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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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Dye sensitized solar cells (DSSCs) are coated with subnanometer oxide coatings to prevent device degradation in ambient humidity and high temperatures.
Three oxygen-free pentazolate salts Na 2 N 5 , NaN 5 and NaN 5 ·N 2 were synthesized from sodium azide NaN 3 and molecular nitrogen N 2 at 50 GPa.
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Metal-organic frameworks (MOFs) are a new category of advanced porous materials undergoing study by many researchers for their vast variety of both novel structures and potentially useful properties arising from them. Their high porosities, tunable structures, and convenient process of introducing both customizable functional groups and unsaturated metal centers have afforded excellent gas sorption and separation ability, catalytic activity, luminescent properties, and more. However, the robustness and reactivity of a given framework are largely dependent on its metal-ligand interactions, where the metal-containing clusters are often vulnerable to ligand substitution by water or other nucleophiles, meaning that the frameworks may collapse upon exposure even to moist air. Other frameworks may collapse upon thermal or vacuum treatment or simply over time. This instability limits the practical uses of many MOFs. In order to further enhance the stability of the framework, many different approaches, such as the utilization of high-valence metal ions or nitrogen-donor ligands, were recently investigated. This review details the efforts of both our research group and others to synthesize MOFs possessing drastically increased chemical and thermal stability, in addition to exemplary performance for catalysis, gas sorption, and separation.
The lithium-sulfur (Li-S) battery is a very promising candidate for the next generation of energy storage systems required for electrical vehicles and grid energy storage applications due to its very high theoretical specific energy (2500 W h kg(-1)). However, low Coulombic efficiency (CE) during repeated Li metal plating/stripping has severely limited the practical application of rechargeable Li-S batteries. In this work, a new electrolyte system based on a high concentration of LiNO3 in diglyme (G2) solvent is developed which enables an exceptionally high CE for Li metal plating/stripping and thus high stability of the Li anode in the sulfur-containing electrolyte. The tailoring of electrolyte properties for the Li anode has proven to be a highly successful strategy for improving the capacity retention and cycle life of Li-S batteries. This electrolyte provides a CE of greater than 99% for over 200 cycles of Li plating/stripping. In contrast, the Li anode cycles for less than 35 cycles (with a high CE) in the state-of-the-art 1 M LiTFSI + 0.3 M LiNO3 in 1,3-dioxolane: 1,2-dimethoxyethane (DOL:DME) electrolyte under the same conditions. The stable Li anode enabled by the new electrolyte may accelerate the applications of high energy density Li-S batteries in both electrical vehicles and large-scale grid energy storage markets.
The thermodynamic stability and melting point of magnesium borohydride were probed under hydrogen pressures up to 1000 bar (100 MPa) and temperatures up to 400 °C. At 400 °C, Mg(BH4)2 was found to be chemically stable between 700 and 1000 bar H2, whereas under 350 bar H2 or lower pressures, the bulk material partially decomposed into MgH2 and MgB12H12. The melting point of solvent-free Mg(BH4)2 was estimated to be 367-375 °C, which was above previously reported values by 40-90 °C. Our results indicated that a high hydrogen backpressure is needed to prevent the decomposition of Mg(BH4)2 before measuring the melting point and that molten Mg(BH4)2 can exist as a stable liquid phase between 367 and 400 °C under hydrogen overpressures of 700 bar or above. The occurrence of a pure molten Mg(BH4)2 phase enabled efficient melt-infiltration of Mg(BH4)2 into the pores of porous templated carbons (CMK-3 and CMK-8) and graphene aerogels. Both transmission electron microscopy and small-angle X-ray scattering confirmed efficient incorporation of the borohydride into the carbon pores. The Mg(BH4)2@carbon samples exhibited comparable hydrogen capacities to bulk Mg(BH4)2 upon desorption up to 390 °C based on the mass of the active component; the onset of hydrogen release was reduced by 15-25 °C compared to the bulk. Importantly, melt-infiltration under hydrogen pressure was shown to be an efficient way to introduce metal borohydrides into the pores of carbon-based materials, helping to prevent particle agglomeration and formation of stable closo-polyborate byproducts.
Solar thermal technologies such as solar hot water and concentrated solar power trough systems rely on spectrally selective solar absorbers. These solar absorbers are designed to efficiently absorb the sunlight while suppressing re-emission of infrared radiation at elevated temperatures. Efforts for the development of such solar absorbers must not only be devoted to their spectral selectivity but also to their thermal stability for high temperature applications. In this work, selective solar absorbers based on two cermet layers are fabricated on mechanically polished stainless steel substrates using a magnetron sputtering technique. The targeted operating temperature is 500–600 °C. A detrimental change in the morphology, phase, and optical properties is observed if the cermet layers are deposited on a stainless steel substrate with a thin nickel adhesion layer, which is due to the diffusion of iron atoms from the stainless steel into the cermet layer forming a FeWO 4 phase. In order to improve thermal stability and reduce the infrared emittance, tungsten is found to be a good candidate for the infrared reflector layer due to its excellent thermal stability and low infrared emittance. Lastly, a stable solar absorptance of ≈0.90 is demonstrated, with a total hemispherical emittance of 0.15 at 500 °C.
The single-phase stability of Cu{sub 2}ZnSnS{sub 4} (CZTS), after an intrinsic defect was incorporated in it, has been examined here for the first time based on ab initio calculations. The stability analysis of such a non-stoichiometric-defect incorporated CZTS shows that the single-phase formation is unlikely at thermodynamic equilibrium conditions. In addition, the effective growth condition of CZTS is determined and quantified for all the elements (Cu-poor, Zn-rich, Sn-poor, and S-rich) to extract maximum photovoltaic efficiency from CZTS. These conditions promote (i) spontaneous formation of Cu vacancy (V{sub Cu}), which might benefit p-type conduction, and (ii) the co-existence of ZnS while suppressing other harmful defects and secondary phases. Further, the results presented here explain the unavailability of single-phase CZTS to date.
