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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

Quantification of Dead Lithium on Graphite Anode under Fast Charging Conditions

A series of computational and experimental studies were conducted to understand the onset of lithium plating and subsequent quantification of dead lithium on graphite electrodes in the design of fast charging batteries. The experiments include titration and relaxation studies for detecting initiation of lithium metal plating for various SOC and C-rates, which are compared against the thermodynamically consistent phase field computational results. The collaborative study on "model graphite electrode" with 2.18 mAh cm-2 nominal capacity at 25 degrees C demonstrates: (1) the macroscopic voltage response during relaxation studies indicate the reintercalation of plated lithium into the graphite anode; (2) for SOC below 60% and low C-Rates, there is no dead lithium; (3) for SOC between 60% to 80%, and C-Rates in the range of 4C-6C show dead lithium both in experiments and simulations; (4) at 100% SOC and 4C-6C rates, large amounts of dead lithium are observed. The study presented here allows us to evaluate the effects of the physical properties of the electrochemical system on plating and stripping kinetics and the amount of dead lithium on graphite electrodes, which determines the cell capacity loss under fast charge.

batteries↗

Actuating Liquid Crystals Rapidly and Reversibly by Using Chemical Catalysis

Abstract Microtubules and catalytic motor proteins underlie the microscale actuation of living materials, and they have been used in reconstituted systems to harness chemical energy to drive new states of organization of soft matter (e.g., liquid crystals (LCs)). Such materials, however, are fragile and challenging to translate to technological contexts. Rapid (sub‐second) and reversible changes in the orientations of LCs at room temperature using reactions between gaseous hydrogen and oxygen that are catalyzed by Pd/Au surfaces are reported. Surface chemical analysis and computational chemistry studies confirm that dissociative adsorption of H 2 on the Pd/Au films reduces preadsorbed O and generates 1 ML of adsorbed H, driving nitrile‐containing LCs from a perpendicular to a planar orientation. Subsequent exposure to O 2 leads to oxidation of the adsorbed H, reformation of adsorbed O on the Pd/Au surface, and a return of the LC to its initial orientation. The roles of surface composition and reaction kinetics in determining the LC dynamics are described along with a proof‐of‐concept demonstration of microactuation of beads. These results provide fresh ideas for utilizing chemical energy and catalysis to reversibly actuate functional LCs on the microscale.

Chemistry↗

Dicyanobenzothiadiazole (DCBT) Organic Dye as a Visible Light Absorbing Strong Photoinduced Oxidant with a 16 Microsecond Long–Lived Excited State

Strong photoinduced oxidants are important to organic synthesis and solar energy conversion, to chemical fuels or electric. For these applications, visible light absorption is important to solar energy conversion and long–lived excited states are needed to drive catalysis. With respect to these desirable qualities, a series of five 5,6–dicyano[2,1,3]benzothiadiazole (DCBT) dyes are examined as organic chromophores that can serve as strong photooxidants in catalytic systems. The series utilizes a DCBT core with aryl groups on the periphery with varying electron donation strengths relative to the core. The dyes are studied via both steady–state and transient absorption and emission studies. Additionally, computational analysis, voltammetry, crystallography, and absorption spectroelectrochemistry are also used to better understand the behavior of these dyes. Ultimately, a strong photooxidant is arrived at with an exceptionally long excited state lifetime for an organic chromophore of 16 µs. Finally, the long–lived excited state photosensitizer is well–suited for use in catalysis, and visible light driven photosensitized water oxidation is demonstrated using a water–soluble photosensitizer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

S-duality in $ T\overline{T} $-deformed CFT

$ T\overline{T} $ deformed conformal field theories can be reformulated as worldsheet theories of non-critical strings. We use this correspondence to compute and study the $ T\overline{T} $ deformed partition sum of a symmetric product CFT. We find that it takes the form of a partition sum of a second quantized string theory with a worldsheet given by the product of the seed CFT and a gaussian sigma model with the two-torus as target space. We show that deformed symmetric product theory admits a natural UV completion that exhibits a strong weak coupling Z 2 duality that interchanges the momentum and winding numbers and maps the $ T\overline{T} $-coupling λ to its inverse 1/λ. The Z 2 duality is part of a full O(2, 2, Z)-duality group that includes a PSL(2, Z) acting on the complexified $ T\overline{T} $ coupling. The duality symmetry eliminates the appearance of complex energies at strong coupling for all seed CFTs with central charge c ≤ 6.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Progress and Challenges in Self-Healing Cementitious Materials

