An investigation is reported of possible kinetic limitations to MgB2 hydrogenation. The role of H–H bond breaking, a necessary first step in the hydrogenation process, is assessed for bulk MgB2, ball-milled MgB2, as well as MgB2 mixed with Pd, Fe and TiF3 additives. The Pd and Fe additives in the MgB2 material exist as dispersed metallic particles in the size range ~5–40 nm diameter. In contrast, TiF3 reacts with MgB2 to form Ti metal, elemental B and MgF2, with the Ti and the MgF2 phases proximate to each other and coating the MgB2 particulates with a film of thickness ~3 nm. Sieverts studies of hydrogenation kinetics are reported and compared to the rate of H–H bond breaking as measured by H-D exchange studies. The results show that H–H bond dissociation does not limit the rate of hydrogenation of MgB2 because H–H bond cleavage occurs rapidly compared to the initial MgB2 hydrogenation. The results also show that surface diffusion of hydrogen atoms cannot be a limiting factor for MgB2 hydrogenation. Instead, it is speculated that it is the intrinsic stability of the B–B extended hexagonal ring structure in MgB2 that hinders the hydrogenation of this material. This supposition is supported by B K-edge x-ray absorption measurements of the materials, which showed spectroscopically that the B–B ring was intact in the material systems studied. The TiF3/MgB2 system was examined further theoretically with reaction thermodynamics and phase nucleation kinetic calculations to better understand the production of Ti metal when TiB2 is thermodynamically favored. The results show that there exist physically reasonable ranges for which nucleation kinetics supersede thermodynamics in determining the reactive pathway for the TiF3/MgB2 system and perhaps for other additive systems as well.
TiCl3 and TiF3 additives are known to facilitate hydrogenation and dehydrogenation in a variety of hydrogen storage materials, yet the associated mechanism remains under debate. Here, experimental and computational studies are reported for the reactivity with hydrogen gas of bulk and ball-milled TiCl3 and TiF3 at the temperatures and pressures for which these additives are observed to accelerate reactions when added to hydrogen storage materials. TiCl3, in either the α or δ polymorphic forms and of varying crystallite size ranging from ∼5 to 95 nm, shows no detectable reaction with prolonged exposure to hydrogen gas at elevated pressures (∼120 bar) and temperatures (up to 200 °C). Similarly, TiF3 with varying crystallite size from ∼4 to 25 nm exhibits no detectable reaction with hydrogen gas. Post-exposure vibrational and electronic structure investigations using Fourier transform infrared spectroscopy and x-ray absorption spectroscopy confirm this analysis. Moreover, there is no significant promotion of H2 dissociation at either interior or exterior surfaces, as demonstrated by H2/D2 exchange studies on pure TiF3. The computed energy landscape confirms that dissociative adsorption of H2 on TiF3 surfaces is thermodynamically inhibited. However, Ti-based additives could potentially promote H2 dissociation at interfaces where structural and compositional varieties are expected, or else by way of subsequent chemical transformations. At interfaces, metallic states could be formed intrinsically or extrinsically, possibly enabling hydrogen-coupled electronic transfer by donating electrons.
The goals of this feasibility study are to determine the technical, regulatory, and economic feasibility of a coastal research vessel powered solely by hydrogen fuel cells, assess the environmental benefits and determine the prospects for refueling such a vessel at the expected ports of call.
The Sandia HyMARC team continued its development of new synthetic, modeling, and diagnostic tools that are providing new insights into all major classes of storage materials, ranging from relatively simple systems such as PdHx and MgH2, to exceptionally complex ones, such as the metal borohydrides, as well as materials thought to be very well-understood, such as Ti-doped NaAlH4. This unprecedented suite of capabilities, capable of probing all relevant length scales within storage materials, is already having a significant impact, as they are now being used by both Seedling projects and collaborators at other laboratories within HyMARC. We expect this impact to grow as new Seedling projects begin and through collaborations with other scientists outside HyMARC. In the coming year, Sandia efforts will focus on the highest impact problems, in coordination with the other HyMARC National Laboratory partners, to provide the foundational science necessary to accelerate the discovery of new hydrogen storage materials.
