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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Entanglement spectra of stabilizer codes: A window into gapped quantum phases of matter

The entanglement spectrum (ES) provides a barometer of quantum entanglement and encodes physical information beyond that contained in the entanglement entropy. In this paper, we explore the ES of stabilizer codes, which furnish exactly solvable models for a plethora of gapped quantum phases of matter. Studying the ES for stabilizer Hamiltonians in the presence of arbitrary weak local perturbations thus allows us to develop a general framework within which the entanglement features of gapped topological phases can be computed and contrasted. In particular, we study models harboring fracton order, both type-I and type-II, and compare the resulting ES with that of both conventional topological order and of (strong) subsystem symmetry protected topological (SSPT) states. We find that nonlocal surface stabilizers (NLSS), a set of symmetries of the Hamiltonian which form on the boundary of the entanglement cut, act as purveyors of universal nonlocal features appearing in the entanglement spectrum. While in conventional topological orders and fracton orders, the NLSS retain a form of topological invariance with respect to the entanglement cut, subsystem symmetric systems—fracton and SSPT phases—additionally show a nontrivial geometric dependence on the entanglement cut, corresponding to the subsystem symmetry. This sheds further light on the interplay between geometric and topological effects in fracton phases of matter and demonstrates that strong SSPT phases harbour a measure of quasilocal entanglement beyond that encountered in conventional SPT phases. Here, we further show that a version of the edge-entanglement correspondence, established earlier for gapped two-dimensional topological phases, also holds for gapped three-dimensional fracton models.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Interpretable design of Ir-free trimetallic electrocatalysts for ammonia oxidation with graph neural networks

The electrochemical ammonia oxidation to dinitrogen as a means for energy and environmental applications is a key technology toward the realization of a sustainable nitrogen cycle. The state-of-the-art metal catalysts including Pt and its bimetallics with Ir show promising activity, albeit suffering from high overpotentials for appreciable current densities and the soaring price of precious metals. Herein, the immense design space of ternary Pt alloy nanostructures is explored by graph neural networks trained on ab initio data for concurrently predicting site reactivity, surface stability, and catalyst synthesizability descriptors. Among a few Ir-free candidates that emerge from the active learning workflow, Pt 3 Ru-M (M: Fe, Co, or Ni) alloys were successfully synthesized and experimentally verified to be more active toward ammonia oxidation than Pt, Pt 3 Ir, and Pt 3 Ru. More importantly, feature attribution analyses using the machine-learned representation of site motifs provide fundamental insights into chemical bonding at metal surfaces and shed light on design strategies for high-performance catalytic systems beyond the d-band center metric of binding sites.

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

Protonation Stimulates the Layered to Rock Salt Phase Transition of Ni‐Rich Sodium Cathodes

Abstract Protonation of oxide cathodes triggers surface transition metal dissolution and accelerates the performance degradation of Li‐ion batteries. While strategies are developed to improve cathode material surface stability, little is known about the effects of protonation on bulk phase transitions in these cathode materials or their sodium‐ion battery counterparts. Here, using NaNiO 2 in electrolytes with different proton‐generating levels as model systems, a holistic picture of the effect of incorporated protons is presented. Protonation of lattice oxygens stimulate transition metal migration to the alkaline layer and accelerates layered‐rock‐salt phase transition, which leads to bulk structure disintegration and anisotropic surface reconstruction layers formation. A cathode that undergoes severe protonation reactions attains a porous architecture corresponding to its multifold performance fade. This work reveals that interactions between electrolyte and cathode that result in protonation can dominate the structural reversibility/stability of bulk cathodes, and the insight sheds light for the development of future batteries.

