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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 433 records · Page 24

Stabilized electrodes for lithium batteries

A structurally inhomogeneous lithium metal oxide material having the Formula (I): y[xLi2MO3•(1-x)LiM′O2]•(1-y)Li1+dM″2−dO4; wherein 0≤x≤1; 0<y<1; 0≤d≤0.33; and wherein the Li1+dM″2−dO4 component comprises a spinel structure, and each of the Li2MO3 and the LiM′2 components thereof comprise layered structures. Each of M, M′, and M″ independently comprises one or more metal ions. The composition of the material of Formula (I) varies across the electrode particles by changing at least one of x, y, d, M, M′ and M″. Electrodes, cells and batteries comprising the lithium metal oxide material are also described.

Thackeray, Michael M.↗

Dimensional reduction upon calcium incorporation in Cs 0.3 (Ca 0.3 Ln 0.7 )PS 4 and Cs 0.5 (Ca 0.5 Ln 0.5 )PS 4

A series of Ca-containing lanthanide thiophosphates has been obtained and their structural evolution from 3D for LnPS 4 and Cs 0.3 (Ln 0.7 Ca 0.3 )PS 4 to 2D in Cs 0.5 (Ln 0.5 Ca 0.5 )PS 4 was shown as a function of Ca content. The first series with an idealized formula of Cs 0.3 (Ca 0.3 Ln 0.7 )PS 4 crystallizes in the R3¯m with combining macron]m space group and belongs to a new structure type that consists of a channel containing [(Ca 0.3 Ln 0.7 )PS 4 ] 0.3– framework, where the channels are occupied by severely disordered Cs + cations. A second new series with formula Cs 0.5 (Ca 0.5 Ln 0.5 )PS 4 crystallizes in the monoclinic C2/c space group and exhibits a layered structure consisting of [(Ca 0.5 Ln 0.5 )PS 4 ] 0.5– layers with Cs + cations located between the layers for charge balance. Together with the parent structure type, LnPS 4 , these three structure types illustrate how the LnPS 4 structure changes with Cs + cation incorporation, reducing its dimensionality from 3D to 2D. The magnetic properties of Cs 0.3 [(Ca 0.3 Ce 0.7 )PS 4 ] and Cs 0.3 [(Ca 0.3 Pr 0.7 )PS 4 ] were studied and revealed no magnetic transition down to 2 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Generalized pulse equations for through-transmission evaluation of arbitrary multilayered structures

Generalized transit time and pulse amplitude equations were derived for modelling the ultrasonic through-transmission wave propagation of an arbitrary n-layered structure. The equations can be programmed into an expert system and used to identify and predict the through-transmission pulse signals from the critical interfaces of a multilayered structure. To test the formulas, the through transmission was measured from one- and three-layered configurations in the laboratory. The experimental measurements were compared with computer-generated data determined using the derived equations. The results verify the validity of the formulas.

Chern, E. James↗

Hydrogen-Doped Polymeric Carbon Monoxide at High Pressure

The ability to control materials stability, bonding, and transformation by thermo-mechanical and chemical means is significant for development of high-energy-density extended solids. We report that doping hydrogen (~10%) in carbon monoxide (CO) can greatly lower the polymerization pressure of CO and enhance the stability of recovered polymeric CO products at ambient conditions. Hydrogen-doped CO crystallizes into well-grown dendrites of β-CO-like phase at 3.2 GPa, which polymerizes to highly unsaturated black polymer (phase I) at ~4.7 (5.8) GPa. Upon further compression, this highly colored polymer transforms into a translucent 3D network structure (phase II) at 6–7 (10–17) GPa and then a transparent 2D layer structure (phase III) at 20–30 (30–60) GPa. A similar series of transformations are also found in pure CO but at considerably higher transition pressures, as noted in parentheses. All polymeric phases are recoverable at ambient conditions, exhibiting an array of phase stability and novel properties such as chemically unstable phase I, highly luminescent phase II, and highly transparent layered phase III. The density of recovered products ranges from ~2.3 g/cm 3 to 3.6 g/cm 3 , depending on the pressure recovered. The recovered products are highly disordered but slowly decompose to crystalline solids of anhydrous polymeric oxalic acid while exhibiting interesting crystal morphologies such as nm-cobs, nm-lamellar layers, and μm-bales. Here, the present first-principles MD simulations suggest that the polymerization occurs at 6 (or 10) GPa in H 2 -doped (or pure) CO. While not directly participating in the reaction, the role of H 2 molecules is to enhance the mobility of CO molecules leading to the polymerization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Comparison of Thermal Diffusivity Degradation of Irradiated Zirlo and SiC-SiC Composite

