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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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At least 1,099 records · Page 61
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Fabrication of hierarchical Lewis acid Sn-BEA with tunable hydrophobicity for cellulosic sugar isomerization

Lewis acid Sn-BEA catalysts with tunable morphology and hydrophobicity were successfully synthesized by the recrystallization of post-synthetic Sn-BEA in the presence of ammonium fluoride (NH4F) and tetraethylammonium bromide (TEABr). Three-dimensionally ordered mesoporous imprinted (3DOm-i) and nanocrystalline Sn-BEA catalysts with hydrophobic surface were synthesized for the first time by the method. This recrystallization method includes the dissolution of crystalline zeolite BEA by fluoride ions and the rearrangement of different types of silanol defects in the presence of TEABr. The method allows the final products to simultaneously inherit the morphology of their parent Al-BEA zeolites, and significantly reduce silanol defects within the catalysts. The Sn-BEA catalysts synthesized from the recrystallization method show largely enhanced catalytic performance for both glucose isomerization and bulky lactose isomerization in different solvents, which is presumably due to the hydrophobic surface and improved molecular transport property in the hierarchical zeolites. The recrystallization approach is a facile and reliable strategy to improve the hydrophobicity of zeolite catalysts with tunable morphologies ranging from nanocrystals to hierarchical structures.

bio-inspired↗
DOE OSTI2022

Thermophysical properties of FLiBe using moment tensor potentials

Fluoride salts are prospective materials for applications in some next-generation nuclear reactors and their thermophysical properties at various conditions are of interest. Experimental measurement of the properties of these salts is often difficult and, in some cases, unfeasible due to challenges from high temperatures, impurity control, and corrosivity. Therefore, accurate theoretical methods are needed for fluoride salt property prediction. In this work, we used moment tensor potentials (MTP) to approximate the potential energy surface of eutectic FLiBe (66.6% LiF – 33.3% BeF2) predicted by the ab initio (DFT-D3) method. Here, we then used the developed potential and molecular dynamics to obtain several thermophysical properties of FLiBe, including radial distribution functions, density, self-diffusion coefficients, thermal expansion, specific heat capacity, bulk modulus, viscosity, and thermal conductivity. Our results show that the MTP potential approximates the potential energy surface accurately and the overall approach yields very good agreement with experimental values. The converged fitting can be obtained with less than 600 configurations generated from DFT calculations, which data can be generated in just 1200 core hours on today's typical processors. The MTP potential is faster than many machine learning potentials and about one order of magnitude slower than widely used empirical molten salt potentials such as Tosi/Fumi.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Enhanced lithium storage capability of FeF 3 ·0.33H 2 O single crystal with active insertion site exposed

Iron fluoride cathode for lithium batteries intrigues researchers for decades due to high capacity and low cost, but suffers from poor electronic and ionic conductivity. Hierarchical micro/nano construction with preferred orientation growth can shorten ion diffusion pathway and facilitate electron transportation without inducing side reactions. FeF 3 ·0.33H 2 O hierarchical microspheres self-assembled by octagonal single crystal slices are prepared. Benefiting from the artful structure, SAED and XRD characterizations confirm that the octagonal single crystal slices provides more lithium ions intercalation positions (4c sites). Electrochemical tests demonstrate that the well designed FeF 3 ·0.33H 2 O single crystal (FFH-S) delivers 30 mAh g -1 higher capacity (172 mAh g -1 at 0.1C) than the common FeF 3 ·0.33H 2 O polycrystal (FFH-P). In-situ XRD combined with theoretic calculation elucidate the difference in lithium storage capacity. Instructive argument that single crystal octagon slices with [110] oriented growth provide more active sites for lithium ions intercalation contributes to the preparation of high performance iron fluoride cathode materials for rechargeable battery.

