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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 955 records · Page 53
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Metastable Intermediates in Amorphous Titanium Oxide: A Hidden Role Leading to Ultra-Stable Photoanode Protection

Metastable intermediates represent a non-equilibrium state of matter that may impose profound impacts to materials properties beyond our understandings of monolithic and equilibrium systems. Here, we report a discovery of hidden metastable intermediates in amorphous TiO 2 thin films and their critical role in electrochemical damage. These intermediates have a non-bulk crystal-like structure and exhibit significantly higher electrical conductivity than both the amorphous and the crystalline phases. When these TiO 2 films are applied to protect Si photoelectrochemical (PEC) photoanodes, the intermediates can induce localized high electrical currents that largely accelerate the etching of the TiO 2 film and the Si electrode underneath. The intermediates can be effectively suppressed by raising their nucleation barrier via reducing the film thickness from 24 to 2.5 nm. The homogeneous amorphous TiO 2 -film-coated Si photoanodes achieved more than 500 h of PEC water oxidation at a steady photocurrent density of over 30 mA·cm –2 .

36 MATERIALS SCIENCE↗
DOE OSTI2020

Enhanced Interfacial Stability of Si Anodes for Li-Ion Batteries via Surface SiO2 Coating

Silicon is a promising alloying anode for lithium-ion batteries owing to its high capacity and low cost. However, its use has been hampered by mechanical failure arising from the large volume change upon cycling and by an insufficiently stable solid-electrolyte interphase (SEI). SEI formation depends on the Si surface, which is often an oxide (SiO x ). In this study we compare three different Si surfaces using Si wafers: 1.3 nm native SiO x , 1.4 nm thermally grown SiO2, and a SiOx-free surface. The oxide-free surface showed the worst electrochemical performance, never exceeding 94% Coulombic efficiency (CE). Furthermore, it also exhibited the thickest SEI and the highest overpotential for lithiation, which correlated with uninhibited electrolyte reduction and the incorporation of P-F species into the SEI. The oxide-coated surfaces performed significantly better, demonstrating a CE above 99% beyond the second cycle, low overpotential for lithiation, and a thinner and more stable SEI. The oxides lower the onset potential for electrolyte reduction, and yield an SEI with fewer P-F species. However, it was found that the CE with the native oxide surface decays from the fifth cycle onwards and correlates with a resurgence of electrolyte reduction. A 1-2 nm thermal SiO 2 coating is optimum for achieving a stable SEI that minimizes side reactions and sustains efficient cycling.

25 ENERGY STORAGE↗
DOE OSTI2018

Mechanical Properties and Chemical Reactivity of Li x SiO y Thin Films

Silicon (Si) is a commonly studied candidate material for next-generation anodes in Li-ion batteries. A native oxide SiO 2 on Si is often inevitable. However, it is not clear if this layer has a positive or negative effect on the battery performance. This understanding is complicated by the lack of knowledge about the physical properties of the SiO 2 lithiation products and by the convolution of chemical and electrochemical effects during the anode lithiation process. In this study, Li x SiO y thin films as model materials for lithiated SiO 2 were deposited by magnetron sputtering at ambient temperature, with the goal of (1) decoupling chemical reactivity from electrochemical reactivity and (2) evaluating the physical and electrochemical properties of Li x SiO y . X-ray photoemission spectroscopy analysis of the deposited thin films demonstrate that a composition close to previous experimental reports of lithiated native SiO 2 can be achieved through sputtering. Our density functional theory calculations also confirm that the possible phases formed by lithiating SiO 2 are very close to the measured film compositions. Scanning probe microscopy measurements show that the mechanical properties of the film are strongly dependent on lithium concentration, with a ductile behavior at a higher Li content and a brittle behavior at a lower Li content. The chemical reactivity of the thin films was investigated by measuring the AC impedance evolution, suggesting that Li x SiO y continuously reacts with the electrolyte, in part because of the high electronic conductivity of the film determined from solid-state impedance measurements. The electrochemical cycling data of the sputter-deposited Li x SiO y /Si films also suggest that Li x SiO y is not beneficial in stabilizing the Si anode surface during battery operation, despite its favorable mechanical properties.