A theoretical comparison is made of the “well to waves” (WTW) greenhouse gas (GHG) and criteria pollutant emissions from the SF-BREEZE high-speed hydrogen PEM fuel cell ferry and the VALLEJO ferry powered by traditional diesel engine technology but constrained to Tier 4 emissions standards. The emissions were calculated for a common maritime mission, the current ferry route between Vallejo CA and San Francisco CA. Calculations are made of the energy required for the SF-BREEZE and VALLEJO to perform the mission route profile. The SF-BREEZE requires 10.1% more fuel energy than the VALLEJO, primarily due to the SF-BREEZE being heavier. Estimates are made for the SF-BREEZE GHG emissions associated with five LH2 fuel production pathways including renewable and non-renewable (fossil-fuel based) methods. Estimates are also made for GHG emissions associated with fossil-diesel production and delivery as well as those for biodiesel, which can be considered a renewable “drop-in” fuel replacement for conventional diesel fuel. We find that the GHG emissions for the SF-BREEZE using non-renewable LH2 are significantly higher than for the Tier 4 diesel-fueled VALLEJO on a per passenger basis. However, using renewable LH2, the GHG emissions for the SF-BREEZE ferry are reduced 75.8% compared to the diesel-fueled VALLEJO operating at Tier 4 emissions standards. We also compare the criteria pollutant emissions (NOx, HC, PM10) for the SF-BREEZE to that of the VALLEJO held to Tier 4 emissions standards fueled by diesel fuel or biodiesel. Hydrogen PEM fuel cell technology dramatically reduces NOx and HC emissions below the most advanced Tier 4 criteria pollutant emissions requirements regardless of whether the LH2 is made by NG reforming or via water electrolysis using 70% renewable energy. Renewable LH2 made with greater than 84% renewable process energy is needed to also drop the SF-BREEZE PM10 emissions below that of Tier 4 for high-speed fuel cell ferry transportation. Overall, the results show that operating a hydrogen fuel cell ferry on nearly 100% renewable hydrogen provides the dramatic reduction in GHG and criteria pollutant emissions commensurate with the problems of global climate change and maritime air pollution worldwide.
Wood, Brandon C.; Stavila, Vitalie S.; Poonyayant, Natchapol; Heo, Tae W.; Ray, Keith G.; Klebanoff, Leonard E.; Udovic, Terrence J.; Lee, Jonathan R.I.; Angboonpong, Natee; Pakawatpanurut, Pasit
Internal interfaces in the Li3N/[LiNH2 + 2LiH] solid-state hydrogen storage system alter the hydrogenation and dehydrogenation reaction pathways upon nanosizing, suppressing undesirable intermediate phases to dramatically improve kinetics and reversibility. Finally, the key role of solid interfaces in determining thermodynamics and kinetics suggests a new paradigm for optimizing complex hydrides for solid-state hydrogen storage by engineering internal microstructure.
We review liquid hydrogen (LH2) as a maritime vessel fuel, from descriptions of its fundamental properties to its practical application and safety aspects, in the context of the San Francisco Bay Renewable Energy Electric Vessel with Zero Emissions (SF-BREEZE) high-speed fuel-cell ferry. Since marine regulations have been formulated to cover liquid natural gas (LNG) as a primary propulsion fuel, we frame our examination of LH2as a comparison to LNG, for both maritime use in general, and the SF-BREEZE in particular. Due to weaker attractions between molecules, LH2is colder than LNG, and evaporates more easily. We describe the consequences of these physical differences for the size and duration of spills of the two cryogenic fuels. The classical flammability ranges are reviewed, with a focus on how fuel buoyancy modifies these combustion limits. We examine the conditions for direct fuel explosion (detonation) and contrast them with initiation of normal (laminar) combustion. Direct fuel detonation is not a credible accident scenario for the SF-BREEZE. For both fuels, we review experiments and theory elucidating the deflagration to detonation transition (DDT). LH2fires have a shorter duration than energy-equivalent LNG fires, and produce significantly less thermal radiation. The thermal (infrared) radiation from hydrogen fires is also strongly absorbed by humidity in the air. Hydrogen permeability is not a leak issue for practical hydrogen plumbing. We describe the chemistry of hydrogen and methane at iron surfaces, clarifying their impact on steel-based hydrogen storage and transport materials. These physical, chemical and combustion properties are pulled together in a comparison of how a LH2or LNG pool fire on the Top Deck of the SF-BREEZE might influence the structural integrity of the aluminum deck. Neither pool fire scenario leads to net heating of the aluminum decking. Overall, LH2and LNG are very similar in their physical and combustion properties, thereby posing similar safety risks. For ships utilizing LH2or LNG, precautions are needed to avoid fuel leaks, minimize ignition sources, minimize confined spaces, provide ample ventilation for required confined spaces, and to monitor the enclosed spaces to ensure any fuel accumulation is detected far below the fuel/air mix threshold for any type of combustion.
Mg(BH4)2 is a promising solid-state hydrogen storage material, releasing 14.9 wt% hydrogen upon conversion to MgB2. Although several dehydrogenation pathways have been proposed, the hydrogenation process is less well understood. Here, we present a joint experimental-theoretical study that elucidates the key atomistic mechanisms associated with the initial stages of hydrogen uptake within MgB2. Fourier transform infrared, X-ray absorption, and X-ray emission spectroscopies are integrated with spectroscopic simulations to show that hydrogenation can initially proceed via direct conversion of MgB2 to Mg(BH4)2 complexes. The associated energy landscape is mapped by combining ab initio calculations with barriers extracted from the experimental uptake curves, from which a kinetic model is constructed. The results from the kinetic model suggest that initial hydrogenation takes place via a multi-step process: molecular H2 dissociation, likely at Mg-terminated MgB2 surfaces, is followed by migration of atomic hydrogen to defective boron sites, where the formation of stable B-H bonds ultimately leads to the direct creation of Mg(BH4)2 complexes without persistent BxHy intermediates. Implications for understanding the chemical, structural, and electronic changes upon hydrogenation of MgB2 are discussed.