25 ENERGY STORAGE↗
DOE OSTI2024

Modeling athermal phonons in novel materials using the G4CMP simulation toolkit

Understanding phonon and charge propagation in superconducting devices plays an important role in both performing low-threshold dark matter searches and limiting correlated errors in superconducting qubits. The Geant4 Condensed Matter Physics (G4CMP) package, originally developed for the Cryogenic Dark Matter Search (CDMS) experiment, models charge and phonon transport within silicon and germanium detectors and has been validated by experimental measurements of phonon caustics, mean charge-carrier drift velocities, and heat pulse propagation times. Here, in this work, we present a concise framework for expanding the capabilities for phonon transport to a number of other novel substrate materials of interest to the dark matter and quantum computing communities, including sapphire (Al 2 O 3 ), gallium arsenide (GaAs), lithium fluoride (LiF), calcium tungstate (CaWO 4 ), and calcium fluoride (CaF 2 ). We demonstrate the use of this framework in generating phonon transport properties of these materials and compare these properties with experimentally-determined values where available.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2015

The use of aluminum nitride to improve Aluminum-26 Accelerator Mass Spectrometry measurements and production of Radioactive Ion Beams

We present results and discuss the use of aluminum nitride as a promising source material for Accelerator Mass Spectrometry (AMS) and Radioactive Ion Beams (RIBs) science applications of 26 Al isotopes. The measurement of 26 Al in geological samples by AMS is typically conducted on Al 2 O 3 targets. However, Al 2 O 3 is not an ideal source material because it does not form a prolific beam of Al- required for measuring low-levels of 26 Al. Multiple samples of aluminum oxide (Al 2 O 3 ), aluminum nitride (AlN), mixed Al 2 O 3 –AlN as well as aluminum fluoride (AlF 3 ) were tested and compared using the ion source test facility and the stable ion beam (SIB) injector platform at the 25-MV tandem electrostatic accelerator at Oak Ridge National Laboratory. Negative ion currents of atomic and molecular aluminum were examined for each source material. It was found that pure AlN targets produced substantially higher beam currents than the other materials and that there was some dependence on the exposure of AlN to air. The applicability of using AlN as a source material for geological samples was explored by preparing quartz samples as Al 2 O 3 and converting them to AlN using a carbothermal reduction technique, which involved reducing the Al 2 O 3 with graphite powder at 1600 °C within a nitrogen atmosphere. The quartz material was successfully converted to AlN. Thus far, AlN proves to be a promising source material and could lead towards increasing the sensitivity of low-level 26 Al AMS measurements. The potential of using AlN as a source material for nuclear physics is also very promising by placing 26 AlN directly into a source to produce more intense radioactive beams of 26 Al.

Janzen, Meghan S.↗
DOE OSTI2019

Use of indentation to study the degradation of photovoltaic backsheets

The ability of electrical insulating materials within a module to act as insulators is a key safety requirement for photovoltaic (PV) technology. Presently, however, the durability of backsheets may not be readily assessed. For example, the mechanical tensile test continues to be developed, and its use has not been validated such that a technically based pass/fail criteria may be established. This study examines the use of simple indentation methods, including durometer hardness and instrumented indentation, as a means to quantitively assess the degradation of PV backsheets. Characteristics including: hardness, modulus, load/displacement profile, creep hold response, and residual impression are explored in an empirical study. Glass/encapsulant/backsheet mini-modules constructed using backsheets including: polyamide (PA), poly(ethylene terephthalate) (PET), polyvinyl fluoride (PVF) laminate ('TPE'), and polyvinylidene fluoride (PVDF) were examined. An M-type durometer as well as Berkovich and cube-corner tips were used in the indentation experiments. Additional characterizations were performed to interpret the indentation measurements including: surface roughness measurements using atomic force microscopy (AFM), a chemical integrity study using Fourier-transform infrared spectroscopy (FTIR), and phase-transition measurements using differential scanning calorimetry (DSC). The results are analyzed in the context of the combined accelerated stress test (C-AST) also explored in this study. Instrumented indentation (i.e., using a Berkovich tip) was able to distinguish between backsheets and quantify the effects of accelerated testing (including up to 60%, 25%, and 20% change in hardness, modulus, and creep displacement, respectively). The embrittlement of the backsheets was not readily assessable using cube-corner indentation. Cracking of the known-bad polyamide backsheet was observed from the C-AST, which was not observed to result from steady state UV weathering.