Zirlo (Zircaloy cladding material from Westinghouse) has been widely used as the fuel cladding material in Light Water Reactors because of its high melting point, low susceptibility to corrosion, good thermal and mechanical shock resistance, and low degradation of mechanical properties under irradiation. But as Zirlo reacts with water at high temperature, which can trigger serious accidents, efforts have been made to explore better candidates to replace Zirlo in the water-cooled reactors. SiC-SiC composite is considered as one of the most viable options due to its comparable mechanical performances and corrosion resistance. However, one of the most important properties, thermal diffusivities of both Zirlo and SiC-SiC composite, and their degradation after irradiation, are not well known yet. Ion-irradiated samples are used to study the thermal property degradation caused by irradiation instead of the neutron-irradiated ones due to the significantly lower radioactivity. The microstructural damage is estimated from the software simulation SRIM/TRIM based on the energy and fluence of the ion, and the target material, and represented by DPA (displacement by atom). Different from neutron-irradiated samples, the damaged layer of ion-irradiated samples is only a few to a few tens of micrometers thick, and the damage is depth dependent. It is impossible to directly measure the bulk property change, and a microscale measurement technique is necessary. Laser-based photothermal reflectance technique is one of the ideal methods to measure local thermal conductivity and diffusivity with high spatial resolution. The main principle of this technique is to heat the solid sample using an intensity-modulated laser, and scan the sample with a constant intensity continuous-wave (CW) laser to detect the thermal wave propagation. On bulk, isotropic material, if the heating laser intensity is modulated as a sine wave, thermal diffusivity of the sample can be derived from the phase lag of the thermal wave, scan distance and modulation frequency in a straight forward manner. By using more specific analytical models, thermal conductivity and diffusivity in complicated cases, such as layered structure materials, composite materials, and/or anisotropic materials, are measurable as well. In this work, thermal diffusivity of the light damage layer of the post-irradiation Zirlo and SiC-SiC composite are measured and compared. The Zirlo sample is irradiated by Ni{sup 9+} ion, and SiC-SiC composite material is irradiated by Si{sup 7+} ion. The peak DPA of both sample is similar as ∼10. For ion-irradiated materials, DPA is known to increase with depth before it reaches the peak, and then sharply drop to zero. In term of light damage layer in this manuscript, we mean by the layer with a DPA smaller than 5% maximum value. In this layer DPA increases slowly and smoothly with depth, and the structure and thus thermal properties are more spatially uniform. For the SiC-SiC composite, the measurements are separately conducted on fibers along radial or axial direction, and on the matrix. Our measurement results show that with similar microstructural damage, thermal diffusivity of matrix SiC reduces more significantly than that of Zirlo. For fiber SiC that has a much lower thermal diffusivity than the matrix SiC before irradiation, the post-irradiation effect on thermal diffusivity is not obvious.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

A monoclinic polymorph of sodium birnessite for ultrafast and ultrastable sodium ion storage

Sodium transition metal oxides with layered structures are attractive cathode materials for sodium-ion batteries due to their large theoretical specific capacities. However, these layered oxides suffer from poor cyclability and low rate performance because of structural instability and sluggish electrode kinetics. In the present work, we show the sodiation reaction of Mn 3 O 4 to yield crystal water free NaMnO 2–y–δ (OH) 2y , a monoclinic polymorph of sodium birnessite bearing Na/Mn(OH) 8 hexahedra and Na/MnO 6 octahedra. With the new polymorph, NaMnO 2–y–δ (OH) 2y exhibits an enlarged interlayer distance of about 7 Å, which is in favor of fast sodium ion migration and good structural stability. In combination of the favorable nanosheet morphology, NaMn 2–y–δ (OH) 2y cathode delivers large specific capacity up to 211.9 mAh g –1 , excellent cycle performance (94.6% capacity retention after 1000 cycles), and outstanding rate capability (156.0 mAh g –1 at 50 C). This study demonstrates an effective approach in tailoring the structural and electrochemical properties of birnessite towards superior cathode performance in sodium-ion batteries.

