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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 721 records · Page 40
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Mapping Competitive Reduction upon Charging in LiNi 0.8 Co 0.15 Al 0.05 O 2 Primary Particles

Side reactions involving surface reduction play a critical role in the failure of LiNi 0.8 Co 0.15 Al 0.05 O 2 to reach its theoretical capacity as a cathode material for Li-ion batteries. While macroscopic consequences are known, the underlying nanoscopic mechanisms are not fully elucidated. By coupling X-ray spectroscopy with several X-ray microscopy modalities, we have spatially resolved the extent of Ni oxidation at several states of charge and uncovered heterogeneity that is hidden when considering ensemble measurements alone. The use of morphologically controlled particles enabled high-resolution imaging of these materials, uncovering gradients of Ni oxidation states within individual primary particles. At high states of charge, these gradients revealed regions of possible oxygen deficiency extending deeper into the particle than previously observed. Surface-sensitive X-ray coupled scanning tunneling microscopy allows oxidation states to be measured at the material's surface, showing predominantly Ni II in the first atomic layer and mixtures of Ni II with Ni III /Ni IV already appearing 1.5 nm into the particle. These results reveal the subtle interplay between irreversible surface transformations and the bulk reactions that ultimately define function, which will refine strategies of surface passivation that are key to overcoming current performance limitations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

High-Voltage, Intermediate-Temperature, Fe- and Al-Mixed Metal Halide Molten Salt for Molten Sodium Battery Energy Storage

An inorganic Fe and Al halide-based, low-temperature molten salt catholyte is described, which, when paired with a molten sodium anode, has high operating potentials rivaling those of Li ion batteries. The newly developed catholyte consists of metal halides FeCl 3 /FeCl 2 –AlCl 3 –NaCl and is intended to cycle between Fe 3+ /Fe 2+ redox couples in the molten salt. The multicomponent molten salt was initially evaluated for phase behavior and basic electrochemical behavior before full battery testing. The assembled battery, utilizing a 20:35:45 (FeCl 3 :AlCl 3 :NaCl) composition, with a 50.83 Ah/kg theoretical gravimetric capacity and a specific energy of 176.95 Wh/kg, was cycled at variable depths of discharge (DoD) and current densities to determine its cycling efficiencies and limitations. In conclusion, preliminary cycling tests showed two operational potential regimes, with higher potential, 3.91 V (vs Na/Na + ), at low DoD and lower potential, 3.39 V (vs Na/Na + ), at high DoD with excellent energy efficiencies and cycling behavior under both regimes.

Aluminum↗
DOE OSTI2022

Electron Binding Energy Spectra of Al n Pt – Clusters—A Combined Experimental and Computational Study

Results of size-selected electron photo-detachment experiments and density functional theory calculations on anionic Al n Pt – , n = 1–7, clusters are presented and analyzed. The measured and calculated spectra of electron binding energies are, overall, in excellent accord with each other. The analysis reveals the general importance of accounting for the multiplicity of structural forms of a given-size cluster that can contribute to its measured spectrum, especially when the clusters are fluxional and/or the conditions of the experiment allow for structural transitions. Here, we show that for the systems studied here, the size-specific peculiarities of the measured spectra can be understood in terms of the combined contributions of corresponding different accessible stable equilibrium conformations, bona-fide transition-state configurations, and electronic-crossing structures that may play the role of effective barriers in electronically nonadiabatic dynamics.

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

Plasmon-Induced CO 2 Conversion on Al@Cu 2 O: A DFT Study

In plasmonic catalysis, localized surface plasmon was leveraged to drive chemical reactions. This approach is promising for catalyzing many challenging reactions at relatively low temperatures and pressures. We apply density functional calculations to provide the insight for the mechanism of plasmon-induced direct CO 2 dissociation on an Al@Cu 2 O core-shell structure, which was observed in a previous experimental study. We show that the interaction of Cu 2 O with CO 2 results in the accessible antibonding states of the adsorbed CO 2 in the range of visible light. Though the intrinsic activation barrier for direct CO 2 dissociation is as high as 3.6 eV, we find that an effective reaction barrier of CO 2 dissociation under photon excitation could be reduced by 2 eV. We also show that the charge transfer is more pronounced in the final state of the dissociation due to the strong hybridization of the dissociated species with Cu 2 O. These results thus provide an explanation for the visible-light-induced direct CO 2 dissociation at relatively low temperature and under ambient pressure. This finding also shows the promising impact of plasmonic catalysis in mitigating carbon emission.