14 SOLAR ENERGY↗
DOE OSTI2020

Characterizing photovoltaic backsheet adhesion degradation using the wedge and single cantilever beam tests, Part II: Accelerated tests

Photovoltaic (PV) backsheets provide critical moisture, mechanical, and electrical insulation to the backside of PV modules, but their continued functionality depends upon their ability to remain well adhered over years of harsh environmental exposure. A study of adhesive strength was conducted on several PV backsheet types exposed to indoor accelerated weathering. Two adhesion tests – the wedge test and single cantilever beam test – were used to measure adhesion energy in four backsheets: two with fluoropolymer-based outer (airside) layers – polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF) – and two with non-fluoropolymer-based outer layers–polyamide (PA) and polyethylene terephthalate (PET). The effects of changes in temperature, ultraviolet (UV) irradiance, relative humidity, and a periodic water spray were studied. The PET-, PVF- and PVDF-based backsheets all showed instances of debonding in an adhesive layer, which is commonly reported. Furthermore, for the PA-, PET-, and PVDF-based backsheets, adhesion energy dropped fairly rapidly with exposure, reaching very low levels by 4000 h. The PVF-based backsheet was relatively robust to weathering. Pull-off of an outer chalking layer in the PA- and PET-based backsheets suggested a sensitivity to UV. Adhesion in these two backsheets was also highly sensitive to changes in moisture level. Changes in UV irradiance and temperature did not show a statistically significant effect on adhesion loss for the exposure levels used. The present work is part of a two-part adhesion study on both field-weathered and indoor-exposed backsheets, and forms a basis for understanding adhesion degradation across a variety of backsheet types and degradation factors.

14 SOLAR ENERGY↗
DOE OSTI2023

Conversion efficiency improvement of ELO GaAs solar cell, deposited on water soluble sacrificial buffer

Here, we demonstrate the improvement of power conversion efficiency of an epitaxially-lifted-off single junction GaAs solar cell deposited on a water-soluble sacrificial buffer architecture by introducing an additional germanium (Ge) interlayer between GaAs and the fluoride buffer. The epitaxial lift-off (ELO) technique has been extensively used to separate III-V device layers from their single crystal GaAs substrates. However, conventional ELO requires the use of concentrated hydrofluoric acid (HF) for extended times to etch out the sacrificial layer, subsequently degrading the surface roughness of the parent wafer. As a result, the wafer has to undergo expensive and intensive chemical mechanical polishing (CMP) processes, costing about 25% of a pristine 6-inch GaAs substrate. In our previous work, we demonstrated a method to eliminating the need for CMP post-processing by using water-assisted ELO (H 2 O-ELO). A water-soluble, 3-layer buffer architecture was developed using alkaline earth compounds. However, devices suffered low performance due to a high defect density in the GaAs active layers. A Ge interlayer was introduced to provide a more favorable surface energy for GaAs growth, which leads to an improvement of GaAs crystal quality. The Ge deposition conditions were optimized to achieve a high-quality Ge layer on triple-layer fluoride buffer. Single junction GaAs devices fabricated on Ge/(Ca,Sr)F 2 /BaF 2 /(Ca,Sr)F 2 showed improvement of solar cell performance parameters featuring increases in V oc by 23.7%, and fill factor (F.F.) by 4.9%, which results in an overall improvement of power conversion efficiency from 10.3% to 12.69%.