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The high-temperature behavior of high-purity, low-density (HP-LD) air plasma sprayed (APS) thermal barrier coatings (TBCs) with NiCoCrAlY bond coats deposited by argon-shrouded plasma spraying is described. The high purity yttria-stabilized zirconia resulted in top coats which are highly resistant to sintering and transformation from the metastable tetragonal phase to the equilibrium mixture of monoclinic and cubic phases. The thermal conductivity of the as-processed TBC is low but increases during high temperature exposure even before densification occurs. The porous topcoat microstructure also resulted in good spallation resistance during thermal cycling. The actual failure mechanisms of the APS coatings were found to depend on topcoat thickness, topcoat density, and the thermal cycle frequency. The failure mechanisms are described and the durability of the HP-LD coatings is compared with that of state-of-the-art electron beam physical vapor deposition TBCs.
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The interaction of water with metal oxide surfaces plays a crucial role in the catalytic and geochemical behavior of metal oxides. In a vast majority of studies, the interfacial structure is assumed to arise from a relatively static lowest energy configuration of atoms, even at room temperature. Using hematite (α-Fe 2 O 3 ) as a model oxide, we show through a direct comparison of in situ synchrotron X-ray scattering with density functional theory-based molecular dynamics simulations that the structure of the ($1\bar{10}2 $) termination is dynamically stabilized by picosecond water exchange. Simulations show frequent exchanges between terminal aquo groups and adsorbed water in locations and with partial residence times consistent with experimentally determined atomic sites and fractional occupancies. Frequent water exchange occurs even for an ultrathin adsorbed water film persisting on the surface under a dry atmosphere. The resulting time-averaged interfacial structure consists of a ridged lateral arrangement of adsorbed water molecules hydrogen bonded to terminal aquo groups. Surface pK a prediction based on bond valence analysis suggests that water exchange will influence the proton-transfer reactions underlying the acid/base reactivity at the interface. Our findings provide important new insights for understanding complex interfacial chemical processes at metal oxide–water interfaces.
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Structure behavior of actinide brannerites ThTi{sub 2}O{sub 6}, Y{sub 0.5}U{sub 0.5}Ti{sub 1.5}Nb{sub 0.5}O{sub 6} and their analog oxide CeTi{sub 2}O{sub 6} was studied at high pressure by using in situ x-ray diffraction, Raman scattering and infra-red absorption techniques, respectively. Brannerite structure was found to be not stable and started to become amorphous at pressures above 20 GPa. Some minor crystalline phase(s) due to phase decomposition was observed in all the three samples during pressurization. In addition, the observed bulk modulus indicated that the actinide-bearing brannerites are more compressible than their analog compound CeTi{sub 2}O{sub 6}, which may be related to the asymmetric 5f electron orbits of actinide elements. - Graphical abstract: Actinide-bearing compounds with brannerite structure and their analog CeTi{sub 2}O{sub 6} are not stable at high pressure. They were amorphized after {approx}20 GPa and a minor pressure-induced phase transition or decomposition process was always observed before amorphization. Highlights: > Phase stability of three brannerites CeTi{sub 2}O{sub 6}, ThTi{sub 2}O{sub 6}, and (U,Y)(Ti,Nb){sub 2}O{sub 6} at high pressures. > Brannerite structure was not stable and became amorphous after {approx}20 GPa. > Actinide-bearing brannerites are easier compressed than their analog compound CeTi{sub 2}O{sub 6}.
The stability of Pt nanoparticles on a carbon support is crucial for the lifespan of polymer electrolyte membrane fuel cells as well as other electrocatalysis systems such as electrolyzers. Here we took the approach of utilizing the covalently grafted polyaniline on carbon to stabilize Pt nanoparticles by simultaneously alleviating the particle migration and mitigating the Ostwald ripening, which are two major mechanisms for loss of the catalyst stability. A comprehensive investigation of the stability and performance of Pt catalyst nanoparticles on these supports reveals that the polyaniline can shift the Pt L edge binding energy and the Pt 4f peak energy, leading to the increased redox potential of the Pt nanoparticles and making them more resistant to oxidation. Interestingly, the highest polyaniline density (50 wt%) does not show the best catalyst stability, rather, the second (33 wt%) demonstrates the best catalyst stability among these catalysts. Combining the XPS, XAS and fuel cell stability studies, we concluded that the locations of the Pt nanoparticles over the polyaniline layer on the carbon surface depend on the surface density of the polyaniline over the carbon surface. The Pt nanoparticles in the 50 wt% polyaniline catalyst are wrapped by the polyaniline polymer but do not sit directly on the carbon surface, while Pt nanoparticles in the 33 wt% polyaniline catalyst sit on the carbon surface and are densely surrounded by the polyaniline polymer. The results show that the mass activity loss is 12.5% while the ECSA (electrochemically active surface area) loss is 37.1% after 30k cycles of accelerating stress test for the 33 wt% polyaniline catalyst, far exceeding the DOE 2020 target for MEA (i.e., mass activity loss < 50%, and ECSA loss < 40%). Overall, the polyaniline has a synergistic effect on mitigating the surface migration and slowing down the Ostwald ripening to stabilize the Pt nanoparticles in fuel cells. The novel strategy to stabilize Pt nanoparticles using polyaniline opens a new pathway in the development of highly stable catalysts: relying on the functionalization group on the carbon support, instead of just focusing on the catalyst itself.