Concrete is the most used man-made material today consisting of a mixture of aggregates (sand, gravel, crashed rock) and paste. The paste component, made up of cement and water, cracks with time. Despite this shortcoming, research towards next-generation cement and concrete has only taken a boost in the past 10-15 years. In particular, self-healing cementitious materials is a research area that has attracted a great deal of attention. A number of reported novel formulations have demonstrated an increase in mechanical and chemical stability with respect to conventional Portland cement, through the addition of inorganic, organic, and even biological additives. This review reports on the latest advances in cement research related to the synthesis of self-healing cements applied in concrete structures. These include geopolymers, engineered cementitious materials (ECC), bacterial cement composites, microencapsulated self-healing materials, shape memory alloys (SMA), and polymer-cement composites. This work describes the performance of each cementitious material and the mechanism responsible for self-healing, including a section on the latest computational modeling studies towards this end. A detailed understanding of these various self-healing cement technologies, including their strengths and weaknesses, is critical at the time of determining the type of structures that these materials could be used for.

Fernandez, Carlos A.↗

Effect of Particle Spreading Dynamics on Powder Bed Quality in Metal Additive Manufacturing

Powder spreading precedes creation of every new layer in powder bed additive manufacturing (AM). The powder spreading process can lead to powder layer defects such as porosity, poor surface roughness and particle segregation. Therefore, the creation of homogeneous layers is the first task for optimal part printing. Discrete element methods (DEM) powder spreading simulations are typically limited to a single layer and/or small number of particles. Therefore, results from such model configurations may not be generalized to multiple layer processes. In this study, a computationally efficient multi-layer powder spreading DEM simulation model is proposed. The model is calibrated experimentally using static Angle of Repose measurements. The adhesion model parameter, cohesive energy density is related to adhesive surface energy and strain energy release rate parameters. The model results show that interaction between particle and the powder spreading rake leads to noticeable variation in packing density, surface roughness, dynamic angle of repose (AOR), particle size distribution, and particle segregation. Finally, the powder model is experimentally validated using a recoater spreading rig to measure the dynamic AOR at spreading speeds consistent with recoating speeds and layer heights used in AM processes.

36 MATERIALS SCIENCE↗

Impact of Different Thermal Gradients on the Dynamics of Cylindrical Lithium-ion Cells Subject to Accelerated Aging and on Module Performance

This study investigates the impacts of applying different thermal gradient patterns to cylindrical lithium-ion cells in a module on cell dynamics (temperatures, current flows, state of charge), module performance (evolution of resistance, capacity, and energy versus cycle number), and module lifetime. The thermal gradients were generated using cooling plates (CPs) with three different flow-field designs, namely, straight, perpendicular, and U-turn. The study uses computational fluid dynamics (CFD), the pseudo-two-dimensional (P2D) battery model, capacity loss and increased impedance due to the growth of a solid-electrolyte-interphase, and the electric current distribution from module terminals to cells that depends on the series-parallel electrical connections among the cells. The impact of the thermal gradient (resulting from the CP designs) on the variability in resistance, current, state of charge, and voltage among the cells was analyzed and linked to differences in the module's performance. Applying a thermal gradient to parallel-connected strings of series-connected cells led to variation in the current through each parallel string and an imbalance in the voltage of series-connected cells. Module performance is poorer when the thermal gradient causes a voltage imbalance than when it causes a current imbalance. Module performance becomes the worst when both current variation and voltage imbalance happen together. For instance, the module's lifetime (estimated as reaching 80% of its initial capacity) varied by 5% to 17.5%, depending on the magnitude and pattern of the imposed thermal gradient. As the relative orientation between thermal gradients and cells' electrical connectivity influences the module's performance, appropriate consideration should be given to the choice of the CP, especially if large thermal gradients are allowed.