14 SOLAR ENERGY↗
DOE OSTI2023

Development and demonstration of a rolling ball viscometer for molten salts with near-minimum liquidus NaCl–KCl

The thermophysical characterization of molten chloride and fluoride salts is a key interest for the development of advanced molten salt nuclear reactors. Viscosity is one thermophysical property of interest; a high-accuracy understanding of this property is necessary for modeling the thermal energy transfer and mass flow rate for a given molten salt system. Only a few methods have consistently been used to measure the viscosity of molten chloride and fluoride salt systems, and large discrepancies have been observed in the literature between independent studies of nearly identical salt systems. As such, exploration of novel measurement methods or implementations may allow for further validation, improved measurement accuracy, and overall improved understanding about optimal approaches for measuring molten salt viscosity. Here, in this study, a novel implementation of the rolling ball viscometry method was used to measure the viscosity of a 44/56 mol % mixture of NaCl–KCl within a temperature range of 714–838 °C, with the intent to demonstrate the feasibility of this technique for molten salt viscosity measurement cross-validation. The purity of this salt was confirmed through laser-induced breakdown spectroscopy. Measured viscosities were approximately 1.3–1.0 cP within this temperature range, and the overall uncertainty was 10.8%, which was determined through Gaussian error propagation. The results agree reasonably well with measured viscosities of similar NaCl–KCl mixtures in the literature (within 2%–20% depending on the temperature and study), although the experimental error in some of these comparative studies may be significant.

47 OTHER INSTRUMENTATION↗
DOE OSTI2018

Understanding Conversion-Type Electrodes for Lithium Rechargeable Batteries

The need/desire to lower the consumption of fossil fuels and its environmental consequences has reached unprecedented levels in recent years. A global effort has been undertaken to develop advanced renewable energy generation and especially energy storage technologies, as they would enable a dramatic increase in the effective and efficient use of renewable (and often intermittent) energy sources. The development of electrical energy storage (EES) technologies with high energy and power densities, long life, low cost, and safe use represents a challenge from both the fundamental science and technological application points of view. While the advent and broad deployment of lithium-ion batteries (LIBs) has dramatically changed the EES landscape, their performance metrics need to be greatly enhanced to keep pace with the ever-increasing demands imposed by modern consumer electronics and especially the emerging automotive markets. Current battery technologies are mostly based on the use of a transition metal oxide cathode (e.g., LiCoO 2 , LiFePO 4 , or LiNiMnCoO 2 ) and a graphite anode, both of which depend on intercalation/insertion of lithium ions for operation. While the cathode material currently limits the battery capacity and overall energy density, there is a great deal of interest in the development of high-capacity cathode materials as well as anode materials. Conversion reaction materials have been identified/proposed as potentially high-energy-density alternatives to intercalation-based materials. Yet, conversion reaction materials react during lithiation to form entirely new products, often with dramatically changed structure and chemistry, by reaction mechanisms that are still not completely understood. This makes it difficult to clearly distinguish the limitations imposed by the mechanism and practical losses from initial particle morphology, synthetic approaches, and electrode preparations. Transition metal compounds such as transition metal oxides, sulfides, fluorides, phosphides, and nitrides can undergo conversion reactions yielding materials with high theoretical capacity (generally from 500 to 1500 mA h g –1 ). Specifically, a number of transition metal oxides and sulfides have shown excellent electrochemical properties as high-capacity anode materials. In addition, some transition metal fluorides have shown great potential as cathode materials for Li rechargeable batteries. In this Account we present mechanistic studies, with emphasis on the use of operando methods, of selected examples of conversion-type materials as both potentially high-energy-density anodes and cathodes in EES applications. We also include examples of the conceptually similar conversion-type reactions involving chalcogens and halogens, with emphasis on the Li–S system. In this case we focus on the problems arising from the low electrical conductivities of elemental sulfur and Li 2 S and the “redox shuttle” phenomena of polysulfides. In addition to mechanistic insights from the use of operando methods, we further cover several key strategies in electrode materials design such as controlling the size, morphology, composition, and architecture.