25 ENERGY STORAGE↗
DOE OSTI2019

Toward Long-Life, Ultrahigh-Nickel Layered Oxide Cathodes for Lithium-Ion Batteries: Optimizing the Interphase Chemistry with a Dual-Functional Polymer

Boosting the Ni content in LiMO 2 (M = Ni, Co, Mn, etc.) layered oxides is a promising way to establish high-energydensity, low-cost cathodes, but the poor cathode surface stability is a daunting challenge for their practical viability. Herein, by constructing a dual-functional binder framework with a conductive polymer - polyaniline (PANI), the ultrahigh-Ni layered oxide cathode (LiNi 0.94 Co 0.06 O 2 ) exhibits significantly improved cyclability, with a capacity retention greatly increased from 47% to 81% over 1,000 cycles in full cells. It is demonstrated that the acidic species (e.g. HF) in the electrolyte can be efficiently scavenged through a protonation process of PANI, hence the cathode surface reactivity is greatly suppressed and the rock-salt phase propagation into bulk structure is considerably alleviated. Furthermore, the PANI binder system effectively prevents both the cathode-electrolyte interphase (CEI) and anode-electrolyte interphase (AEI) from degrading to a thick “triple-layer” architecture upon extensive cycling, resulting in more robust, thinner CEI and AEI with regulated interphasial chemistry. Moreover, the delocalized π-conjugated electrons along the backbone of PANI facilitate fast electron transfer and promote rate capability even at low temperatures (-20 °C). Finally, this work sheds light on rational binder engineering for developing high-energy-density lithium-ion batteries with acceptable cycle life.

25 ENERGY STORAGE↗
NASA NTRS2007

Development of Training Programs to Optimize Planetary Ambulation

Astronauts experience disturbances in functional mobility following their return to Earth due to adaptive responses that occur during exposure to the microgravity conditions of space flight. Despite significant time spent performing in-flight exercise routines, these training programs have not been able to mitigate postflight alterations in postural and locomotor function. Therefore, the goal of our two inter-related projects (NSBRI-ground based and ISS flight study, "Mobility") is to develop and test gait training programs that will serve to optimize functional mobility during the adaptation period immediately following space flight, thereby improving the safety and efficiency of planetary ambulation. The gait training program entails manipulating the sensory conditions of treadmill exercise to systematically challenge the balance and gait control system. This enhances the overall adaptability of locomotor function enabling rapid reorganization of gait control to respond to ambulation in different gravitational environments. To develop the training program, we are conducting a series of ground-based studies evaluating the training efficacy associated with variation in visual flow, body loading, and support surface stability during treadmill walking. We will also determine the optimal method to present training stimuli within and across training sessions to maximize both the efficacy and efficiency of the training procedure. Results indicate that variations in both visual flow and body unloading during treadmill walking leads to modification in locomotor control and can be used as effective training modalities. Additionally, the composition and timing of sensory challenges experienced during each training session has significant impact on the ability to rapidly reorganize locomotor function when exposed to a novel sensory environment. We have developed the capability of producing support surface variation during gait training by mounting a treadmill on a six-degree-of-freedom motion device. This hardware development will allow us to evaluate the efficacy of this type of training in conjunction with variation in visual flow and body unloading.

Bloomberg, J. J.↗
DOE OSTI2020

Dispersity-Driven Stabilization of Coexisting Morphologies in Asymmetric Diblock Copolymer Thin Films

Despite decades of research, characterization of the effects of polymer chain dispersity on the structural properties of block copolymer thin films remains challenging. Here we present an integrated experimental and modeling approach to characterize the morphology of thin films containing asymmetric diblock copolymers. Specifically, we used synergistic neutron reflectivity (NR) and self-consistent field theory (SCFT)-based modeling to realize unexpected morphology of thin films containing asymmetric copolymers. Using NR, a highly stable and reproducible mixed phase of coexisting cylinders and lamellar domains was discovered in asymmetric poly(deuterated-styrene-b-n butyl methacrylate) (dPS-PBMA) copolymer thin films containing 34% volume fraction of dPS. SCFT reveals how to obtain such a thermodynamically stable morphology in the presence of disperse majority block and asymmetric interactions of polymer species with surfaces. Stabilization of the coexisting domains is a consequence of the depth segregation based on chain-length distribution. The asymmetric chains microphase-separate into cylindrical domains close to the substrate and near-symmetric chains form lamellar domains at the air interface. In the absence of dispersity, the coexistence of cylindrical and lamellar domains is thermodynamically unstable because of the absence of depth segregation. Overall, such an effect of dispersity on diblock copolymer thin-film morphology reveals a unique and powerful strategy to create coexisting nanoscale domains and tailor properties of thin films.

