James L. Horan

The Effect of Heteropoly Acids on Stability of PFSA PEMs under Fuel Cell Operation

Membranes were cast from mixtures of the 3M perfluorinated sulfonic acid ionomer [side chain -O-(CF 2 ) 4 -SO 3 H] and various heteropoly acids (HPAs) at a 10 or 20 wt % doping level. Membrane electrode assemblies (MEAs) fabricated from these membranes were subjected to a fuel cell testing protocol from 70 to 100°C under relatively dry conditions, dew point of 70°C, to avoid leaching of the HPA. The most significant finding was that the more stable HPAs, H 4 SiW 12 O 40 , α-H 3 P 2 W 18 O 62 , and H 6 P 2 W 21 O 71 , reduce the rate of F - by over half and improve the power of the MEA by 9% under these conditions.

Copolymerization of Divinylsilyl-11-silicotungstic Acid with Butyl Acrylate and Hexanediol Diacrylate: Synthesis of a Highly Proton-Conductive Membrane for Fuel-Cell Applications

Highly conducive to high conductivity: Polyoxometalates were incorporated in the backbone of a hydrocarbon polymer to produce proton-conducting films. These first-generation materials contain large, dispersed clusters of polyoxometalates. Although the morphology of these films is not yet optimal, they already demonstrate practical proton conductivities and proton diffusion within the clusters appears to be very high.

Designing Alkaline Exchange Membranes from Scratch

Abstract : There is increasing interest in the alkaline exchange membrane (AEM) fuel cells as this device, if realized, could allow the use of inexpensive metal catalysts and the oxidation of a variety of convenient liquid fuels. While there have been some dramatic early achievements, there is still a need for a fundamental study of anion transport, cation stability and the formation of robust thin films in this area. We have undertaken a comprehensive study of AEMs where theory is linked to well-defined model systems, both in solution and in the solid state, which are characterized using very careful environmental control such that the models can be validated and used predictively. We are also fabricating a number of random copolymer AEMs that can be produced readily in large quantities, allowing us to understand film formation coupled with transport and stability. Those based on perfluorinated backbones invite interesting comparisons with the analogous proton exchange membranes.

Phosphonic Acid Based Proton Exchange Membrane

Phosphonic acid based fuel cell membranes show promise for making polymer electrolyte membranes that can operate at higher temperatures, >100C and low relative humidity. A copolymer of vinyl phosphonic acid with vinyl zirconium phosphonate has been synthesized into a clear, flexible, amorphous membrane. Chemical characterization has been accomplished using EDX, FTIR and CPMAS NMR. XRD and SAXS have been used to confirm an amorphous nature. EIS and PFGSE NMR have been used to characterize the ionic transport through the membrane on different length scales.

Novel Hybrid Heteropoly Acid/Polymer Ionomers With Very High Proton Conductivity

We have fabricated proton conducting films using monomers based on vinyl substituted silicotungstic acid heteropoly acids (HPAs) and acrylate co-monomers. In this work we probe the morphology of this system based on increasing the weight loading of the HPA to 85 wt%. Although impressive proton conductivities can be achieved with these films under hotter and drier operating conditions than in conventional proton exchange membranes, the materials have mechanical limitations. We have begun to develop more practical systems in which ester and methylene groups are eliminated from the polymer backbone.

Designing a New Ionomer from Scratch - Pushing Polypoms to the Limit

We have fabricated proton conducting films using monomers based on vinyl substituted silicotungstic acid heteropoly acids (HPAs) and acrylate co-monomers. In this work we probe the limits of this system based on increasing the weight loading of the HPA to 85 wt%. Although impressive proton conductivities can be achieved with these films under hotter and drier operating conditions than in conventional proton exchange membranes, the materials have mechanical limitations. We show that very different film morphologies can be prepared based on whether or not the film is polymerized thermally or by UV light. In general the UV cured films have superior proton conductivity, but have a linear morphology resulting in a brittle film. The thermally cured films have a clustered morphology with good mechanical attributes but have poor proton conductivity.

V.C.2 Advanced Hybrid Membranes for Next Generation PEMFC Automotive Applications

• Show that heteropoly acid (HPA)-containing films can be fabricated thin and have a low area specific resistance (ASR) at the temperature of an automotive fuel cell stack and at higher temperatures likely to be operational transients whilst also functioning as an electrical resistor. • Increase HPA loading and organization for maximum proton conduction in a functionalized commercial fluoroelastomer manufactured by 3M.

Heteropoly acid functionalized fluoroelastomer with outstanding chemical durability and performance for vehicular fuel cells

To further facilitate commercialization of automotive fuel cells, durability concerns need to be addressed. Currently the addition of a mechanical support in the membrane is able to adequately solve issues of mechanical degradation, but chemical degradation via oxygenated radical attack remains an unsolved challenge. Typical mitigation strategies use cerium or manganese species to serve as radical scavengers, but these ions are able to migrate in the membrane and even leach out of the system. The approach used in this study is to covalently link and immobilize a heteropoly acid (HPA), more specifically 11-silicotungstic acid (HSiW11), a lacunary HPA of the Keggin structure to a fluoroelastomer, serving as both a radical decomposition catalyst and the proton conducting acid. This dual functionality allows for both high content of radical scavenging species and high ion-exchange capacity. An efficient three step, high yield (77%), commercially viable synthesis for this polymer is reported. The synthesis route for making this new heteropoly acid functionalized polymer is confirmed using infrared spectroscopy (IR), nuclear magnetic resonance (NMR) spectroscopy, and thermogravimetric analysis (TGA). The material exhibits clustering of the HSiW11 moieties, resulting in a poorly connected proton conducting phase when dry, but excellent conductivity is achieved at elevated humidities (0.298 S cm−1 at 80 °C and 95% RH). The proton conductivity shows an enhancement above 60 °C due to a softening of the polymer, as shown by DSC. Under an aggressive chemical accelerated stress test (AST), 90 °C, 30% RH, zero current, and pure O2, the PolyHPA losses only 0.05 V of open circuit voltage (OCV) after 500 h, greatly out performing any other material reported in the literature. For comparison, the Nafion® N211 fuel cell drops below 0.8 V after only 76 h under the same conditions. In fuel cell testing the PolyHPAs have outstanding chemical stability and also possess very low in situ high frequency resistance (HFR) leading to high performance (1.14 W cm−2 at 2 A cm−2), compared to 1.11 W cm−2 for the Nafion® N211 fuel cell at the same current. At 75 wt% HSiW11 loading, the fuel cell HFR showed a 22% decrease over N211.

Development of alkaline fuel cells.

This project focuses on the development and demonstration of anion exchange membrane (AEM) fuel cells for portable power applications. Novel polymeric anion exchange membranes and ionomers with high chemical stabilities were prepared characterized by researchers at Sandia National Laboratories. Durable, non-precious metal catalysts were prepared by Dr. Plamen Atanassovs research group at the University of New Mexico by utilizing an aerosol-based process to prepare templated nano-structures. Dr. Andy Herrings group at the Colorado School of Mines combined all of these materials to fabricate and test membrane electrode assemblies for single cell testing in a methanol-fueled alkaline system. The highest power density achieved in this study was 54 mW/cm2 which was 90% of the project target and the highest reported power density for a direct methanol alkaline fuel cell.