Impact of Platinum Primary Particle Loading on Fuel Cell Performance: Insights from Catalyst/Ionomer Ink Interactions.

A variety of electrochemical energy conversion technologies, including fuel cells, rely on solution-processing techniques (via inks) to form their catalyst layers (CLs). The CLs are heterogeneous structures, often with uneven ion-conducting polymer (ionomer) coverage and underutilized catalysts. Various platinum-supported-on-carbon colloidal catalyst particles are used, but little is known about how or why changing the primary particle loading (PPL, or the weight fraction of platinum of the carbon-platinum catalyst particles) impacts performance. By investigating the CL gas-transport resistance and zeta (ζ)-potentials of the corresponding inks as a function of PPL, a direct correlation between the CL high current density performance and ink ζ-potential is observed. This correlation stems from likely changes in ionomer distributions and catalyst-particle agglomeration as a function of PPL, as revealed by pH, ζ-potential, and impedance measurements. These findings are critical to unraveling the ionomer distribution heterogeneity in ink-based CLs and enabling enhanced Pt utilization and improved device performance for fuel cells and related electrochemical devices.

Modifying the Electrocatalyst-Ionomer Interface via Sulfonated Poly(ionic liquid) Block Copolymers to Enable High-Performance Polymer Electrolyte Fuel Cells.

Polymer electrolyte membrane fuel cell (PEMFC) electrodes with a 0.07 mgPt cm-2 Pt/Vulcan electrocatalyst loading, containing only a sulfonated poly(ionic liquid) block copolymer (SPILBCP) ionomer, were fabricated and achieved a ca. 2× enhancement of kinetic performance through the suppression of Pt surface oxidation. However, SPILBCP electrodes lost over 70% of their electrochemical active area at 30% RH because of poor ionomer network connectivity. To combat these effects, electrodes made with a mix of Nafion/SPILBCP ionomers were developed. Mixed Nafion/SPILBCP electrodes resulted in a substantial improvement in MEA performance across the kinetic and mass transport-limited regions. Notably, this is the first time that specific activity values determined from an MEA were observed to be on par with prior half-cell results for Nafion-free Pt/Vulcan systems. These findings present a prospective strategy to improve the overall performance of MEAs fabricated with surface accessible electrocatalysts, providing a pathway to tailor the local electrocatalyst/ionomer interface.

Dictating Pt-Based Electrocatalyst Performance in Polymer Electrolyte Fuel Cells, from Formulation to Application.

In situ electrochemical diagnostics designed to probe ionomer interactions with platinum and carbon were applied to relate ionomer coverage and conformation, gleaned from anion adsorption data, with O2 transport resistance for low-loaded (0.05 mgPt cm-2) platinum-supported Vulcan carbon (Pt/Vu)-based electrodes in a polymer electrolyte fuel cell. Coupling the in situ diagnostic data with ex situ characterization of catalyst inks and electrode structures, the effect of ink composition is explained by both ink-level interactions that dictate the electrode microstructure during fabrication and the resulting local ionomer distribution near catalyst sites. Electrochemical techniques (CO displacement and ac impedance) show that catalyst inks with higher water content increase ionomer (sulfonate) interactions with Pt sites without significantly affecting ionomer coverage on the carbon support. Surprisingly, the higher anion adsorption is shown to have a minor impact on specific activity, while exhibiting a complex relationship with oxygen transport. Ex situ characterization of ionomer suspensions and catalyst/ionomer inks indicates that the lower ionomer coverage can be correlated with the formation of large ionomer aggregates and weaker ionomer/catalyst interactions in low-water content inks. These larger ionomer aggregates resulted in increased local oxygen transport resistance, namely, through the ionomer film, and reduced performance at high current density. In the water-rich inks, the ionomer aggregate size decreases, while stronger ionomer/Pt interactions are observed. The reduced ionomer aggregation improves transport resistance through the ionomer film, while the increased adsorption leads to the emergence of resistance at the ionomer/Pt interface. Overall, the high current density performance is shown to be a nonmonotonic function of ink water content, scaling with the local gas (H2, O2) transport resistance resulting from pore, thin film, and interfacial phenomena.

Enhanced Hydrothermal Stability of γ-Al2O3 Catalyst Supports with Alkyl Phosphonate Coatings.

In this study, monolayers formed from organophosphonic acids were employed to stabilize porous γ-Al2O3, both as a single component and as a support for Pt nanoparticle catalysts, during exposure to hydrothermal conditions. To provide a baseline, structural changes of uncoated γ-Al2O3 catalysts under model aqueous phase reforming conditions (liquid water at 200 °C and autogenic pressure) were examined over the course of 20 h. These changes were characterized by X-ray diffraction, NMR spectroscopy, N2 physisorption, and IR spectroscopy. It was demonstrated that γ-alumina was rapidly converted into a hydrated boehmite (AlOOH) phase with significantly decreased surface area. Deposition of alkyl phosphonate groups on γ-alumina drastically inhibited the formation of boehmite, thereby maintaining its high specific surface area over 20 h of treatment. 27Al MAS NMR spectra demonstrated that hydrothermal stability increased with alkyl tail length despite lower P coverages. Although the inhibition of boehmite formation by the phosphonic acids was attributed primarily to the formation of Al2O3-PO x bonds, it was found that use of longer-chain octadecylphosphonic acids led to the most pronounced effect. Phosphonate coatings on Pt/γ-Al2O3 improved stability without adversely affecting the rate of a model reaction, catalytic hydrogenation of 1-hexene.