Effect of GDM Pairing on PEMFC Performance in Flow-Through and Dead-Ended Anode Mode.

Asymmetric gas diffusion media (GDM) pairing, which feature distinct GDM at the anode and cathode of the proton electrolyte membrane fuel cell (PEMFC), enhance water management compared to symmetric pairing of GDM (anode and cathode GDM are identical). An asymmetric pairing of Freudenberg GDM (H24C3 at anode and H23C2 at cathode) reduces ohmic resistances by up to 40% and oxygen transport resistances by 14% en route to 25% higher current density in dry gas flows. The asymmetric GDM pairing effectively hydrates the membrane electrode assembly (MEA) while minimizing liquid water saturation in the cathode compared to a commonly used symmetric GDM pairing of SGL 29BC at the anode and cathode. Superior water management observed with asymmetric GDM in flow-through mode is also realized in dead-ended anode (DEA) mode. Compared to the symmetric GDM pairing, the asymmetric GDM pairing with Freudenberg GDM increases cell voltage at all current densities, extends and stabilizes steady-state voltage behavior, slows voltage decay, and vastly reduces the frequency of anode purge events. These results support that the asymmetric Freudenberg GDM combination renders the PEMFC less prone to anode water saturation and performance loss from the anticipated increase in water back-diffusion during DEA mode operation.

Internal Morphologies of Cycled Li-Metal Electrodes Investigated by Nano-Scale Resolution X-ray Computed Tomography.

While some commercially available primary batteries have lithium metal anodes, there has yet to be a commercially viable secondary battery with this type of electrode. Research prototypes of these cells typically exhibit a limited cycle life before dendrites form and cause internal cell shorting, an occurrence that is more pronounced during high-rate cycling. To better understand the effects of high-rate cycling that can lead to cell failure, we use ex situ nanoscale-resolution X-ray computed tomography (nano-CT) with the aid of Zernike phase contrast to image the internal morphologies of lithium metal electrodes on copper wire current collectors that have been cycled at low and high current densities. The Li that is deposited on a Cu wire and then stripped and deposited at low current density appears uniform in morphology. Those cycled at high current density undergo short voltage transients to >3 V during Li-stripping from the electrode, during which electrolyte oxidation and Cu dissolution from the current collector may occur. The effect of temperature is also explored with separate cycling experiments performed at 5 and 33 °C. The resulting morphologies are nonuniform films filled with voids that are semispherical in shape with diameters ranging from hundreds of nanometers to tens of micrometers, where the void size distributions are temperature-dependent. Low-temperature cycling elicits a high proportion of submicrometer voids, while the higher-temperature sample morphology is dominated by voids larger than 2 µm. In evaluating these morphologies, we consider the importance of nonidealities during extreme charging, such as electrolyte decomposition. We conclude that nano-CT is an effective tool for resolving features and aggressive cycling-induced anomalies in Li films in the range of 100 nm to 100 µm.

Fabrication Method for Laboratory-Scale High-Performance Membrane Electrode Assemblies for Fuel Cells.

Custom catalyst-coated membranes (CCMs) and membrane electrode assemblies (MEAs) are necessary for the evaluation of advanced electrocatalysts, gas diffusion media (GDM), ionomers, polymer electrolyte membranes (PEMs), and electrode structures designed for use in next-generation fuel cells, electrolyzers, or flow batteries. This Feature provides a reliable and reproducible fabrication protocol for laboratory scale (10 cm2) fuel cells based on ultrasonic spray deposition of a standard Pt/carbon electrocatalyst directly onto a perfluorosulfonic acid PEM.

Bromomethane Contamination in the Cathode of Proton Exchange Membrane Fuel Cells.

The effects of bromomethane (BrCH3), an airborne contaminant, on the performance of a single PEMFC are compared with that of another halocarbon, chlorobenzene. Under a constant current of 1 A cm-2 and at 45 °C, 20 ppm bromomethane causes approximately 30% cell voltage loss in approximately 30 h, as opposed to much more rapid performance degradation observed with chlorobenzene. Electrochemical impedance spectroscopy, cyclic voltammetry, linear scanning voltammetry, and polarization measurements are applied to characterize the temporary electrochemical reaction effect and permanent performance effects. X-ray absorption spectroscopy is used to confirm that Br is adsorbed on the Pt electrocatalyst surface. We conclude that airborne bromomethane poisons a PEMFC in a different way from chlorobenzene because it is largely hydrolyzed to bromide, Br-, which is then excluded from the Pt catalyst by the negatively charged Nafion ionomer. The little Br- and bromomethane that adsorbs on the Pt surface can be partially removed by cycling but causes some irreversible surface area loss.

Physical Chemistry Research Toward Proton Exchange Membrane Fuel Cell Advancement.