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

Nanoscale Compositional Mapping of Commercial LiNi 0.8 Co 0.15 Al 0.05 O 2 Cathodes Using Atom Probe Tomography

Nickel-rich cathodes provide improved specific capacity that lead to higher gravimetric energy density, critical for electric vehicles. However, poor long-term capacity retention at elevated temperatures/high C-rates (the rate of charge and discharge on a battery) stem from material issues: surface phase changes, corrosive side reactions with the electrolyte, ion dissolution and propagation of cracks. Introducing dopants, developing nanoscale surface coatings and graded core-shell structures have all improved the electrochemical performance of nickel-rich cathodes. However, a material level understanding on the effect of Li composition and distribution in Ni-rich cathodes is limited, due to a lack of characterization methods available that can directly image Li at the nanoscale. Hence, it is critical to establish methods such as atom probe tomography (APT), having both nanometer scale spatial resolution and high compositional sensitivity to quantitatively analyze battery cathodes. To fully realize its potential as a method for quantitative compositional analysis of commercial Li-ion batteries, we provide a comprehensive description of the challenges in sample preparation and analyze the dependency of the analysis parameters, specifically laser pulse energy on the measured stoichiometry of elements in a high Ni content cathode material; LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA). In this work, our findings show the stoichiometry variations cannot be explained by charge state ratios or Ga implantation damage alone during FIB preparation, indicating that additional factors such as crystallographic orientation may need to be considered to achieve quantitative nanoscale compositional analysis of such battery cathodes using APT.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Probing Interactions between Adsorbed Polymers and γ-Al 2 O 3 Using Solid-State NMR

The interactions between polymers and metal oxide surfaces affect the physical properties of polymer composites and the selectivity of catalysts used for plastic conversion. Gauging the strengths of these interactions and how they depend on adsorption conformations and polymer structure is nevertheless quite challenging. Herein, we evaluate whether a recently introduced dynamic nuclear polarization-based surface-to-atom distance measurement method can be used to gauge the specific interactions between five vinyl polymers and an oxide support (alumina). The adsorption conformations of polymer monolayers were studied using site-specific 13 C{ 27 Al} rotational-echo saturation-pulse double-resonance (RESPDOR) experiments. The method is effective in revealing the average distance between the adsorbed polymer and the surface, as well as the fraction of the monomers that are adsorbed. Polymers that possess larger side chains are more weakly adsorbed, as evidenced by their formation of more numerous loop and tail structures. In conclusion, the measured RESPDOR dephasing data further reveals that polymer adsorption conformations are largely disordered and involve few hydrogen bonding interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Solar Thermochemical Redox Cycling Using Ga- and Al-Doped LSM Perovskites for Renewable Hydrogen Production

Solar thermochemical hydrogen production using redox-active metal oxides is a promising pathway for the production of green hydrogen and synthetic fuel precursors. Herein, the perovskite material (La 0.6 Sr 0.4 ) 0.95 Mn 0.8 Ga 0.2 O 3–δ (LSMG6482) is identified as a promising metal oxide for thermochemical water splitting. LSMG6482, along with more-established water splitters ceria and (La 0.6 Sr 0.4 ) 0.95 Mn x Al 1–x O 3–δ (LSMA) perovskites, is experimentally characterized via thermogravimetric (TGA) analysis and high-temperature water splitting in a reactor simulating solar concentrating conditions. TGA analysis demonstrated that LSMG6482 has high and stable oxygen exchange capacity under controlled pO 2 redox cycling, demonstrated by large changes in oxygen nonstoichiometry (δ) relative to ceria. Water splitting experiments using laser heating (T red = 1400 °C, T ox = 1200 °C) resulted in H 2 yields of 165.1 μmol g –1 for the candidate LSMG6482 composition, exceeding that of all benchmark materials tested. Under high conversion oxidation conditions, where H 2 is cointroduced with H 2 O (150 ≤ nH 2 O/nH 2 ≤ 500), H 2 yields were greatest for LSMG6482 and LSMA6482, up to four times that of ceria at the highest nH 2 O/nH 2 conditions. Crystallographic analysis showed that over the course of experimentation, there is some secondary phase growth for all perovskite compositions, except for LSMA6482, but there was no observable degradation in H 2 yields.

