick, Aaron ^[3];

^[4];

^[3]; Stevens, Mark J. ^[2];

^[2];

^[1]

Univ. of Pennsylvania, Philadelphia, PA (United States)
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Center for Integrated Nanotechnologies (CINT)
Florida State Univ., Tallahassee, FL (United States)
Université Grenoble Alpes, Grenoble (France). CNRS, CEA, IRIG-SyMMES

Designing polymers with controlled nanoscale morphologies and scalable synthesis is of great interest in the development of fluorine-free materials for proton-exchange membranes in fuel cells. This study focuses on a precision polyethylene with phenylsulfonic acid branches at every fifth carbon, p5PhSA, with a high ion-exchange capacity (4.2 mmol/g). The polymers self-assemble into hydrophilic and hydrophobic co-continuous nanoscale domains. In the hydrated state, the hydrophilic domain, composed of polar sulfonic acid moieties and water, serves as a pathway for efficient mesoscopic proton conductivity. The morphology and proton transport of p5PhSA are evaluated under hydrated conditions using in situ X-ray scattering and electrochemical impedance spectroscopy techniques. Additionally, at 40 °C and 95% relative humidity, the proton conductivity of p5PhSA is 0.28 S/cm, which is four times greater than Nafion 117 under the same conditions. Atomistic molecular dynamics (MD) simulations are also used to elucidate the interplay between the structure and the water dynamics. The MD simulations show strong nanophase separation between the percolated hydrophilic and hydrophobic domains over a wide range of water contents. The percolated hydrophilic nanoscale domain facilitates the rapid proton transport in p5PhSA and demonstrates the potential of precise hydrocarbon-based polymers as processible and effective proton-exchange membranes.

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Research Organization:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF); Agence Nationale de la Recherche (ANR)

Grant/Contract Number:: NA0003525; DMR 1904767; PIRE 1545884; ANR-15-PIRE-0001-01; ANR-15-PIRE-0001-04

OSTI ID:: 1817735

Report Number(s):: SAND-2021-9255J; 698241

Journal Information:: Chemistry of Materials, Vol. 33, Issue 15; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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