25 ENERGY STORAGE↗
DOE OSTI2018

Inactivation of 4-Oxalocrotonate Tautomerase by 5-Halo-2-hydroxy-2,4-pentadienoates

5-Halo-2-hydroxy-2,4-pentadienoates (5-halo-HPDs) are reportedly generated in the bacterial catabolism of halogenated aromatic hydrocarbons by the meta-fission pathway. The 5-halo-HPDs, where the halogen can be bromide, chloride, or fluoride, result in the irreversible inactivation of 4-oxalocrotonate tautomerase (4-OT), which precedes the enzyme that generates them. The loss of activity is due to the covalent modification of the nucleophilic amino-terminal proline. Mass spectral and crystallographic analysis of the modified enzymes indicates that inactivation of 4-OT by 5-chloro- and 5-bromo-2-hydroxy-2,4-pentadienoate follows a mechanism different from that for the inactivation of 4-OT by 5-fluoro-2-hydroxy-2,4-pentadienoate. The 5-chloro and 5-bromo derivatives undergo 4-OT-catalyzed tautomerization to their respective α,β-unsaturated ketones followed by attack at C5 (by the prolyl nitrogen) with concomitant loss of the halide. For the 5-fluoro species, the presence of a small amount of the α,β-unsaturated ketone could result in a Michael addition of the prolyl nitrogen to C4 followed by protonation at C3. The fluoride is not eliminated. Here, these observations suggest that the inactivation of 4-OT by a downstream metabolite could hamper the efficacy of the pathway, which is the first time that such a bottleneck has been reported for the meta-fission pathway.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Elucidating the Redox Behavior during Atomic Layer Deposition on Lithium-Ion Battery Cathode Materials

Atomic layer deposition (ALD) has emerged as a promising technology for applying ultrathin protective coatings on lithium-ion battery (LIB) cathode surfaces to improve their cycling stability. While there have been numerous reports evaluating the electrochemical performance of these surface-modified cathode materials, the chemical changes induced on the surface of the cathode materials upon ALD coating are not fully studied. This paper describes a systematic investigation to understand the interfacial changes of 12 different cathode materials upon coating with aluminum oxide (Al 2 O 3 ) using trimethyl aluminum (TMA) and H 2 O, and aluminum fluoride (AlF 3 ) using TMA and hydrogen fluoride pyridine (HFPy). Here, the surface composition of these cathode materials, which range from simple transition metal oxides (e.g. NiO and MnO) to complex multi-element cathode materials (e.g. LiNi x Mn 1-x-y Co y O 2 , NMC), was studied via X-ray photoelectron spectroscopy (XPS). The XPS measurements reveal that the transition metals in the cathode materials undergo selective oxidation/reduction depending upon the nature of the precursor, the coating, and the cathode material. The ability to chemically modify the surface of cathode materials via vapor-phase precursor adsorption will open new avenues to systematically control the interface of the cathode materials in LIBs that are not possible by conventional coating methods.

25 ENERGY STORAGE↗
DOE OSTI2018

Zero Thermal Expansion and Abrupt Amorphization on Compression in Anion Excess ReO 3 -Type Cubic YbZrF 7

In this paper, heat treatment of cubic YbZrF 7 , after quenching from 1000 °C, leads to a material displaying precisely zero thermal expansion at ~300 K and negative thermal expansion at lower temperatures. The zero thermal expansion is associated with a minimum in the lattice constant at ~300 K. X-ray total scattering measurements are consistent with a previously proposed model in which the incorporation of interstitial fluoride into the ReO 3 -related structure leads to both edge and corner sharing coordination polyhedra. The temperature dependence of the experimental pair correlation functions suggests that the expansions of edge and corner sharing links partly compensate for one another, supporting the hypothesis that the deliberate incorporation of excess fluoride into ReO 3 structure materials can be used as a design strategy for controlling thermal expansion. Cubic YbZrF 7 has a bulk modulus, K 0 , of 55.4(7) GPa and displays pronounced pressure-induced softening [K 0 ' = -27.7(6)] prior to an abrupt amorphization on compression above 0.95 GPa. Finally, the resulting glass shows a single sharp scattering maximum at Q ~ 1.6 Å –1 .