08 HYDROGEN↗
DOE OSTI2025

Quasielastic and Inelastic Neutron Scattering Study of Ultraconfined Water in Natural Mordenite ((Ca,Na 2 ,K 2 )Al 2 Si 10 O 24 ·7H 2 O)

Mordenite ((Ca,Na 2 ,K 2 )Al 2 Si 10 O 24 ·7H 2 O) is a natural and synthetic nanoporous zeolite containing several channels of different sizes in its structure. Because of this, its structure provides an important opportunity to study the relationship between confined and ultraconfined water as these channels have sizes between those typical of these water environments. In this study, the properties of water molecules in these environments were analyzed using inelastic and quasielastic neutron spectroscopy of a natural mordenite. The quasielastic spectra showed the presence of nonfreezing, mobile water molecules through the entire temperature range of the measurements, but very little anisotropy of the dynamics measured along and perpendicular to the channels. Faster and slower quasi-elastic neutron scattering (QENS) components may be consistent with the presence of two separate classes of water molecules in mordenite. Inelastic neutron spectroscopy also found no evidence of directional anisotropy. In conclusion, the strong intensity characteristic of neutron recoil on protons from highly mobile water molecules at low temperature (5 K), along with a significant shift of water librational band to lower energies and the O–H stretching modes to high energies, indicate that the hydrogen bonds acting on these water molecules in mordenite resemble those in liquid water rather than ice.

Crystal structure↗
DOE OSTI2022

Extraordinary Strain Hardening from Dislocation Loops in Defect-Free Al Nanocubes

The complex interaction of crystalline defects leads to strain hardening in bulk metals. Metals with high stacking fault energy (SFE), such as aluminum, tend to have low strain hardening rates due to an inability to form stacking faults and deformation twins. Here, we use in situ SEM mechanical compressions to find that colloidally synthesized defect-free 114 nm Al nanocubes combine a high linear strain hardening rate of 4.1 GPa with a high strength of 1.1 GPa. These nanocubes have a 3 nm self-passivating oxide layer that has a large influence on mechanical behavior and the accumulation of dislocation structures. Post-compression TEM imaging reveals stable prismatic dislocation loops and the absence of stacking faults. MD simulations relate the formation of dislocation loops and strain hardening to the surface oxide. These results indicate that slight modifications to surface and interfacial properties can induce enormous changes to mechanical properties in high SFE metals.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Large Destabilization of (TiVNb)-Based Hydrides via (Al, Mo) Addition: Insights from Experiments and Data-Driven Models

High-entropy alloys (HEAs) represent an interesting alloying strategy that can yield exceptional performance properties needed across a variety of technology applications, including hydrogen storage. Examples include ultrahigh volumetric capacity materials (BCC alloys → FCC dihydrides) with improved thermodynamics relative to conventional high-capacity metal hydrides (like MgH 2 ), but still further destabilization is needed to reduce operating temperature and increase system-level capacity. Here, in this work, we demonstrate efficient hydride destabilization strategies by synthesizing two new Al 0.05 (TiVNb) 0.95–x Mo x (x = 0.05, 0.10) compositions. We specifically evaluate the effect of molybdenum (Mo) addition on the phase structure, microstructure, hydrogen absorption, and desorption properties. Both alloys crystallize in a bcc structure with decreasing lattice parameters as the Mo content increases. The alloys can rapidly absorb hydrogen at 25 °C with capacities of 1.78 H/M (2.79 wt %) and 1.79 H/M (2.75 wt %) with increasing Mo content. Pressure-composition isotherms suggest a two-step reaction for hydrogen absorption to a final fcc dihydride phase. The experiments demonstrate that increasing Mo content results in a significant hydride destabilization, which is consistent with predictions from a gradient boosting tree data-driven model for metal hydride thermodynamics. Furthermore, improved desorption properties with increasing Mo content and reversibility were observed by in situ synchrotron X-ray diffraction, in situ neutron diffraction, and thermal desorption spectroscopy.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Impact of Synthetic Parameters on Structure and Electrochemistry of High-Entropy Layered Oxide LiNi 0.2 Co 0.2 Mn 0.2 Al 0.2 Fe 0.2 O 2

Here, this study explored a high-entropy layered oxide (HELO), LiNi 0.2 Co 0.2 Mn 0.2 Al 0.2 Fe 0.2 O 2 , prepared by coprecipitation followed by heat treatment. Coprecipitation yielded a kinetically favored product, and the subsequent heat treatment under various temperatures and times allowed tuning the material toward more thermodynamically favored structures. Refinement of X-ray powder diffraction (XRD) revealed that after 450 °C treatment, ~12% of the Ni 2+ in the structure was located within the lithium cation layer. After heat treatment at 600, 700, and 800 °C, there was a continued decrease of Ni 2+ in the lithium cation layer to 9.3, 6.3, and 3.7%, respectively. Longer heat treatment times at 800 °C decreased the level to 2.5%. Electrochemical behavior was evaluated by cyclic voltammetry, galvanostatic cycling, rate capability testing, and electrochemical impedance spectroscopy, where increased loaded voltage, functional capacity, rate capability, and decreased impedance were observed for samples treated at higher temperatures with lower cation mixing. X-ray absorption near edge spectroscopy (XANES) data indicated that the redox activity of Ni and Co was dominant in the electrochemistry, while the participation of Mn or Fe was minimal. The level of Ni oxidation state change between charge and discharge related to the heat treatment temperature where the samples with high cation mixing showed lower capacity consistent with some Ni 3+ in the transition metal layer inaccessible for electron transfer. Longer heat treatment times at 800 °C did not continue to provide a benefit in electrochemical function even with some additional reduction in cation mixing.