25 ENERGY STORAGE↗

Hybrid Grid Techniques for Propulsion Applications

During the past decade, computational simulation of fluid flow for propulsion activities has progressed significantly, and many notable successes have been reported in the literature. However, the generation of a high quality mesh for such problems has often been reported as a pacing item. Hence, much effort has been expended to speed this portion of the simulation process. Several approaches have evolved for grid generation. Two of the most common are structured multi-block, and unstructured based procedures. Structured grids tend to be computationally efficient, and have high aspect ratio cells necessary for efficently resolving viscous layers. Structured multi-block grids may or may not exhibit grid line continuity across the block interface. This relaxation of the continuity constraint at the interface is intended to ease the grid generation process, which is still time consuming. Flow solvers supporting non-contiguous interfaces require specialized interpolation procedures which may not ensure conservation at the interface. Unstructured or generalized indexing data structures offer greater flexibility, but require explicit connectivity information and are not easy to generate for three dimensional configurations. In addition, unstructured mesh based schemes tend to be less efficient and it is difficult to resolve viscous layers. Recently hybrid or generalized element solution and grid generation techniques have been developed with the objective of combining the attractive features of both structured and unstructured techniques. In the present work, recently developed procedures for hybrid grid generation and flow simulation are critically evaluated, and compared to existing structured and unstructured procedures in terms of accuracy and computational requirements.

Koomullil, Roy P.↗

High spatial resolution neutron imaging of lithium-ion batteries: Correlating microstructure and lithium transport

Thick electrodes for lithium-ion batteries can increase the overall energy density, but increasing the electrode thickness introduces charge transport limitations. These limitations may be mitigated through proper electrode structuring. Here, high spatial resolution neutron imaging was used to understand the correlation between microstructure and lithium transport in lithium-ion anodes. Batteries with distinct graphite anode microstructures were produced and studied with high spatial resolution in operando neutron radiography to observe the effects of structure on transport. High spatial resolution neutron computed tomography was performed following in operando neutron radiography. X-ray computed tomography and scanning electron microscopy were used to observe the finer scale anode structure to complement neutron imaging. Solvent-free anodes containing a tightly-packed layered structure confined lithium movement close to the separator. This structure limited capacity, but supported better rate capability. Conversely, a more open pore structure in the wet cast anodes yielded higher capacity with reduced rate capability. Together, these results show that lithium distributions can be controlled by the macroscopic structure of the electrodes, the microstructural pore network, and the microscale active areas that support electrochemical reactions. Furthermore, multimodal imaging applying the complementary strengths of neutron and X-ray methods is shown as a tool for advancing battery design.

25 ENERGY STORAGE↗

Stiff, Strong Splice For A Composite Sandwich Structure

New type of splice for composite sandwich structure reduces peak shear stress in structure. Layers of alternating fiber orientation interposed between thin ears in adhesive joint. Developed for structural joint in spar of helicopter rotor blade, increases precision of control over thickness of adhesive at joint. Joint easy to make, requires no additional pieces, and adds little weight.

Schmaling, D.↗

Gas Permeable Chemochromic Compositions for Hydrogen Sensing

A (H2) sensor composition includes a gas permeable matrix material intermixed and encapsulating at least one chemochromic pigment. The chemochromic pigment produces a detectable change in color of the overall sensor composition in the presence of H2 gas. The matrix material provides high H2 permeability, which permits fast permeation of H2 gas. In one embodiment, the chemochromic pigment comprises PdO/TiO2. The sensor can be embodied as a two layer structure with the gas permeable matrix material intermixed with the chemochromic pigment in one layer and a second layer which provides a support or overcoat layer.