36 MATERIALS SCIENCE↗
NASA NTRS1986

Investigation of chord ratio, stagger, decalage angle, and flap angle for dual wing configurations

Aerodynamical closely coupled dual wing configurations of unequal chords are investigated for medium speed general aviation applications. Vortex panel and momentum boundary layer analysis are utilized for the two-dimensional predictions. A multi-surface vortex lattice method is used for the three-dimensional predictions. In the process of searching for the highest lift to drag ratio upper airfoil to lower airfoil chord ratios, both greater than and less than one, are investigated in terms of stagger, decalage angle, and gap. With the optimum chord ratio, at the optimum stagger and gap, proper spanwise decalage distribution is shown to yield the lowest two dimensional drag results. Various wing taper ratios and wing twists are investigated to increase wing efficiency. Comparisons are made between optimized dual and optimized single wing configurations both with the same fuselage, stabilator surfaces, engines, payload, and fuel. The dual wing configuration is shown to have significantly less drag and hence longer range than the conventional single wing configuration.

Selberg, B. P.↗
DOE OSTI2019

Cooling Induced Surface Reconstruction during Synthesis of High-Ni Layered Oxides

Transition metal layered oxides have been the dominant cathodes in lithium-ion batteries, and among them, high-Ni ones (LiNi x Mn y Co z O 2 ; x ≥ 0.7) with greatly boosted capacity and reduced cost are of particular interest for large-scale applications. The high Ni loading, on the other hand, raises the concern of surface instability and poor rate performance. The rational design of synthesis leading to layered LiNi 0.7 Mn 0.15 Co 0.15 O 2 with greatly enhanced rate capability is reflected, by implementing a quenching process alternative to the general slow cooling. In situ synchrotron X-ray diffraction, coupled with surface analysis, is applied to studies of the synthesis process, revealing cooling-induced surface reconstruction involving Li 2 CO 3 accumulation, formation of a Li-deficient layer and Ni reduction at the particle surface. The reconstruction process happens predominantly at high temperatures (above 350 °C) and is highly cooling-rate dependent, implying that surface reconstruction can be suppressed through synthetic control, i.e., quenching to improve the surface stability and rate performance of the synthesized materials. These findings may provide guidance to rational synthesis of high-Ni cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2024

The Role of Non-Local Effects on Surface Sensible Heat Flux Under Different Types of Thermal Structures Over the Arctic Sea-Ice Surface

The effects of atmospheric thermal structure on the surface energy flux are poorly understood over the Arctic sea-ice surface. Here, we explore the mechanism of sensible heat exchange under different types of thermal structures over the Arctic sea-ice surface by using data collected during the Multidisciplinary drifting Observatory for the Study of Arctic Climate expedition. The quadrant analysis indicates that strong surface temperature inversions below 100 m enhance non-local effects on the positive (upward) sensible heat flux ($\overline{w'θ'}$) through entrainment of large eddies from the convective boundary layer aloft. However, strong surface inversions restrict the contributions of large eddies to the negative (downward) $\overline{w'θ'}$ due to intensified surface stability. By inspecting the existing parameterization schemes, we found that the European Center for Medium-Range Weather Forecasts Integrated Forecasting System scheme fails to predict the impacts of non-local processes on the positive $\overline{w'θ'}$, and an adjustment term to correct the bias of parameterized $\overline{w'θ'}$ is proposed.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1958

Estimation of Directional Stability Derivatives at Small Angles and Subsonic and Supersonic Speeds

