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Impact of Hydration and Sulfonation on the Morphology and Ionic Conductivity of Sulfonated Poly(phenylene) Proton Exchange Membranes

Macromolecules

Sorte, Eric G.; Paren, Benjamin A.; Rodriguez, Christina G.; Fujimoto, Cy F.; Jenkins, Cassandria E.; Abbott, Lauren J.; Lynd, Nathaniel A.; Winey, Karen I.; Frischknecht, Amalie F.; Alam, Todd M.

Multiple computational and experimental techniques are used to understand the nanoscale morphology and water/proton transport properties in a series of sulfonated Diels-Alder poly(phenylene) (SDAPP) membranes over a wide range of temperature, hydration, and sulfonation conditions. New synthetic methods allow us to sulfonate the SDAPP membranes to much higher ion exchange capacity levels than has been previously possible. Nanoscale phase separation between the hydrophobic polymer backbone and the hydrophilic water/sulfonic acid groups was observed for all membranes studied. We find good agreement between structure factors calculated from atomistic molecular dynamics (MD) simulations and those measured by X-ray scattering. With increasing hydration, the scattering ionomer peak in SDAPP is found to decrease in intensity. This intensity decrease is shown to be due to a reduction of scattering contrast between the water and polymer and is not indicative of any loss of nanoscale phase separation. Both MD simulations and density functional theory (DFT) calculations show that as hydration levels are increased, the nanostructure morphology in SDAPP evolves from isolated ionic domains to fully percolated water networks containing progressively weaker hydrogen bond strengths. The conductivity of the membranes is measured by electrical impedance spectroscopy and the equivalent proton conductivity calculated from pulsed-field-gradient (PFG) NMR diffusometry measurements of the hydration waters. Comparison of the measured and calculated conductivity reveals that in SDAPP the proton conduction mechanism evolves from being dominated by vehicular transport at low hydration and sulfonation levels to including a significant contribution from the Grötthuss mechanism (also known as structural diffusion) at higher hydration and sulfonation levels. The observed increase in conductivity reflects the impact that changing hydration and sulfonation have on the morphology and hydrogen bond network and ultimately on the membrane performance.

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TYPE Journal Article YEAR 2019
ScopusOSTIDOI

Diels alder polyphenylene anion exchange membrane for nonaqueous redox flow batteries

Journal of the Electrochemical Society

Small, Leo J.; Pratt, Harry P.; Fujimoto, Cy F.; Anderson, Travis M.

Here highly conductive, solvent-resistant anionic Diels Alder polyphenylene (DAPP) membranes were synthesized with three different ionic contents and tested in an ionic liquid-based nonaqueous redox flow battery (RFB). These membranes display 3-10× increase in conductivity in propylene carbonate compared to some commercially available (aqueous) anion exchange membranes. The membrane with an ion content of 1.5 meq/g (DAPP1.5) proved too brittle for operation in a RFB, while the membrane with an ion content of 2.5 meq/g (DAPP2.5) allowed excessive movement of solvent and poor electrochemical yields (capacity fade). Despite having lower voltage efficiencies compared to DAPP2.5, the membrane with an intermediate ion content of 2.0 meq/g (DAPP2.0) exhibited higher coulombic efficiencies (96.4% vs. 89.1%) and electrochemical yields (21.6% vs. 10.9%) after 50 cycles. Crossover of the electroactive species was the primary reason for decreased electrochemical yields. Analysis of the anolyte and catholyte revealed degradation of the electroactive species and formation of a film at the membrane-solution interface. Increases in membrane resistance were attributed to mechanical and thermal aging of the membrane; no chemical change was observed. Improvements in the ionic selectivity and ionic conductivity of the membrane will increase the electrochemical yield and voltage efficiency of future nonaqueous redox flow batteries.

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TYPE Journal Article YEAR 2016
ScopusOSTIDOI

Poly(phenylene)-based anion exchange membranes for alkaline fuel cells

ECS Transactions

Hibbs, M.R.; Fujimoto, Cy F.; Cornelius, C.J.

Cationic polymer membranes that conduct free anions comprise an enabling research area for alkaline membrane fuel cells and other solid-state electrochemical devices that operate at high pH. The synthesis of anion exchange membranes based on a poly(phenylene) backbone prepared by a Diels-Alder reaction is demonstrated as a potential material for alkaline fuel cells. The poly(phenylene)s have benzylic methyl groups that are converted to bromomethyl groups by a radical reaction. Cationic polymers result from conversion of the bromomethyl groups to ionic moieties by quaternization with trimethylamine in the solid state. The conversion to benzyltrimethyl ammonium groups is incomplete as evidenced by the differences between the IEC values measured by titration and the theoretical IECs based on 1H NMR measurements. The anion exchange membranes formed from these polymers have hydroxide ion conductivities as high as 50 mS/cm in liquid water and they are stable under highly basic conditions at elevated temperatures. ©The Electrochemical Society.

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TYPE Conference YEAR 2009
ScopusOSTI

Advanced proton-exchange materials for energy efficient fuel cells

Cornelius, Christopher J.; Fujimoto, Cy F.; Hickner, Michael A.; Staiger, Chad S.

The ''Advanced Proton-Exchange Materials for Energy Efficient Fuel Cells'' Laboratory Directed Research and Development (LDRD) project began in October 2002 and ended in September 2005. This LDRD was funded by the Energy Efficiency and Renewable Energy strategic business unit. The purpose of this LDRD was to initiate the fundamental research necessary for the development of a novel proton-exchange membranes (PEM) to overcome the material and performance limitations of the ''state of the art'' Nafion that is used in both hydrogen and methanol fuel cells. An atomistic modeling effort was added to this LDRD in order to establish a frame work between predicted morphology and observed PEM morphology in order to relate it to fuel cell performance. Significant progress was made in the area of PEM material design, development, and demonstration during this LDRD. A fundamental understanding involving the role of the structure of the PEM material as a function of sulfonic acid content, polymer topology, chemical composition, molecular weight, and electrode electrolyte ink development was demonstrated during this LDRD. PEM materials based upon random and block polyimides, polybenzimidazoles, and polyphenylenes were created and evaluated for improvements in proton conductivity, reduced swelling, reduced O{sub 2} and H{sub 2} permeability, and increased thermal stability. Results from this work reveal that the family of polyphenylenes potentially solves several technical challenges associated with obtaining a high temperature PEM membrane. Fuel cell relevant properties such as high proton conductivity (>120 mS/cm), good thermal stability, and mechanical robustness were demonstrated during this LDRD. This report summarizes the technical accomplishments and results of this LDRD.

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TYPE SAND Report YEAR 2005
OSTIDOI

Bio micro fuel cell grand challenge final report

Apblett, Christopher A.; Novak, James L.; Hudgens, James J.; Podgorski, Jason R.; Brozik, Susan M.; Flemming, Jeb H.; Ingersoll, David I.; Eisenbies, Stephen E.; Shul, Randy J.; Cornelius, Christopher J.; Fujimoto, Cy F.; Schubert, William K.; Hickner, Michael A.; Volponi, Joanne V.; Kelley, Michael J.; Zavadil, Kevin R.; Staiger, Chad S.; Dolan, Patricia L.; Harper, Jason C.; Doughty, Daniel H.; Casalnuovo, Stephen A.; Kelley, John B.; Simmons, Blake S.; Borek, Theodore T.; Meserole, Stephen M.; Alam, Todd M.; Cherry, Brian B.; Roberts, Greg

Abstract not provided.

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TYPE SAND Report YEAR 2005
OSTIDOI
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57 Results