14 SOLAR ENERGY↗
DOE OSTI2018

Combining CO 2 Reduction with Ethane Oxidative Dehydrogenation by Oxygen-Modification of Molybdenum Carbide

The surface properties that determine the selectivity of Mo 2 C catalysts in ethane oxidative dehydrogenation with CO 2 as a soft oxidant were investigated using a combination of pulse experiments and in-situ spectroscopic methods. Oxygen modification was discovered to be crucial for inhibiting the cleavage of the C–C bond in ethane and enhancing the production of ethylene. Here, the addition of the Fe promoter accelerated the formation of surface oxygen species and stabilized them from reduction by ethane, leading to a shorter induction period, higher ethylene yield, and improved stability.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Multivariate Bayesian Optimization of CoO Nanoparticles for CO 2 Hydrogenation Catalysis

The hydrogenation of CO 2 holds promise for transforming the production of renewable fuels and chemicals. However, the challenge lies in developing robust and selective catalysts for this process. Transition metal oxide catalysts, particularly cobalt oxide, have shown potential for CO 2 hydrogenation, with performance heavily reliant on crystal phase and morphology. Achieving precise control over these catalyst attributes through colloidal nanoparticle synthesis could pave the way for catalyst and process advancement. Yet, navigating the complexities of colloidal nanoparticle syntheses, governed by numerous input variables, poses a significant challenge in systematically controlling resultant catalyst features. We present a multivariate Bayesian optimization, coupled with a data-driven classifier, to map the synthetic design space for colloidal CoO nanoparticles and simultaneously optimize them for multiple catalytically relevant features within a target crystalline phase. The optimized experimental conditions yielded small, phase-pure rock salt CoO nanoparticles of uniform size and shape. These optimized nanoparticles were then supported on SiO 2 and assessed for thermocatalytic CO 2 hydrogenation against larger, polydisperse CoO nanoparticles on SiO 2 and a conventionally prepared catalyst. The optimized CoO/SiO 2 catalyst consistently exhibited higher activity and CH 4 selectivity (ca. 98%) across various pretreatment reduction temperatures as compared to the other catalysts. This remarkable performance was attributed to particle stability and consistent H* surface coverage, even after undergoing the highest temperature reduction, achieving a more stable catalytic species that resists sintering and carbon occlusion.

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

Constraining Erosion Rates and Landscape Evolution With In Situ 10 Be and 26 Al Cosmogenic Nuclides at Table Mountain, Antarctica

Abstract This study investigates surface weathering and sediment preservation at Table Mountain, a high‐elevation, hyperarid, polar landscape in the Transantarctic Mountains. We report cosmogenic nuclide concentrations ( 10 Be and 26 Al) in quartz from bedrock surfaces, erratic boulder lag, and cobbles embedded within Sirius Group sediments to quantify erosion rates. In situ 10 Be and 26 Al depth profiles from a 2.95 m permafrost core in the Sirius Group further constrain surface erosion rates and elucidate landscape stability. Measured 10 Be and 26 Al concentrations from two sandstone bedrock surfaces adjacent to Sirius Group sediments give erosion rates of 0.18–0.28 m/Myr. An erratic sandstone boulder within the lag above the Sirius Group yields erosion rates of ∼0.42 ± 0.03 m/Myr, whereas two cobbles embedded within the Sirius Group yield higher rates of 0.81–1.12 m/Myr. Depth profiles of in situ 10 Be and 26 Al indicate no vertical mixing of Sirius Group permafrost since deposition. Depth profile models are best explained by erosion rates of 0.53 +0.13 / −0.12 m/Myr, and an exposure age of 0.78 +0.06 / −0.08 Ma. We view the model “age” to represent the ∼0.8‐million‐year time‐scale for surface lowering equivalent to one attenuation length of cosmic ray production to achieve steady‐state conditions. Continual exhumation of embedded clasts from within the Sirius Group results in an accumulation of clasts forming the observed erosional lag deposit covering the landscape. Our erosion rates of the Sirius Group surface based on in situ 10 Be and 26 Al depth profiles are an order‐of‐magnitude larger than those based on meteoric 10 Be infiltration and further clarification is required.