Battery thermal management↗

Kinetic isotope effects for dissociative recombination of tritiated ketenyl ion ( 3 HCCO + ): A surface-hopping ab initio molecular dynamics study

Dissociative recombination (DR) reactions are important when modeling charged species in the presence of free electrons. While experimental measurements of DR reaction rates are challenging, surface hopping ab initio molecular dynamics (SH-AIMD) simulations provide an attractive alternative. SH-AIMD is especially well-suited for estimating branching ratios, i.e., the relative rates of competing production channels, for DR reactions. Although the radiolysis of diatomic tritium has been studied experimentally, previous attempts to model these systems have failed to account for isotope effects in DR reactions. Previous SH-AIMD studies have also not investigated tritium isotope effects for the branching ratios of DR reactions. In this study, we compute the DR branching ratios of the protiated and tritiated ketenyl ion. Comparison with literature values for the protiated branching ratios provides confidence in the reliability of our SH-AIMD results. Our simulations predict a significant increase of the HC + CO branching ratio for the tritiated system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-order finite element method for atomic structure calculations

We introduce featom, an open source code that implements a high-order finite element solver for the radial Schrödinger, Dirac, and Kohn-Sham equations. The formulation accommodates various mesh types, such as uniform or exponential, and the convergence can be systematically controlled by increasing the number and/or polynomial order of the finite element basis functions. The Dirac equation is solved using a squared Hamiltonian approach to eliminate spurious states. Here, to address the slow convergence of the $κ=±1$ states due to divergent derivatives at the origin, we incorporate known asymptotic forms into the solutions. We achieve a high level of accuracy (10 -8 Hartree) for total energies and eigenvalues of heavy atoms such as uranium in both Schrödinger and Dirac Kohn-Sham solutions. We provide detailed convergence studies and computational parameters required to attain commonly required accuracies. Finally, we compare our results with known analytic results as well as the results of other methods. In particular, we calculate benchmark results for atomic numbers (Z) from 1 to 92, verifying current benchmarks. We demonstrate significant speedup compared to the state-of-the-art shooting solver dftatom. An efficient, modular Fortran 2008 implementation, is provided under an open source, permissive license, including examples and tests, wherein particular emphasis is placed on the independence (no global variables), reusability, and generality of the individual routines.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Efficient Screening of Bi–Metallic Electrocatalysts for Glycerol Valorization

Glycerol is a byproduct of biodiesel production and, as such, it is of limited economic value. By means of electrooxidation, glycerol can be used as a feedstock for scalable hydrogen production, in addition to conversion to value-added products. The development of novel and efficient catalytic electrode materials for the anodic side of the reaction is a key towards a hydrogen-based energy economy. In the present study, a computational screening protocol combining DFT, scaling relations, and microkinetic modeling allows for a rational selection of novel catalysts that can deliver efficient glycerol electrooxidation, low cost of production, and environmental sustainability. Activity and chemical selectivity towards hydrogen production on pure metal catalysts is discussed in terms of volcano-shaped plots. We find that the selectivity in the glycerol oxidation reaction is influenced by a different energy landscape when in the presence of water and best classified by a comparison of O—H and C—H bond-breaking barriers. In addition, we screened 3570 bi-metallic catalysts in the AB (L1 0 ) and A 3 B (L1 2 ) ordered structures for activity, stability, price, and toxicity. By filtering based on the criteria for toxicity, resistance to oxidation, miscibility, and price, we have identified 5 L1 0 structured catalysts (AgPd, AuPd, PtSb, CuPt, and AgPt) and 20 L1 2 catalysts (Ga 3 Ta, In 3 Ta, Ir 3 W, Ir 3 Mo, Cu 3 Pt, Ir 3 Ta, Ir 3 Re, Pd 3 Bi, Pd 3 Cu, Pd 3 W, Pd 3 Co, Pd 3 Sn, Pd 3 Mo, Pd 3 Ag, Pd 3 Ga, Pd 3 Ta, Au 3 Ru, Pd 3 In, Au 3 Ir, and Pd 3 Au) that are all predicted to show high activity. We also identify an additional 37 L1 0 and 92 L1 2 structured electrocatalysts with an anticipated medium-high activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Strength-conductivity synergy via lean alloy design: A study on novel solid stir extrusion of an Al-2Cu-0.1 Nb-0.15Zr (~wt.%) alloy

