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  1. Uniformity, performance, and durability of roll-to-roll-coated iridium oxide electrolyzer catalyst layers

    This work investigates the use of roll-to-roll coating methods for the production of iridium oxide catalyst layers for proton exchange membrane water electrolyzers. Catalyst layers were produced using two coating methods: slot die and gravure. By varying the solids content of the catalyst ink and coating process variables loadings between 0.08 and 0.64 mgIr cm−2 were prepared with relatively high spatial uniformity. However, at loadings below 0.2 mgIr cm−2 microscopy reveals voids in the catalyst layer due to similar length scales of catalyst agglomerates and overall layer thickness. Electrochemical testing shows that these voids do not impact initial membrane electrodemore » assembly performance but lead to increased performance losses after potential cycling compared to spray coated catalyst layers.« less
  2. Degradation Effects at the Porous Transport Layer/Catalyst Layer Interface in Polymer Electrolyte Membrane Water Electrolyzer

    The porous transport layer (PTL)/catalyst layer (CL) interface plays a crucial role in the achievement of high performance and efficiency in polymer electrolyte membrane water electrolyzers (PEMWEs). This study investigated the effects of the PTL/CL interface on the degradation of membrane electrode assemblies (MEAs) during a 4000 h test, comparing the MEAs assembled with uncoated and Ir-coated Ti PTLs. Our results show that compared to an uncoated PTL/CL interface, an optimized interface formed when using a platinum group metal (PGM) coating, i.e., an iridium layer at the PTL/CL interface, and reduced the degradation of the MEA. The agglomeration and formationmore » of voids and cracks could be found for both MEAs after the long-term test, but the incorporation of an Ir coating on the PTL did not affect the morphology change or oxidation of IrO x in the catalyst layer. In addition, our studies suggest that the ionomer loss and restructuring of the anodic MEA can also be reduced by Ir coating of the PTL/CL interface. Optimization of the PTL/CL interface improves the performance and durability of a PEMWE.« less
  3. The effect of ink ball milling time on interparticle interactions and ink microstructure and their influence on crack formation in rod-coated catalyst layers

    This work investigates the influence of ballmilling (sometimes also referred to as jar roller milling) time on cathode catalyst layer (CL) inks and electrode properties using formulations and coating methods relevant for industrial manufacturing. Four CL inks with the same composition were milled for 24, 48, 72, or 96 h. Rheological investigation of these inks showed a reduction of elastic moduli and steady-shear viscosity with continuous ink milling, which is correlated to a decrease in particle-particle interactions as well as formation of smaller agglomerates. Optical microscopy (OM) analysis of the fabricated electrodes revealed a trend in surface crack formation; formulationsmore » milled for 24 h contained the lowest average surface crack area percentages of 0.370% at heavy-duty loadings of ~0.300 mgPt cm-2, compared to 2.418% for the ink milled for 96 h. Further characterization of the CL through transmission electron microscopy (TEM) imaging showed a decrease in the mean agglomerate and pore size with milling time. Furthermore, these smaller electrode features were consistent with reduced fracture resistance and, hence, development of larger stresses during drying. Our results highlight the need to consider ink processing as an important component in defect-free CL manufacturing.« less
  4. Optimization of Extended-Surface PtNi Nanowire Oxygen Reduction Electrocatalysts Produced via Atomic Layer Deposition