58 GEOSCIENCES↗
DOE OSTI2022

Multiple magnetic orders in LaFeAs 1-x P x O uncover universality of iron-pnictide superconductors

The iron-pnictide superconductors have generated tremendous excitement as the competition between magnetism and superconductivity has allowed unique in-roads towards elucidating a microscopic theory of unconventional high-temperature superconductivity. In addition to the stripe spin density wave ($C^a_{2M}$) phase observed in the parent compounds of all iron-pnictide superconductors, two novel magnetic orders have recently been discovered in different parent structures: an out-of-plane collinear double-Q ($C^c_{4M}$) structure in the hole-doped (Ca, Sr, Ba) 1-x (Na) x Fe 2 As 2 and Ba 1-x K x Fe 2 As 2 families, and a spin vortex crystal “hedgehog” ($C^{ab}_{4M}$) structure in the CaKFe 4 As 4 family. Using neutron diffraction, we demonstrate that LaFeAs 1-x P x O contains all three magnetic orders within a single-phase diagram as a function of substitution, all of which compete strongly with superconductivity. Our experimental observations combined with theoretical modeling demonstrate how the reduction in electronic correlations by chemical substitution results in larger Fermi surfaces and the sequential stabilization of multiple magnetic anisotropies. Our work presents a unified narrative for the competing magnetic and superconducting phases observed in various iron-pnictide systems with different crystal structures and chemistry.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2026

Curvilinear magnetic effects in helicoid nanotubes

We report the fabrication and characterization of ferromagnetic helicoid nanotubes with a tunable surface curvature and chirality. Through combining focused electron beam induced deposition and magnetron sputtering we realize these complex curvilinear magnetic architectures. Electron holography reveals two distinct states: a single domain remanent state, with a magnetic chirality governed by the geometric chirality, and a vortex-anti-vortex domain wall, preferentially forming at areas of lower curvature. Micromagnetic simulations reveal how the geometry, specifically pitch and local surface curvature, affects the stability and formation of magnetic domain walls. Furthermore, we show that the interplay between magnetic and geometric chirality has a strong impact on domain wall motion, whereby a right-handed geometric chirality leads to faster domain wall motion and a left-handed geometry hinders domain wall transport. The results shown here highlight the potential of 3D magnetic architectures in spintronic devices and offer insights into how geometry and curvature affect the magnetization, the distribution of magnetic solitons and the motion of domain walls.

3D Nanomagnetism↗
DOE OSTI2017

Isoreticular expansion of polyMOFs achieves high surface area materials

The concept of isoreticular chemistry has become a core principle in metal–organic framework (MOF) materials. Isoreticular chemistry has shown that organic ligands of different sizes, but with a common geometry/symmetry can be used to generate MOFs of related topologies, but with expanded pore sizes and volumes. In this study, polymer–MOF hybrid materials (polyMOFs) with a UiO (UiO = University of Oslo) architecture are shown to adhere to the principle of isoreticular expansion, generating polyMOFs with large surface areas and enhanced stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Vertical Co 9 S 8 hollow nanowall arrays grown on a Celgard separator as a multifunctional polysulfide barrier for high-performance Li–S batteries