36 MATERIALS SCIENCE↗
DOE OSTI2020

Lewis Acidity and Basicity: Another Measure of Carbene Reactivity

The structural and energetic reactivities of various carbenes are evaluated against a standard electrophile (proton) and a standard nucleophile (fluoride). The proton and fluoride affinities of the carbenes studied provide an increased understanding of reactivity modes and mechanisms. General classification of carbenic reactivity as a singlet nucleophilic carbene or a singlet electrophilic carbene is facilitated by this present study, and a need for further classification means along the border between electrophilic and nucleophilic reactivity is considered. The results are based on electronic structure calculations at the composite correlated molecular orbital theory G3MP2 level.

Stein, Trent H.↗
DOE OSTI2022

Reactions of Atomic Thorium and Uranium Cations with SF 6 Studied by Guided Ion Beam Tandem Mass Spectrometry

The fundamental chemistry of the thorium and uranium fluorides continues to be an area of interest because of the use of thorium and uranium fluoride compounds in nuclear fuel systems. Here, we study the reaction of thorium cations with sulfur hexafluoride for the first time and revisit the reaction of uranium cations with sulfur hexafluoride. By using guided ion beam tandem mass spectrometry, we explore the reaction pathways that become accessible well above thermal energies (E ~ 0.04 eV). Overall, we find that both Th + and U + react very efficiently with SF 6 , approaching the collision limit at both thermal and elevated energies. Here, the primary products observed at low energies include Th 1–3 + , UF 1–4 + , and SF 1–4 + , all of which are formed in barrierless, exothermic processes. SF 5 + was also observed, although the pressure dependence of this channel reveals that SF 5 + forms exothermically through secondary reactions, which the energy dependences suggest result from reactions between ThF 2 + and UF 3 + with SF 6 . At higher energies, both AnF 3 + products are observed to decay to AnF + + F 2 and both SF 4 + and SF 2 + exhibit cross sections with endothermic features. For both systems, the rise in SF 4 + can be attributed to a secondary collision between AnF + with SF 6 on the basis of the pressure dependence of the SF 4 + channel at higher energies and the rise in SF 2 + appears to result from the decomposition of SF 3 + to SF 2 + + F.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Structural Characterization of Uranium Tetrafluoride Hydrate (UF 4 ·2.5H 2 O)

Uranium tetrafluoride is an important intermediate in the nuclear fuel cycle. Facile synthesis of its hydrate, uranium tetrafluoride hydrate (UF 4 ·2.5H 2 O), has recently been reported. The hydrate forms by contacting anhydrous UF 4 with neat H 2 O at room temperature for 24 h or by exposing anhydrous UF 4 to high relative humidity (>90%) conditions for several weeks. These pathways are of clear environmental relevance. Further understanding of the structure and optical spectra of UF 4 ·2.5H 2 O, especially of the water molecules, is therefore necessary. Herein, the structure of UF 4 ·2.5H 2 O was probed using time-of-flight neutron powder diffraction to improve understanding of the crystalline water environments in the structure. The complete structure was elucidated and compared to a previously reported partial structure for UF 4 ·2.5H 2 O and a predicted complete structure from density functional theory. The crystalline structure exhibits three distinct water environments: two of the three water sites are bound to uranium, and the third water is unbound or “free”. Furthermore, the completed structure reveals an extensive hydrogen bonding network involving water–fluorine and water–water interactions. One bound water site participates in hydrogen bonding with nearby fluoride ligands (O–H···F–U), and the second bound water site participates in hydrogen bonding with the unbound water (O–H···O) and a nearby fluoride ligand (O–H···F–U); the unbound water participates in hydrogen bonding with bound water (O–H···O–U). Low-temperature experiments and thermal analysis indicate UF 4 ·2.5H 2 O is thermally stable from 10 to 358 K, undergoes dehydration at higher temperatures, and is nearly dehydrated at 473 K. Structural measurements provide foundational understanding and will inform future investigations of the thermal and environmental stability of UF 4 ·2.5H 2 O.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