25 ENERGY STORAGE↗
DOE OSTI2025

Unveiling the Interfacial Reconstruction Mechanism Enabling Stable Growth of the Delafossite PdCoO 2 on Al 2 O 3 and LaAlO 3

Delafossites, composed of noble metal (A + ) and strongly correlated sublayers (BO 2 – ), form natural superlattices with highly anisotropic properties. These properties hold significant promise for various applications, but their exploitation hinges on the successful growth of high-quality thin films on suitable substrates. Unfortunately, the unique lattice geometry of delafossites presents a significant challenge to thin-film fabrication. Different delafossites grow differently, even when deposited on the same substrate, ranging from successful epitaxy to complete growth suppression. These variations often lack a clear correlation to obvious causes like lattice mismatch. Unidentified stabilization mechanisms appear to enable growth in certain cases, allowing these materials to form stable thin films or act as buffer layers for subsequent delafossite growth. This study employs advanced scanning transmission electron microscopy techniques to investigate the nucleation mechanism underlying the stable growth of PdCoO 2 films on Al 2 O 3 and LaAlO 3 substrates grown via molecular-beam epitaxy. Our findings reveal the presence of a secondary phase within the substrate surface that stabilizes the films. This mechanism deviates from the conventional understanding of strain relief mechanisms at oxide heterostructure interfaces and differs significantly from those observed for Cu-based delafossites.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Elucidating the Role of Water on Limonene Oxidation with H 2 O 2 over γ -Al 2 O 3

Limonene oxide, which is produced from limonene epoxidation, is a valuable molecule that can be applied in flavor, fragrance, and renewable polymer applications. A catalytic reaction system using H 2 O 2 with γ-Al 2 O 3 and ethyl acetate (EtOAc) as the solvent has been explored as an effective system for this reaction. In these previous studies, a number of postulates have been proposed as to how water affects the reaction; therefore, the focus of this work is to elucidate the role of water in limonene epoxidation. While not impacting the selectivity to limonene oxide, the amount of water in the reaction system is shown to significantly impact the limonene reactivity. Furthermore, through both addition of excess water and removal of water with a Dean–Stark apparatus, the control of the H 2 O 2 /H 2 O ratio is demonstrated to be the primary factor controlling reactivity. In contrast, changes in limonene concentrations for a specific H 2 O 2 /H 2 O ratio are shown to have little impact on the reaction rate. This study shows that the competitive adsorption of H 2 O 2 and water on the catalyst surface is key in explaining the water impact on the reaction performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Reply to Comment by Peterie Et Al. on “Accelerated Fill‐Up of the Arbuckle Group Aquifer and Links to U.S. Midcontinent Seismicity”

Abstract Peterie et al. question one observation in our paper: associating pressure increases to injection volumes at distances of up to 25 km from an injection well. In this reply, we show that the comment misunderstands our analysis and the evidence that led to this conclusion. We also show that gauge‐depth‐corrected pressures, used by the authors to produce statewide pressure maps, are discrepant with the static fluid level data, provided in our original compilation and analysis. The discrepancies are a result of the pressure correction method employed, which naïvely substitutes formation pressure for bottomhole pressure to calculate wellbore fluid density. Their linearly interpolated pressure maps, based on sparse data, contain interpolation and extrapolation artifacts that contradict injection trends in the state, the Theis solution, and the superposition principle. We reiterate that pressure and static fluid level increases in Class I wells existed prior to 2013, most notably in central Kansas, where recent earthquakes are cited in the comment as evidence of a pressure plume emanating from the Kansas‐Oklahoma border, 90 km away. We show that the space‐time pattern of seismicity in this area is inconsistent with a northward propagating pressure plume and, instead, seismicity appears to be centered on and near a cluster of high‐rate injection wells, two of which are among the highest rate wells in the state. These observations, along with recent M4 + earthquakes during continued decreases in wastewater injection in southern Kansas and northern Oklahoma, question the usefulness of the comment for understanding and managing societally significant earthquakes.