Lithium–sulfur (Li–S) batteries have been regarded as one of the most promising next-generation energy-storage devices, due to their low cost and high theoretical energy density (2600 W h kg -1 ). However, the severe dissolution of lithium polysulfides (LiPSs) and the fatal shuttle effect of the sulfur cathode seriously hinder the practical applications of Li–S batteries. To address such issues, we present here, for the first time, a novel metal organic framework (MOF)-derived Co 9 S 8 nanowall array with vertical hollow nanoarchitecture and high electrical conductivity, which is grown in situ on a Celgard separator (Co 9 S 8 –Celgard) via a feasible and scalable liquid-reaction approach, as an efficient barrier for LiPSs in Li–S batteries. Benefiting from the direct in situ growth of vertical Co 9 S 8 hollow nanowall arrays as a multifunctional polar barrier, the Co 9 S 8 –Celgard separator possesses large surface area, excellent mechanical stability, and particularly strong LiPS-trapping ability via chemical and physical interactions. With these advantages, even with a pure sulfur cathode with a high sulfur loading of 5.6 mg cm -2 , the Li–S cells with the Co 9 S 8 –Celgard separator exhibit outstanding electrochemical performance: the initial specific capacity is as high as 1385 mA h g -1 with a retention of 1190 mA h g -1 after 200 cycles. The cells deliver a high capacity of 530 mA h g -1 at a 1C rate (1675 mA g -1 ) even after an impressive number of 1000 cycles with an average capacity fade of only 0.039% per cycle, which is promising for long-term cycling application at high charge/discharge current densities, and pouch-type Li–S cells with the Co 9 S 8 –Celgard separator display excellent cycling performance. When the optimized cathode with the sulfur loading in well-designed yolk–shelled carbon@Fe 3 O 4 (YSC@Fe 3 O 4 ) nanoboxes is employed, the cell with Co 9 S 8 –Celgard delivers a high initial capacity of 986 mA h g -1 at a 1C rate with a capacity retention as high as 83.2% even after a remarkable number of 1500 cycles. In conclusion, this work presents a strategy to grow on the separator a multifunctional polar interlayer with unique nanoarchitecture and high conductivity to chemically and physically trap the LiPSs, thus significantly enhancing the performance of Li–S batteries.

25 ENERGY STORAGE↗
DOE OSTI2026

2D nanoconfinement distorts the solvation structure of hydroxide but not of hydronium

Understanding ion-specific behavior in nanoconfined water is essential for controlling charge transport and selectivity in two-dimensional membranes. Motivated by recent experiments revealing anomalous dielectric and transport behavior of water confined between hBN sheets, we use machine-learning-accelerated first-principles molecular dynamics to investigate the interfacial propensities of hydronium and hydroxide ions under similar confinement. We find that hydronium remains interfacial across all confinement regimes, whereas hydroxide shifts toward the interior as the environment becomes more bulk-like. This contrasting behavior reflects the combined influence of hydrogen bonding, interfacial water layering, and the polarization of hBN, which collectively stabilize hydronium at the surface while making hydroxide slightly more favorable within the structured interior. These findings expose an asymmetry in ion-surface coupling and establish a microscopic origin for hydronium’s enhanced interfacial affinity. The results provide mechanistic insight into ion partitioning in two-dimensional channels and highlight the collective structuring of confined water as a key determinant of interfacial ion thermodynamics.

organic↗
DOE OSTI2023

Effect of substrate and growth method on vanadium dioxide thin films by RF magnetron sputtering: Vanadium metal oxidation vs reactive sputtering

Vanadium dioxide (VO 2 ) undergoes a metal–insulator phase transition at ~70 °C and has attracted substantial interest for potential applications in electronics, including those in neuromorphic computing. The vanadium–oxygen system has a rather complicated phase diagram, and controlling the stoichiometry and the phase of thin films of vanadium oxides is a well-known challenge. Here, we explore the novel combination of two methods of VO 2 thin film deposition using off-axis RF magnetron sputtering on (100)- and (111)-oriented yttria-stabilized zirconia (YSZ) substrates: reactive sputtering of vanadium in an oxygen environment and sputtering of vanadium metal followed by oxidation to VO 2 . Interestingly, the reactive sputtering process on both substrate orientations yields the metastable semiconducting VO 2 (B) phase, which is structurally stabilized by the YSZ surface. The metal sputtering and oxidation process on YSZ produces mainly the equilibrium monoclinic (or M1) phase of VO 2 that exhibits a metal–insulator transition. Using this method, we obtained thin films of (010)-textured polycrystalline VO 2 (M1) that show a metal–insulator transition with an on/off ratio larger than 1000.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Molecular dynamics studies of knotted polymers