Aluminum alloys find wide applications in power and transmission cables, and electrical conductors due to their advantageous properties of high electrical conductivity, and lower cost per unit. However, the lower tensile strength compared to copper poses a challenge for the mechanical stability of aluminum-based cables. In this study, we addressed this issue by adopting a process-based alloy design approach, creating a lean alloy with a dilute composition of Al-2Cu-0.1 Nb-0.15Zr (~wt.%). Here, the alloy was processed using a friction stir based novel SolidStir® (SSE) technique, followed by low-temperature aging. The resulting aluminum wire exhibited improved strength (240 MPa) while simultaneously enhancing electrical conductivity (64%IACS). The study employed computational simulations (Thermocalc) and experimental techniques (differential scanning calorimetry and transmission electron microscopy) to thoroughly investigate the microstructure. Microstructural examinations revealed that the precipitation kinetics in SSE and SSE+aged conditions played a significant role in enhancing strength and electrical conductivity. These findings demonstrate the successful achievement of high strength and high electrical conductivity in aluminum wire through a lean alloy design approach.

36 MATERIALS SCIENCE↗

Effects of water on the kinetics of acetone hydrogenation over Pt and Ru catalysts

We employed an approach combining reaction kinetics measurements at steady state conditions, electronic structure calculations employing density functional theory, and microkinetic modeling for acetone hydrogenation to provide insights into the effects of water on metal catalyst surfaces for the hydrogenation of oxygenates over a wide range of reaction conditions. Elucidation of the repulsive interactions due to adsorbed water molecules at various reaction conditions provides a basis to formulate rate expressions for heterogeneous catalytic processes of biomass oxygenates. Reaction kinetics experiments were carried out at partial pressures of H 2 , acetone, water and helium in the range of 0.51-0.79, 0.02-0.13, 0.08-0.23, 0-0.28 atm, respectively. We show that the addition of water enhances the hydrogenation rate at 353 K and 1 atm on oxophilic metal catalysts such as Ru/C, whereas the same promotional effect of water is not observed for Pt-based catalysts. Microkinetic model predictions for the hydrogenation of acetone on Ru in the absence and presence of water, using enthalpies and entropies obtained from DFT calculations, were in agreement with the experimentally observed reaction orders and activation barriers. The model shows that a water-assisted hydroxypropyl path is expected to be the favored path on Ru with a rate-determining step of H-OH-mediated hydrogenation of C 3 H 6 OH (i.e., the hydroxypropyl intermediate formed by H 2 O-mediated initial hydrogenation of acetone) to produce isopropyl alcohol (IPA). Furthermore, hydrogen, acetone, hydroxypropyl intermediate and hydroxyl species were predicted to be abundant on the Ru surface with a high coverage of nearly 85%. Lastly, the combined studies of computational and experimental catalysis on hydrogenation reactions help to elucidate the mechanistic role of water on metal catalyzed reactions for producing chemical building blocks from biomass-derived oxygenates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Feasibility of using crystal channeling for the beam loss mitigation in slow extraction at 8GeV

In the accelerator applications of slow extraction for High Energy Physics (HEP), one of the prime challenges is the mitigation of beam losses, which is becoming increasingly critical with the continuous rise in beam power. A significant breakthrough was achieved earlier at CERN through the successful deployment of proton beam channeling in a crystal at 400GeV, effectively diverting the beam away from extraction septa and offering new avenues for improving slow extraction efficiency. However, a crucial question remains whether this approach is still effective at lower and medium proton beam energies. In this paper, we present the promising results of the computer simulation studies of the septum shadowing at 8GeV for the Mu2e project slow extraction at Fermilab. In conclusion, across the wide range of beam parameters, the beam loss reduction is shown to range between 40% and factor of three.