Hydrogen fuel cells, the most common type of which are proton exchange membrane fuel cells (PEMFCs), are on a rapid path to commercialization. We credit physical chemistry research in oxygen reduction electrocatalysis and theory with significant breakthroughs, enabling more cost-effective fuel cells. However, most of the physical chemistry has been restricted to studies of platinum and related alloys. More work is needed to better understand electrocatalysts generally in terms of properties and characterization. While the advent of such highly active catalysts will enable smaller, less expensive, and more powerful stacks, they will require better understanding and a complete restructuring of the diffusion media in PEMFCs to facilitate faster transport of the reactants (O2) and products (H2O). Even Ohmic losses between materials become more important at high power. Such lessons from PEMFC research are relevant to other electrochemical conversion systems, including Li-air batteries and flow batteries.

Experimental methods for quantifying the activity of platinum electrocatalysts for the oxygen reduction reaction.

A tutorial is provided for methods to accurately and reproducibly determine the activity of Pt-based electrocatalysts for the oxygen reduction reaction in proton exchange membrane fuel cells and other applications. The impact of various experimental parameters on electrocatalyst activity is demonstrated, and explicit experimental procedures and measurement protocols are given for comparison of electrocatalyst activity to fuel cell standards. (To listen to a podcast about this article, please go to the Analytical Chemistry multimedia page at pubs.acs.org/page/ancham/audio/index.html.).

Triarylphosphine-stabilized platinum nanoparticles in three-dimensional nanostructured films as active electrocatalysts.

Ligand-stabilized platinum nanoparticles (Pt NPs) can be used to build well-defined three-dimensional (3-D) nanostructured electrodes for better control of the catalyst architecture in proton exchange membrane fuel cells (PEMFCs). Platinum NPs of 1.7 +/- 0.5 nm diameter stabilized by the water-soluble phosphine ligand, tris(4-phosphonatophenyl)phosphine (TPPTP, P(4-C6H4PO3H2)3), were prepared by ethylene glycol reduction of chloroplatinic acid and subsequent treatment of the isolated nanoparticles with TPPTP. The isolated TPPTP-stabilized Pt NPs were characterized by multinuclear magnetic resonance spectroscopy (31P and 195Pt NMR), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and extended X-ray absorption fine structure (EXAFS). The negatively charged TPPTP-Pt NPs were electrostatically deposited onto a glassy carbon electrode (GCE) modified with protonated 4-aminophenyl functional groups (APh). Multilayers were assembled via electrostatic layer-by-layer deposition with cationic poly(allylamine HCl) (PAH). These multilayer films are active for the key hydrogen fuel cell reactions, hydrogen oxidation (anode) and oxygen reduction (cathode). Using a rotating disk electrode configuration, fully mass-transport limited kinetics for hydrogen oxidation was obtained after 3 layers of TPPTP-Pt NPs with a total Pt loading of 4.2 microg/cm2. Complete reduction of oxygen by four electrons was achieved with 4 layers of TPPTP-Pt NPs and a total Pt loading of 5.6 microg/cm2. A maximum current density for oxygen reduction was reached with these films after 5 layers resulting in a mass-specific activity, i(m), of 0.11 A/mg(Pt) at 0.9 V. These films feature a high electrocatalytic activity and can be used to create systematic changes in the catalyst chemistry and architecture to provide insight for building better electrocatalysts.

Sonochemically induced decomposition of energetic materials in aqueous media.

This study demonstrates that ultrasound rapidly degrades the energetic compounds RDX (cyclo-1,3,5-trinitramine-2,4,6-trimethylene) and ADN (ammonium dinitramide) in aqueous microheterogeneous media. The conditions for effective degradation of these nitramines, as monitored by UV absorption spectroscopy, were determined by varying sonication time, the heterogeneous phase and its suspension density, and the concentration of NaOH. In the presence of 5 mg/ml of aluminum powder and at pH approximately 12 (10 mM NaOH), 74% of the RDX and 86% of the ammonium dinitramide (ADN) in near-saturated solutions decompose within the first 20 min of sonication (20 kHz; 50 W; < or =5 degrees C). Sonication without Al powder and base yields minimal degradation of either RDX and ADN (approximately 5-10%) or the nitrite/nitrate ions that are expected byproducts during RDX and ADN degradation. Sonication at high pH in the presence of dispersed aluminosilicate zeolite, alumina, or titanium dioxide also yields minimal degradation. Preliminary electrochemical studies and product analyses indicate that in situ ultrasonic generation of metallic aluminum and/or aluminum hydride drives reductive denitration of the nitramines. Sonochemical treatment in the presence of a reductant offers an effective and rapid waste remediation option for energetic waste compounds.

Transmission electron microscopy studies of the nanoscale structure and chemistry of Pt50Ru50 electrocatalysts.

The structural and chemical heterogeneity of 2.5-nm Pt50Ru50 electrocatalysts was studied by transmission electron microscopy using selected area diffraction, lattice imaging, electron-energy loss spectroscopy, and energy-dispersive X-ray spectroscopy. The catalysts with the highest methanol oxidation activities exhibit oxidation-induced phase separation on the nanoscale to from Pt-rich metal embedded in Ru-rich hydrous and anhydrous oxide. Reduction of the oxide-on metal samples produces a true bimetallic face-centered cubic Pt50Ru50 alloy, with 275 times lower oxidation activity.