Molecular dynamics calculations have been used to explore the influence of knots on the strength of a polymer strand. In particular, the mechanism of breaking 31, 41, 51, and 52 prime knots has been studied using two very different models to represent the polymer: (1) the generic coarse-grained (CG) bead model of polymer physics and (2) a state-of-the-art machine learned atomistic neural network (NN) potential for polyethylene derived from electronic structure calculations. While there is a broad overall agreement between the results on the influence of the pulling rate on chain rupture based on the CG and atomistic NN models, for the simple 31 and 41 knots, significant differences are found for the more complex 51 and 52 knots. Notably, in the latter case, the NN model more frequently predicts that these knots can break not only at the crossings at the entrance/exit but also at one of the central crossing points. The relative smoothness of the CG potential energy surface also leads to stabilization of tighter knots compared to the more realistic NN model.

DelloStritto, Mark (ORCID:0000000206785860)↗
DOE OSTI2021

Surface structure of mass-selected niobium oxide nanoclusters on Au(111)

The structures formed by the deposition of mass-selected niobium oxide clusters, Nb 3 O y ( y = 5, 6, 7), onto Au(111) were studied by scanning tunneling microscopy. The as-deposited Nb 3 O 7 clusters assemble into large dendritic structures that grow on the terraces as well as extend from the top and bottom of step edges. The Nb 3 O 6 cluster also forms dendritic assemblies but they are generally much smaller in size. The assemblies are composed of smaller discrete structures (<1 nm) which are likely to be single clusters. Furthermore, the dendritic assemblies for both the Nb 3 O 7 and Nb 3 O 6 clusters have fractal dimensions of about 1.7 which is very close to that expected for simple diffusion limited aggregation. Annealing the Nb 3 O 7,6 /Au(111) surfaces up to 550 K results in changes in assembly sizes and increases in heights, while heating to 700 results in the disruption of the assemblies into smaller structures. By contrast, the as-deposited Nb 3 O 5 /Au(111) surface at RT exhibits compact cluster structures which become 3D nanoparticles when annealed above 550 K. Differences in the observed surface structures and thermal stability are attributed to differences in metal-oxygen stoichiometry which can influence cluster binding energies, mobility and inter-cluster interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Constructive molecular configurations for surface-defect passivation of perovskite photovoltaics

Surface trap-mediated nonradiative charge recombination is a major limit to achieving high-efficiency metal-halide perovskite photovoltaics. The ionic character of perovskite lattice has enabled molecular defect passivation approaches through interaction between functional groups and defects. However, a lack of in-depth understanding of how the molecular configuration influences the passivation effectiveness is a challenge to rational molecule design. In this work, the chemical environment of a functional group that is activated for defect passivation was systematically investigated with theophylline, caffeine, and theobromine. When N-H and C=O were in an optimal configuration in the molecule, hydrogen-bond formation between N-H and I (iodine) assisted the primary C=O binding with the antisite Pb (lead) defect to maximize surface-defect binding. A stabilized power conversion efficiency of 22.6% of photovoltaic device was demonstrated with theophylline treatment.

14 SOLAR ENERGY↗
DOE OSTI2023

Stronger Tropical Cyclone–Induced Ocean Cooling in Near-Coastal Regions Compared to the Open Ocean

