Publications

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Hydrogen produced through low-temperature water electrolysis using anion exchange membranes (AEM) combines the benefits of liquid-electrolyte alkaline electrolysis and solid-polymer proton exchange membrane electrolysis. The anion conductive ionomers in the oxygen-producing anode and hydrogen-producing cathode are a critical part of the three-dimensional electrodes. The ionomer in the hydrogen-producing cathode facilitates hydroxide ion conduction from the cathode catalyst to the anode catalyst, and water transport from the anode to the cathode catalyst through the AEM. This ionomer also binds the catalyst particles to the porous transport layer. In this study, the cathode durability was improved by use of a self-adhesive cathode ionomer to chemically bond the cathode catalyst particles to the porous transport layer. It was found that the cathode ionomers with high ion exchange capacity (IEC) were more effective than low IEC ionomers because of the need to transport water to the cathode catalyst and transport hydroxide away from the cathode. The cathode durability was improved by using ionomers which were soluble in the spray-coated cathode ink. Optimization of the catalyst and ionomer content within the cathode led to electrolysis cells which were both mechanically durable and operated at low voltage.

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In this report, we investigate the thermal reduction of the octahedral perovskite BaCe0.25Mn0.75O3(BCM) using in situ electron energy loss spectroscopy (EELS) in an aberration-corrected transmission electron microscope (TEM). The 12R-polytype of BCM is known to demonstrate high solar thermochemical hydrogen production capacity. In situ EELS measurements show that Mn is the active redox cation in BCM, undergoing thermal reduction from Mn4+to Mn3+during heating to 700 °C inside the TEM under a high vacuum. The progressive reduction of Mn4+during oxygen vacancy (Ov) formation was monitored as a function of temperature. Additionally, atomic-resolution scanning transmission electron microscopy identified two different types of twin boundaries present in the oxidized and reduced form of 12R-BCM, respectively. These two types of twin boundaries were shown, via computational modeling, to modulate the site-specific Ovformation energies in 12R-BCM. It is concluded that these types of atomic defects provide sites more energetically favorable for Ovformation during thermal reduction.

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A direct comparison between electron transparent transmission electron microscope (TEM) samples prepared with gallium (Ga) and xenon (Xe) focused ion beams (FIBs) is performed to determine if equivalent quality samples can be prepared with both ion species. We prepared samples using Ga FIB and Xe plasma focused ion beam (PFIB) while altering a variety of different deposition and milling parameters. The samples' final thicknesses were evaluated using STEM-EELS t/λ data. Using the Ga FIB sample as a standard, we compared the Xe PFIB samples to the standard and to each other. We show that although the Xe PFIB sample preparation technique is quite different from the Ga FIB technique, it is possible to produce high-quality, large area TEM samples with Xe PFIB. We also describe best practices for a Xe PFIB TEM sample preparation workflow to enable consistent success for any thoughtful FIB operator. For Xe PFIB, we show that a decision must be made between the ultimate sample thickness and the size of the electron transparent region.

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The resurgence of interest in a hydrogen economy and the development of hydrogen-related technologies has initiated numerous research and development efforts aimed at making the generation, storage, and transportation of hydrogen more efficient and affordable. Solar thermochemical hydrogen production (STCH) is a process that potentially exhibits numerous benefits such as high reaction efficiencies, tunable thermodynamics, and continued performance over extended cycling. Although CeO₂ has been the de facto standard STCH material for many years, more recently 12R-Ba₄CeMn₃O₁₂ (BCM) has demonstrated enhanced hydrogen production at intermediate H₂/H₂O conditions compared to CeO₂, making it a contender for large-scale hydrogen production. However, the thermo-reduction stability of 12R-BCM dictates the oxygen partial pressure (pO₂) and temperature conditions optimal for cycling. In this study, we identify the formation of a 6H-BCM polytype at high temperature and reducing conditions, experimentally and computationally, as a mechanism and pathway for 12R-BCM decomposition. 12R-BCM was synthesized with high purity and then controllably reduced using thermogravimetric analysis (TGA). Synchrotron X-ray diffraction (XRD) data is used to identify the formation of a 6H-Ba₃Ce_0.75Mn_2.25O₉ (6H-BCM) polytype that is formed at 1350 degrees C under strongly reducing pO₂. Density functional theory (DFT) total energy and defect calculations show a window of thermodynamic stability for the 6H-polytype consistent with the XRD results. These data provide the first evidence of the 6H-BCM polytype and could provide a mechanistic explanation for the superior water-splitting behaviors of 12R-BCM.

Low-Z nanocrystalline diamond (NCD) grids have been developed to reduce spurious fluorescence and avoid X-ray peak overlaps or interferences between the specimen and conventional metal grids. Here, the low-Z NCD grids are non-toxic and safe to handle, conductive, can be subjected to high-temperature heating experiments, and may be used for analytical work in lieu of metal grids. Both a half-grid geometry, which can be used for any lift-out method, or a full-grid geometry that can be used for ex situ lift-out or thin film analyses, can be fabricated and used for experiments.

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The fabrication of long-lived electrical contacts to thermoelectric Bi₂Te₃-based modules is a challenging problem due to chemical incompatibilities and rapid diffusion rates. Previously, technical guidance from SAND report 2015-7203 selected electroplated Au as the preferred method for fabrication of long-lived contacts because of concerns that the grain structure of sputtered/physical vapor deposited (PVD) Au contacts can evolve during aging. We have re-evaluated PVD Au contacts and show that they are appropriate for long-life service. We measure grain size and morphology at different aging times under accelerated temperature gradient conditions, and we show that the PVD Au contacts are stable and remain relatively unchanged. The PVD Au fabricated here is not subject to the deterioration observed in the previous report.

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