11 Search Results

Steady-shear rheology showing evolution of the microstructure of iridium oxide catalyst inks of PEM water electrolyzers with aging time.

While anion exchange membrane water electrolyzers (AEMWEs) have achieved significant performance advances in recent decades, overpotentials remain high relative to their proton exchange membrane water electrolyzer (PEMWE) counterparts, requiring AEMWE-specific catalyst layer design strategies to further advance this technology. In this work, the role of the ionomer in catalyst layer structure and quality, catalyst layer stability, and ion conduction for supporting electrolyte-fed AEMWEs is assessed for catalyst layers composed of NiFe₂O₄ and PiperION TP85 from Versogen at variable ionomer contents (0–30 wt %) for tests up to 200 h. The results reveal that, for supporting electrolyte-fed AEM devices, the ionomermore » is not required for ion conduction through the catalyst layer. Instead, the ionomer is found to play a critical role in catalyst layer structure and stability, where intermediate ionomer contents lead to the lowest overpotentials, highest effective surface areas, and lowest catalyst layer resistances. Catalyst layer stability is found to be a function of both catalyst adhesion and ionomer loss. These results show that an ionomer may be selected which is not of the same chemistry as the anion exchange membrane, mitigating ionomer stability concerns throughout the catalyst layer and offering a pathway towards highly active and stable AEMWEs.« less

Abstract We investigate the effect of alcohol fraction (isopropanol, IPA) in a binary water‐alcohol solvent mixture on the shear and extensional rheological properties, as well as the role of viscoelasticity on fiber formation of poly(acrylic acid) (PAA) in electrospinning. Comparison of the scaling of both specific viscosities η _sp and extensional relaxation times λ _E of PAA in water–IPA mixtures, showed stronger scaling compared to salt‐free aqueous polyelectrolyte solutions, except for the η _sp in the unentangled regime displaying a polyelectrolyte‐like scaling η _sp  ~ c ^0.5 for all IPA%. Such deviation suggested IPA induces association/aggregation of PAA. However, the trendsmore » between η _sp and λ _E magnitudes as a function of IPA% differ for concentrations compared in the entangled regime. The η _sp as well as their elastic moduli exhibit a maximum, whereas λ _E increases monotonically with IPA%, suggesting a complex interplay of various interactions are dictating their structure in water‐IPA mixtures, affecting their shear and extensional response differently. Electrospinning experiments showed increasing IPA% reduces the onset of both beaded and uniform fibers. Analysis using dimensionless numbers indicated the enhancement of their elasticity by IPA, and the consequent stabilizing effect on their jets/filaments against break‐up during electrospinning, plays a role in the improvement of their fiber formation.« less

Leveraging the interactions between ionomer and catalyst can increase the performance of proton exchange membrane fuel cells. The impacts of the equivalent weight (EW) of perfluorosulfonic acid–based ionomers on the platinum group metal-free electrode structure and fuel cell performance have not been fully explored. Four membrane electrode assemblies (MEAs) were prepared by using a commercial Fe–N–C catalyst, two perfluorosulfonic acid ionomers with different EWs, that is, Aquivion 720 (A720) and Nafion 1100 (N1100), and two ionomer-to-catalyst (I/C) ratios. The four MEAs were characterized to understand the impact of the ionomer EW and content on the capacitance, proton conductivity, and massmore » transport on the cathode. The mass transport resistance was measured for the first time using a new oxygen reduction reaction limiting current method enabling to couple the effects of oxygen diffusion with liquid water generation. Low EW ionomer combined with a moderate I/C results in improved performance due to its enhanced proton conductivity. However, when used at high I/C, it can cause severe water flooding at high current density due to the enhanced liquid water uptake, especially at high relative humidity, resulting in lower catalyst utilization and higher mass transport resistance.« less

We investigate the effect of the poly(acrylic acid) (PAA) carrier polymer concentration on the microstructure and rheological properties of catalyst inks for electrospun polymer–electrolyte membrane fuel-cell catalyst layers. Characterization of an ink microstructure using oscillatory shear rheology showed that the catalyst particles (platinum on carbon) are significantly agglomerated in the absence of PAA or an ionomer. Both the ionomer and PAA promoted the stability of the particles against agglomeration via electrosteric stabilization by adsorbing onto the particle surface. Increasing the PAA concentration increased the stability of the particles (or reduced the agglomerated structure) due to increasing PAA coverage onto themore » free surface area of the particles. However, beyond a certain increase in concentration, PAA was found to predominantly remain as an excess free polymer in the ink due to an insufficient free/available surface area on the particles for further PAA coverage. Extensional rheology measurements demonstrated that PAA enhances the extensional viscosities of the inks. Consequently, increasing the PAA concentration in the ink promoted the evolution of uniform nanofibers. However, beyond a certain concentration, a significant increase in the shear viscosities of the inks led to defective fiber morphologies because of the onset of flow instabilities. Electrochemical performance comparisons between catalyst layers with different PAA concentrations showed maximum performance at the PAA concentration that led to the least agglomerated structure of the catalyst, most uniform fiber morphologies, and low concentrations of free (non-adsorbing) PAA in the electrode. These results provide a rationale for optimization of electrospun catalyst nanofibers for both spinnability and electrochemical performance.« less