Abstract Tropical cyclones (TC) often induce strong mixing in the upper ocean that generates a trail of cooler sea surface temperature (Twake) in their wakes. The Twake can affect TC intensity, so its prediction is important, especially in coastal regions where TCs can make landfall. Coastal Twakes are often more complex than those in the open ocean due to the influences of coastline geometry, highly variable water depth, continental runoff, and shelf processes. Using observational data since 2002, here we show a significantly stronger global mean Twake in coastal regions compared to offshore regions. Temperature stratification is the main driver of stronger coastal Twakes in the North Atlantic and east Pacific. In the northwest Pacific and north Indian Ocean, the differences between coastal and offshore Twakes are smaller due to compensation between TC forcings and ocean stratification. The north Indian Ocean is unique in the Northern Hemisphere because salinity stratification plays a major role on the spatial distribution of Twake. In the South Pacific Ocean, TC intensity and translation speed are crucial for explaining coastal–offshore Twake differences, while ocean stratification and mixed layer depth are more important for the coastal–offshore Twake differences in the south Indian Ocean. These findings suggest that coastal–offshore differences in ocean stratification need to be properly represented in models in order to capture changes in TC-induced ocean cooling as storms approach landfall. Significance Statement Landfalling tropical cyclones (TCs) often cause considerable damage in coastal regions with dense human populations. Understanding TC–ocean interaction and how it differs between coastal and offshore regions can help predict TC intensity prior to landfall. Sea surface cooling after TC passage is an important proxy for TC–ocean interaction. A global evaluation of coastal TC-induced cooling has not been conducted. Using data covering two decades, we show significantly stronger TC-induced surface cooling in coastal regions compared to offshore regions at the global scale and in all basins except the northwest Pacific and north Indian Ocean. The difference is driven mainly by upper-ocean conditions in the North Atlantic, east Pacific, and south Indian Ocean, and by TC characteristics in the South Pacific.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2018

Symmetry Breaking Induced Activation of Nanocrystal Optical Transitions

We have analysed the effect of symmetry breaking on the optical properties of semiconductor nanocrystals due to doping by charged impurities. Using doped CdSe nanocrystals as an example, we show the effects of a Coulomb center on the exciton fine-structure and optical selection rules using symmetry theory and then quantify the effect of symmetry breaking on the exciton fine structure, modelling the charged center using a multipole expansion. The model shows that the presence of a Coulomb center breaks the nanocrystal symmetry and affects its optical properties through mixing and shifting of the hole spin and parity sublevels. This symmetry breaking, particularly for positively charged centers, shortens the radiative lifetime of CdSe nanocrystals even at room temperature, in qualitative agreement with the increase in PL efficiency observed in CdSe nanocrystals doped with positive Ag charge centers [A. Sahu et.al., Nano Lett. 12 , 2587, (2012)]. The effect of the charged center on the photoluminescence and the absorption spectra is shown, with and without the presence of compensating charges on the nanocrystal surface. While spectra of individual nanocrystals are expected to shift and broaden with the introduction of a charged center, configuration averaging and inhomogeneous broadening are shown to wash out these effects. The presence of compensating charges at the NC surface also serves to stabilize the band edge transition energies relative to NCs with no charge centers.

bio-inspired↗
DOE OSTI2020

Modeling Metallic Fuel using Peridynamics

Based on available modeling and simulation capabilities of peridynamics module in MOOSE framework for oxide fuel, the overall goal of this project is to further develop the peridynamics capabilities for modeling metallic fuel. It includes two major tasks: 1) develop validated scheme to handle the shape tensor singularity due to insufficient active neighbors of a material particle in the peridynamic correspondence model for fracture problems, and 2) develop failure modeling scheme including failure criterion for metallic fuels. Before the peridynamics can be applied to model metallic fuel, the formulation instability of the peridynamic correspondence model should be addressed. The PI first worked on developing new stabilization method to improve the performance of the peridynamic correspondence model and reduce the possibility of getting a singular shape tensor while applying the model for fracture problems. The new stabilization scheme uses bond-associated weight function rather than bond-associated horizon. Compared to bondassociated horizon stabilized method, this new stabilization scheme has better performance with improved prediction accuracy and reduced free surface effect. Using this newly developed stabilization, materials models from BISON can be directly used in peridynamics for metallic fuels, such as fission rate and burnup dependent creep and swell models. Publication of this work is under preparation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