43 PARTICLE ACCELERATORS↗

Performance analysis of integrated Nuclear-Solar Energy system sharing same molten salt thermal energy storage

Advanced nuclear reactors may be deployed with integrated thermal energy storage to improve flexibility and maximize revenue. This presents opportunities for thermal integration with concentrating solar power (CSP) to generate component synergies and/or improve performance. Here in this study, a computational model is developed for an integrated nuclear and CSP system that both share the same molten salt thermal energy storage (TES). Optimized dispatch schedules are developed subject to various market conditions, and the ratio of the nuclear to CSP thermal output is also varied. Performance of the combined system is compared to separate nuclear and solar plants, to determine if there is an overall benefit that can be derived from sharing the TES. Given sufficient volatility in electricity prices (e.g., under CAISO market conditions), synergies of up to 8% in net revenue are observed as a result of sharing the same TES, primarily due to improved revenue from enabling operation of the turbine closer to its design point, as well as being able to better take advantage of higher electricity prices. The synergy benefits are largest when the nuclear and solar plants have similar thermal output. However, when prices are less volatile the opposite behavior can be observed and it can be preferable to operate the nuclear plant as a baseload generator.

14 SOLAR ENERGY↗

Design of a novel carbon/carbon composite microvascular solar receiver

Solar thermal power tower systems are the primary technology being proposed for solar electricity from thermal energy. Operational limits on these towers are often driven by mechanical properties under significant thermal loads, particularly at the receiver where incoming flux is converted to thermal energy. While the solar receiver’s efficiency is largely driven by its optical properties, thermomechanical stresses on the receiver limits the operational envelope. One pathway to higher efficiency is greater allowable solar fluxes on the receiver but novel materials are required. The present study uses computational fluid dynamics to describe a parametric design space for a microvascular carbon/carbon composite solar receiver as a new material option for high flux solar receivers. Simulations are conducted for different microvascular geometries considering the role of material properties and heat transfer fluids, for the impact on thermal efficiency, and allowable strain. Results show that microscale receiver modules made of the proposed carbon/carbon composite could achieve thermal efficiencies over 90% and full-scale receivers can achieve up to 85% thermal efficiency for the design explored considering realistic strain limits, flux levels, and material properties. These values are highly dependent on the heat transfer fluid pairing, the through plane thermal conductivity of the carbon/carbon composite, the path architecture of the microscale receiver, and the incident solar flux profiles.

14 SOLAR ENERGY↗

Switching limits of top-gated carbon nanotube field-effect transistors

The performance limits of carbon nanotube field-effect transistors (CNFETs) based on a recently reported process are studied by computational techniques at temperatures between 300 K and 4 K. Here, the impact of band-to-band tunneling (BTBT) and source-to-drain tunneling (SDT) is examined for devices with varying gate length through the use of simulations based on the non-equilibrium Green’s function (NEGF) formalism, and calibrated to measurements. Additionally, the case of junctionless chemical doping profiles is analyzed in contrast to electrostatic doping recently reported for test structures. The switching limits of CNFETs are further explored for devices based on carbon nanotubes (CNTs) with more favorable electronic structures.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Defect Energetics in Pseudo-Cubic Mixed Halide Lead Perovskites from First-Principles

Owing to the increasing popularity of lead-based hybrid perovskites for photovoltaic (PV) applications, it is crucial to understand their defect energetics and its influence on their optoelectronic properties. In this work, we simulate various point defects in pseudocubic structures of mixed iodide-bromide and bromide-chloride methylammonium lead perovskites with the general formula MAPbI 3-y Br y or MAPbBr 3-y Cl y (where y is between 0 and 3), and use first-principles based density functional theory computations to study their relative formation energies and charge transition levels. We identify vacancy defects and Pb on MA antisite defect as the lowest energy native defects in each perovskite. Here, we observe that while the low energy defects in all MAPbI 3-y Br y systems only create shallow transition levels, the Br or Cl vacancy defects in the Cl-containing pervoskites have low energy and form deep levels which become deeper for higher Cl content. We examine the structures and density of states of pure and defect-containing perovskite systems to obtain an understanding of the nature of defect levels. Further, we study extrinsic substitution by different elements at the Pb site in MAPbBr 3 , MAPbCl 3 , and the 50-50 mixed halide perovskite, MAPbBr 1.5 Cl 1.5 , and identify some transition metals that create lower energy defects than the dominant intrinsic defects and also create midgap charge transition levels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