Methods are presented for estimating the directional stability derivative increments contributed by the stabilizing surfaces of subsonic and supersonic aircraft. These methods are strictly applicable at zero angle of attack and small angles of sideslip. The procedure of totaling the incremental coefficients to obtain an estimation of the total empennage side-force and yawing-moment coefficient derivatives is also shown, together with numerical examples. A correlation is presented between estimated and experimental incremental coefficients which indicates that the methods of this report generally estimate the increment of side force gained by the addition of a panel to within +/-10 percent of the experimental value while the yawing-moment increment is generally estimated to within +/-20 percent. This is true for both subsonic and supersonic Mach numbers. An example application of the methods to one of the problems in directional stability, that of minimizing the effect of Mach number on the side-force coefficient derivative of the empennage, is discussed.

Goodwin, Frederick K.↗
DOE OSTI2024

Entropy-Stabilized Multication Fluorides as a Conversion-Type Cathode for Li-Ion Batteries–Impact of Element Selection

Metal fluorides (e.g., FeF 2 and FeF 3 ) have received attention as conversion-type cathode materials for Li-ion batteries due to their higher theoretical capacity compared to that of common intercalation materials. However, their practical use has been hindered by low round-trip efficiency, voltage hysteresis, and capacity fading. Cation substitution has been proposed to address these challenges, and recent advancements in battery performance involve the introduction of entropy stabilization in an attempt to facilitate reversible conversion reactions by increasing configurational entropy. Building on this concept, high entropy fluorides with five cations were synthesized by using a simple mechanochemical route. In order to examine the impact of element selection, Co 0.2 Cu 0.2 Ni 0.2 Zn 0.2 Fe 0.2 F 2 (HEF-Fe) was compared with Co 0.2 Cu 0.2 Ni 0.2 Zn 0.2 Mg 0.2 F 2 (HEF-Mg), replacing electrochemically inactive Mg with Fe as an active participant in the conversion reaction. Combining electrochemical measurements with first-principles calculations, high-resolution electron microscopy, and synchrotron X-ray analysis, HEFs’ battery performances and conversion reaction mechanisms were investigated in detail. The results highlighted that replacement of Mg with Fe was beneficial, with enhanced capacity, rate capability, and surface stability. In addition, it was found that HEF-Fe showed similar cycle stability without an electrochemically inactive element. In conclusion, these findings provide valuable insights for the design of high entropy multielement fluorides for improved Li-ion battery performance.

25 ENERGY STORAGE↗
NASA NTRS1961

Static Stability and Control of Canard Configurations at Mach Numbers from 0.70 to 2.22 - Triangular Wing and Canard with Twin Vertical Tails

The static aerodynamic characteristics of a canard airplane configuration having twin vertical stabilizing surfaces are presented. The model consisted of a wing and canard both of triangular plan form and aspect ratio 2 mounted on a Sears-Haack body of fineness ratio 12.5 and two swept and tapered wing-mounted vertical tails of aspect ratio 1.35. Data are presented for Mach numbers from 0.70 to 2.22 and for angles of attack from -6 to +18 deg. at 0 and 5 deg. sideslip. Tests were made with the canard off and with the canard on. Nominal canard deflection angles ranged from 0 to 10 deg. The Reynolds number was 3.68 x 10(exp 6) based on the wing mean aerodynamic chord. Selected portions of the data obtained in this investigation are compared with previously published results for the same model having a single vertical tail instead of twin vertical tails. Without the canard, the directional stability at supersonic Mach numbers and high angles of attack was improved slightly by replacing the single tail with twin tails. However, at a Mach number of 0.70, the directional stability of the twin-tail model deteriorated rapidly with increasing angle of attack above 10 deg. and fell considerably below the level for the single-tail model. At subsonic speeds the directional stability of the twin-tail model with the canard was comparable to that for the single-tail model and at supersonic speed it was considerably greater at high angles of attack. Unlike the single-tail model, the twin-tail model at 50 sideslip exhibited an unstable break in the variation of pitching-moment coefficient with lift coefficient near 10 deg. angle of attack for 0.70 Mach number.