    Polymer electrolyte membrane fuel cells (PEMFCs) produce electricity with only heat and water as byproducts, but sluggish kinetics of the oxygen reduction reaction (ORR) at the cathode and durability limitations restrict widespread commercialization, motivating the development of advanced catalysts. In this research, extended-surface platinum nickel (PtNi) nanowires (NWs) synthesized using the scalable atomic layer deposition (ALD) technique are investigated with the goal of exploring the durability benefits of high-aspect-ratio electrocatalysts and the tunability of beneficial kinetic properties. The surface and bulk composition and the structure of the PtNi NWs were investigated as a function of a series of postsynthesis modifications.more » The results from a combination of electron microscopy and X-ray spectroscopy characterization techniques were correlated to electrochemical performance to gain a comprehensive understanding of the structure-property-performance relationships. The robust structure of the ALD-derived NWs enabled additional postsynthesis optimization steps, which were not possible with previous-generation materials synthesized via spontaneous galvanic displacement, resulting in a catalyst with beneficial properties for catalyst kinetics as well as improved durability. Our study demonstrates potential pathways toward further improving the performance of this class of materials through optimization of bulk and surface properties of the catalyst.« less
  5. Microscopy-based Multi-technique, Multi-scale Characterization of Polymer Electrolyte Membrane Devices

    This paper will cover recent developments of both fuel cell and electrolyzer catalysts and catalyst layers, and the vital role of each technique in obtaining a comprehensive picture of how to improve constituent interactions within the device.
  6. Exploring the Interface of Skin-Layered Titanium Fibers for Electrochemical Water Splitting

    Water electrolysis is the key to a decarbonized energy system, as it enables the conversion and storage of renewably generated intermittent electricity in the form of hydrogen. However, reliability challenges arising from titanium-based porous transport layers (PTLs) have hitherto restricted the deployment of next-generation water-splitting devices. Here, it is shown for the first time how PTLs can be adapted so that their interface remains well protected and resistant to corrosion across ˜4000 h under real electrolysis conditions. It is also demonstrated that the malfunctioning of unprotected PTLs is a result triggered by additional fatal degradation mechanisms over the anodic catalystmore » layer beyond the impacts expected from iridium oxide stability. Now, superior durability and efficiency in water electrolyzers can be achieved over extended periods of operation with less-expensive PTLs with proper protection, which can be explained by the detailed reconstruction of the interface between the different elements, materials, layers, and components presented in this work.« less
  7. Investigation of the Microstructure and Rheology of Iridium Oxide Catalyst Inks for Low-Temperature Polymer Electrolyte Membrane Water Electrolyzers

    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
  8. Thermal Activation of a Copper-Loaded Covalent Organic Framework for Near-Ambient Temperature Hydrogen Storage and Delivery

    Copper(II) formate is efficiently incorporated into the pores of a 2D imine-based covalent organic framework (COF) via coordination with the phenol and imine groups. The coordinated metal ion is then reduced to Cu(I) with a thermal treatment that evolves CO2. After loading with hydrogen gas, the majority of H2 desorbs from the coordinatively saturated Cu(II) COF at temperatures < -100 degrees C. However, the activated Cu(I) COF retains adsorbed H2 above room temperature. Adsorption/desorption of H2 was highly reversible. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) strongly supports a molecular hydrogen interaction with Cu(I). A Kissinger analysis of variable rampmore » rate desorption experiments estimates the enthalpy of H2 desorption from Cu(I) at 15 kJ mol-1. The results represent an advance toward practical H2 storage and delivery in a lightweight, stable, and highly versatile material.« less
  9. ZIF 67 Based Highly Active Electrocatalysts as Oxygen Electrodes in Water Electrolyzer

    Mitigating high overpotential losses originating from the sluggish oxygen evolution reaction (OER) during water electrolysis is key to establishing a sustainable hydrogen generation technique. In this article, we report a Co-imidazolate framework (ZIF 67) as an OER catalyst that exhibits high activity in both a three electrode cell and an electrolyzer. Additionally, Fe, Ni, and Zn have been incorporated into ZIF 67 to evaluate their effects on the OER activity of ZIF 67. Due to the high charge conductivity of ZIF 67, none of the reported catalyst was carbonized at high temperature, a process that is generally accompanied by significantmore » mass loss. Finally, in addition to being highly active, these catalysts are scalable which makes them promising candidates for application in commercial power markets.« less

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"Zaccarine, Sarah"

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