Ansari, Esmail↗
DOE OSTI2021

Spin texture induced by non-magnetic doping and spin dynamics in 2D triangular lattice antiferromagnet h -Y(Mn,Al)O 3

Novel effects induced by nonmagnetic impurities in frustrated magnets and quantum spin liquid represent a highly nontrivial and interesting problem. A theoretical proposal of extended modulated spin structures induced by doping of such magnets, distinct from the well-known skyrmions has attracted significant interest. Here, we demonstrate that nonmagnetic impurities can produce such extended spin structures in h-YMnO 3 , a triangular antiferromagnet with noncollinear magnetic order. Using inelastic neutron scattering (INS), we measured the full dynamical structure factor in Al-doped h-YMnO 3 and confirmed the presence of magnon damping with a clear momentum dependence. Our theoretical calculations can reproduce the key features of the INS data, supporting the formation of the proposed spin textures. As such, our study provides the first experimental confirmation of the impurity-induced spin textures. It offers new insights and understanding of the impurity effects in a broad class of noncollinear magnetic systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Modeling antiphase boundary energies of Ni 3 Al-based alloys using automated density functional theory and machine learning

Antiphase boundaries (APBs) are planar defects that play a critical role in strengthening Ni-based superalloys, and their sensitivity to alloy composition offers a flexible tuning parameter for alloy design. Here, we report a computational workflow to enable the development of sufficient data to train machine-learning (ML) models to automate the study of the effect of composition on the (111) APB energy in Ni 3 Al-based alloys. We employ ML to leverage this wealth of data and identify several physical properties that are used to build predictive models for the APB energy that achieve a cross-validation error of 0.033 J m –2 . We demonstrate the transferability of these models by predicting APB energies in commercial superalloys. Moreover, our use of physically motivated features such as the ordering energy and stoichiometry-based features opens the way to using existing materials properties databases to guide superalloy design strategies to maximize the APB energy.

36 MATERIALS SCIENCE↗
DOE OSTI2023

A deep neural network regressor for phase constitution estimation in the high entropy alloy system Al-Co-Cr-Fe-Mn-Nb-Ni

High Entropy Alloys (HEAs) are composed of more than one principal element and constitute a major paradigm in metals research. The HEA space is vast and an exhaustive exploration is improbable. Therefore, a thorough estimation of the phases present in the HEA is of paramount importance for alloy design. Machine Learning presents a feasible and non-expensive method for predicting possible new HEAs on-the-fly. A deep neural network (DNN) model for the elemental system of: Mn, Ni, Fe, Al, Cr, Nb, and Co is developed using a dataset generated by high-throughput computational thermodynamic calculations using Thermo-Calc. The features list used for the neural network is developed based on literature and freely available databases. A feature significance analysis matches the reported HEAs phase constitution trends on elemental properties and further expands it by providing so far-overlooked features. The final regressor has a coefficient of determination ( r 2 ) greater than 0.96 for identifying the most recurrent phases and the functionality is tested by running optimization tasks that simulate those required in alloy design. The DNN developed constitutes an example of an emulator that can be used in fast, real-time materials discovery/design tasks.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Grain Boundary Effects on Radiation Damage and Tritium Diffusion in Li–Al–O Ceramics from Molecular Dynamics and Experiments

Understanding irradiation damage and tritium transport in LiAlO2 ceramics is essential for their deployment in tritium-producing burnable absorber rods (TPBARs). Grain boundaries (GBs) play an important role in governing radiation response and tritium transport in LiAlO2 and its secondary phase LiAl5O8. Using molecular dynamics simulations, we investigated defect evolution and tritium diffusion during displacement cascades in single-crystal and bicrystal LiAlO2 and LiAl5O8 at 600 K. The results reveal that GBs suppress the damage in the LiAlO2 bicrystals as compared to single crystals, via interstitial emission. The effect is more pronounced for Li defects, than for Al and O. In LiAl5O8 the damage reduction due to introduction of GB is less pronounced overall. Tritium diffusion coefficients at GBs are higher by factors of 2–10 relative to diffusion inside grain bulk. The effect is particularly pronounced in LiAlO2, where S5, S17, and S25 GBs promote rapid tritium transport, whereas LiAl5O8 exhibits slower diffusion due to reduced free volume at its GBs. These findings evince a trade-off that while GBs mitigate radiation damage by absorbing interstitials, they simultaneously provide fast pathways for tritium migration which is not desirable for TPBAR application. The mechanistic insights gained here establish a foundation for microstructural design strategies to balance radiation tolerance and tritium retention in ceramic breeder materials.

Roy, Ankit↗