Peterson, Victor L.↗
DOE OSTI2025

Alkali Cation Inhibition of Imidazolium-Mediated Electrochemical CO 2 Reduction on Silver

Imidazolium-based ionic liquids have led to enhanced CO 2 electroreduction activity due to cation effects at the cathode surface, stabilizing the reaction intermediates and decreasing the activation energy. In aqueous media, alkali cations are also known to improve CO 2 reduction activity on metals such as Ag, with the enhancement attributed to electrical double layer effects and trending with the size of the alkali cation. However, the effect of a mixed catholyte solution of alkali cations in the presence of an imidazolium-based ionic liquid has not been well-explored. Herein, 1-ethyl-3-methylimidazolium tetrafluoroborate, [EMIM][BF 4 ], in water was investigated with alkali salts to unravel the interaction effects for CO 2 electroreduction on Ag. Although both [EMIM] + and alkali cations have individually improved CO 2 to CO conversion on Ag in water, electrochemical results showed that alkali cations hindered imidazolium-mediated CO 2 electroreduction in most conditions. Li + , in particular, was sharply inhibitory compared to other alkali cations and strongly redirected the selectivity to hydrogen evolution. The nature of the alkali cation inhibition was investigated with spectroscopic techniques, including in situ surface-enhanced Raman spectroscopy (SERS) and dynamic electrochemical impedance spectroscopy (DEIS). Along with computational insights from density functional theory (DFT), the electrochemical and spectroscopic data suggest that alkali cations inhibit [EMIM]-mediated CO 2 reduction by competing for surface adsorption sites, preventing the potential-dependent structural reorientation of imidazolium, and promoting hydrogen evolution by bringing solvated water to the cathode surface.

cations↗
DOE OSTI2022

Crossover Effects in Lithium–Metal Batteries with a Localized High Concentration Electrolyte and High–Nickel Cathodes

While crossover effects, such as transition–metal dissolution, are well–understood in lithium–ion batteries, there is a limited understanding of the effect of crossed–over chemical species in cells with oxide cathodes and lithium–metal anodes. In this work, the effects of cathode–to–anode and anode–to–cathode crossover are explored in cells with a high–nickel cathode, lithium–metal anode, and a localized high–concentration electrolyte (LHCE). Dramatic differences are found among cells; a lithium–metal anode paired with a high–nickel cathode has three times less solid–electrolyte interphase growth than a lithium–metal anode paired with lithium metal. Meanwhile, the cathode paired with lithium metal has 2–3 times higher capacity fade than the same cathode paired with graphite. Decomposition and crossover of the FSI salt is identified as the main source of these changes. The fluorine in the salt is first stripped off at the lithium–metal anode, and the remaining sulfur and nitrogen cross over to the cathode. Although the reduction in fluorine content harms the surface stability of the cathode, the lithium–metal anode benefits from the increased fluorine content. Furthermore, because the lithium–metal anode is typically the bottleneck for cells with thin lithium, crossover is a major factor in the enhanced performance of lithium–metal batteries with LHCE.

25 ENERGY STORAGE↗
DOE OSTI2026

Shapeshifting Nanocatalyst for CO2 Conversion

The conversion of CO2 into high-value chemicals through a photoreduction reaction in water is a promising route to reduce the dependence on fossil fuels. Enhancing selectivity toward hydrocarbons or alcohols can be achieved by Ag-Cu alloys. However, the stabilized surface state created by Ag-Cu interactions is still poorly understood. In this work, multi-modal in situ X-ray experiments reveals underlying mechanisms and the evolution of Ag-Cu nanoparticles under CO2 reduction reaction (CO2RR) conditions. Both morphological and chemical changes of Ag and Cu species induced by diffusion mechanics are tracked during nanocatalyst operation. The initial spheroid Ag-Cu nanoparticles are composed of a Cu-rich shell and Ag-rich core. The reduction treatment promotes Ag migration toward the surface. During photocatalytic CO2 reduction reaction, Cu atoms migrate back to the surface, forming Ag-Cu-O species. The study observes the surface oxidation of Cu(0) to Cu+ and the presence of Ag at the sub-surface region. Furthermore, nanoparticles change their shape, decreasing their specific surface area, driven by Cu diffusion during the CO2 photoreduction reaction. The results provide invaluable insights into the dynamic restructuring of the catalyst under reaction conditions and into the active species responsible for CO2 conversion.