This work investigates how local ionomer/platinum (Pt) interactions and ionomer distribution in electrospun Pt/Vulcan nanofiber electrodes impact ionomer coverage, proton accessibility, and oxygen reduction reaction (ORR) performance in proton-exchange membrane fuel cells. Insights from various in situ electrochemical diagnostics were utilized in conjunction with ex situ microscopic characterization to understand how the electrode microstructure—both at the aggregate level and near the ionomer/platinum interface—is affected by electrospinning in comparison to ultrasonic spraying. The effect of the carrier polymer poly(acrylic acid) (PAA) concentration from 5–20 wt % (with respect to total ink solids) on the resulting nanofiber morphology is discussed. Electron microscopymore » observations and CO displacement measurements indicated that Pt/Vulcan nanofibers prepared with a higher PAA concentration (15 wt %) were conformally coated with a film of ionomer on the exterior of the fiber, which resulted in an overall lower ionomer coverage on both Pt and carbon throughout the fiber diameter. In contrast, 10 wt % PAA leads to a uniform intrafiber distribution of the ionomer within the fibers, increasing the overall ionomer coverage and proton accessibility under both wet and dry conditions. These differences in the local ionomer coverage on Pt between 10 and 15 wt % PAA were also attributed to differences in the adsorption/interaction affinities between PAA and the ionomer onto the catalyst surface in the ink using zeta potential measurements. Additional fuel cell electrochemical tests on the electrospun electrodes show improvements in ORR kinetics and high-current-density H₂/air performance compared to the ultrasonically sprayed electrodes.« less

In this paper, we present an investigation of the microstructure and rheological behavior of catalyst inks consisting of Fe–N–C platinum group metal-free catalysts and a perfluorosulfonic acid ionomer in a dispersion medium (DM) of water and 1-propanol (nPA). The effects of the ionomer-to-catalyst (I/C) ratio and weight percentage of water (H₂O %) in the DM on the ink microstructure were studied. Steady-shear and dynamic-oscillatory-shear rheology, in combination with synchrotron X-ray scattering, was utilized to understand interparticle interactions and the level of agglomeration of the inks. In the absence of the ionomer, the inks were significantly agglomerated, approaching a gel-like microstructuremore » for catalyst concentrations as low as 2 wt %. The effect of H₂O % in the DM on particle agglomeration was found to vary with particle concentration. In concentrated inks (≥2 wt % catalyst), increasing H₂O % was found to increase agglomeration because of the hydrophobic nature of the catalysts. In dilute inks (<1 wt % catalyst), the trend was reversed with increasing H₂O %, suggesting that electrostatic interactions are dominating the behavior. In inks with 5 wt % catalyst, the addition of an ionomer was found to significantly stabilize the catalyst against agglomeration. Maximum stability was observed at 0.35 I/C for all DM H₂O % studied. At high ionomer concentrations (I/C > 0.35), interesting differences were observed between nPA-rich inks (H₂O % ≤ 50%) and H₂O-rich (82% H₂O) inks. The nPA-rich inks remained predominantly stable—ink viscosity only weakly increased with I/C and the Newtonian behavior was maintained for I/C up to 0.9. In contrast, the H₂O-rich inks exhibited a significant increase in viscoelasticity with increasing I/C, suggesting flocculation of the catalyst by the ionomer. These differences suggest that the nature of the interactions between the ionomer and catalyst is highly dependent on the H₂O % in the DM.« less

In this study, 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 mg_Pt 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) showmore » 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.« less

Here, we present an investigation of the structure and rheological behavior of catalyst inks for low-temperature polymer electrolyte membrane water electrolyzers. The ink consists of iridium oxide (IrO₂) catalyst particles and a Nafion ionomer dispersed in a mixture of 1-propanol and water. The effects of ionomer concentration and catalyst concentration on the microstructure of the catalyst ink were studied. Studies on dilute inks (0.1 wt % IrO₂) using zeta potential and dynamic light scattering measurements indicated a strong adsorption of the ionomer onto the catalyst particles which resulted in an increase in the ..zeta..-potential and the z-average diameter. Steady-shear andmore » dynamic-oscillatory-shear rheological measurements of concentrated IrO₂ dispersions (35 wt % IrO₂) indicated that the particles are strongly agglomerated in the absence of the ionomer. The addition of even a small amount of the ionomer (2.4 wt % with respect to total solids) caused the rheology to transition from shear thinning to Newtonian because of the reduction in agglomerated structure due to stabilization of the aggregates by the ionomer, consistent with the behavior of dilute inks. At intermediate ionomer loadings, between 2.4 and 9 wt %, the viscosity increased with increasing ionomer wt %, though remained Newtonian, predominantly due to the increasing ionomer volume fraction in the ink. For ionomer loadings greater than 9 wt %, the particles were found to be flocculated, likely induced by a dispersed ionomer. The flocculated inks exhibited strong shear-thinning and gel-like behaviors in steady-shear and oscillatory-shear rheology. The onset of flocculation was found to be sensitive to the catalyst concentration, where below 35 wt % of IrO₂, flocculation was not observed. The rheological observations were further verified by ultra-small-angle X-ray scattering.« less