CO2 reduction reaction↗
DOE OSTI2021

Effect of Ligand Polarity on the Internal Dipoles and Ferroelectric Distortion in BaTiO 3 Nanocubes

Here, surface adsorbates and surrounding matrix species have been demonstrated to affect the properties of nanoscale ferroelectrics and nanoscale ferroelectric composites; potentially counteracting performance losses that can occur in small particle sizes. In this work, the effects of nonpolar oleic acid (OA) and polar tetrafluoroborate (BF 4 - ) ligand capping on the surface of various sizes of BaTiO 3 nanocubes have been investigated with combined neutron diffraction and neutron pair distribution function (PDF), density functional theory (DFT), and ab initio molecular dynamics (AIMD) methods. The low real space PDF region provides an unobstructed view of rhombohedral (split short and long) Ti-O distances in BaTiO 3 nanocubes, mimicking the well-established order-disorder local structure found in bulk BaTiO 3 . Interestingly, the intermediate-range order in nanocubes is found to be orthorhombic, rather than tetragonal. It is concluded that polar ligands adsorbed at BaTiO 3 surfaces stabilize the correlation length scale of local rhombohedral distortions in ferroelectric nanoparticles relative to nonpolar ligands.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

A comparative study on cubic and tetragonal Ce-ZrO 2 supported Rh catalysts for N 2 O decomposition

Zirconium oxide (ZrO 2 ) exhibits strong synergy with cerium oxide (CeO 2 ), acting as a structural and electronic promoter during catalytic redox reactions. As a result, Ce-ZrO 2 composite oxides are widely used as supports in various catalytic systems. In our previous work, we demonstrated that the incorporation of Zr 4+ into the CeO 2 lattice significantly enhanced Rh dispersion, improved redox ability, and stabilized surface Rh species, which collectively boosted the de-N 2 O activity of Rh/Ce-ZrO 2 catalysts. Building on these findings, the present study emphasizes that the crystallographic phase of Ce-ZrO 2 , governed by the Ce/Zr ratio, plays a decisive role in tuning the physicochemical environment of Rh active sites and thereby optimizing catalytic performance. In conclusion, tailoring the Ce/Zr ratio to favor the cubic fluorite structure emerges as a promising strategy for the rational design of highly active and stable catalysts for N 2 O decomposition and potentially other redox-sensitive environmental applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Selective activation of methane C–H bond in the presence of methanol

Direct methane to methanol (MTM) conversion over heterogeneous catalysts is a promising route for valorization of methane. The methane C-H bond activation is considered as the key step of the MTM and is the focus of considerable research activity. However, the formed methanol typically suffers from overoxidation largely due to the cleavage of a methanol C-H bond, whose bond dissociation energy is ca. 0.5 eV lower than that of the methane C-H bond, which usually translates to a transition state energy of the methanol C-H bond cleavage that is ca. 0.55 eV lower than that of methane whenever the reactions proceed through a radical mechanism. Furthermore, we propose a general approach for decreasing the transition state energy difference between the CH 4 and CH 3 OH C-H bond dissociation. When a metal-oxide supported cationic transition metal atom and a neighboring oxygen on the oxide surface serve as the active site, the transition state energy difference through a surface-stabilized pathway can be noticeably narrowed as compared with that of a radical pathway. For Ir, Pt and Rh-doped anatase TiO 2 (101), the CH 4 C-H bond activation can be preferred over that of CH 3 OH at significant methanol mole fraction. Also, for PdAu alloys containing adsorbed oxygen and positively charged Pd, calculations suggest in agreement with recent experiments (Science 367 (6474), 193-197) that the CH 4 C-H bond can be selectively activated in the presence of CH 3 OH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