Bokerman, Gary↗

Impact of surface hydrophilicity on the ordering and transport properties of bicontinuous microemulsions

Microemulsions (MEs) have many industrial applications, where recent developments have shown that MEs can be utilized for electrochemical applications, including potentially in redox flow batteries. However, understanding the structure and dynamics of these systems, including at a surface, is needed to direct and rationally control their electrochemical behavior. While bulk solution measurements have provided insight into their structure, their assembly at an interface also impacts the electron (to the electrode) and ion (across the surfactant) charge transfer processes in the system. To address this shortcoming, neutron reflectivity experiments and molecular simulations have been completed that document the near surface structure of a series of deuterated water (D 2 O)/polysorbate-20/toluene MEs on hydrophilic and amphiphilic surfaces. These results show that the microemulsions form complex layered structures near a hard electrode surface, where most layers are not purely one component. Decreasing the D 2 O concentration in the ME increases the number of and purity of the layers established on the solid surface. These lamellar-type layers transition from the surface to the bulk microemulsion as a series of mixed layers (i.e., containing oil, water, and surfactant) that are consistent with perforated lamellae. Additionally, these mixed lamellae appear to become more perforated with oil and water pathways on an amphiphilic surface. Furthermore, the purity and thickness of these layers will influence the accessibility of an electrode by redox active species, as well as ion transport required to satisfy the electroneutrality condition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Generalized pulse equations for through-transmission evaluation of arbitrary multilayered structures

Generalized transit-time and pulse-amplitude equations have been derived for modeling the ultrasonic through-transmission wave propagation of an arbitrary n-layered structure. The equations can be programmed into an expert system and used to identify and predict the through-transmission pulse signals from the critical interfaces of a multilayered structure. To test the formulas, the through-transmission responses from one- and three-layered configurations were measured in the laboratory and compared with computer-generated data that were determined using the derived equations. The results verify the validity of the formulas.

Chern, E. James↗

Lattice hardening due to vacancy diffusion in (GeTe) m Sb 2 Te 3 alloys

GeTe-Sb 2 Te 3 alloys have been widely studied for use in rewritable media, and in recent years, they have emerged as excellent thermoelectric materials, with reports of z T > 2 for Ge-rich compositions. GeTe-Sb 2 Te 3 alloys exhibit a solid-state phase transition from a layered structure with rhombohedral symmetry to a cubic rocksalt structure, which plays an important role in their thermoelectric behavior. In this work, we investigate the impact of the phase transition on the thermal expansion and elastic moduli of (GeTe) 17 Sb 2 Te 3 using high-temperature X-ray diffraction and resonant ultrasound spectroscopy. The high-temperature elastic moduli of GeTe, Sb 2 Te 3 , and Bi 2 Te 3 were also measured for comparison. Although it is typical for materials to soften with increasing temperature due to thermal expansion, our study reveals anomalous hardening of the elastic moduli in (GeTe) 17 Sb 2 Te 3 at temperatures below the phase transition, followed by further hardening at the transition temperature. In contrast, the elastic moduli of GeTe, Sb 2 Te 3 , and Bi 2 Te 3 soften with increasing temperature. We attribute the anomalous hardening of (GeTe) 17 Sb 2 Te 3 to the gradual vacancy diffusion accompanying the transition from a layered to a cubic structure. The stiffening elastic moduli lead to increasing speed of sound, which impacts the lattice thermal conductivity by flattening the temperature dependence.

36 MATERIALS SCIENCE↗

Gravitational evidence for an undifferentiated Callisto

Before the arrival of the Galileo spacecraft at Jupiter, models for the interior structure of the four galilean satellites--Io, Europa, Ganymede and Callisto-ranged from uniform mixtures of rock and ice (that is, undifferentiated objects) or rocky cores surrounded by a mantle of water ice. Now it appears that Io has a large metallic core and that Ganymede is strongly differentiated, most probably into a three-layer structure consisting of a metallic core, a silicate mantle and a deep outer layer of ice. Direct information on the interior structure of Callisto determined from previous spacecraft fly-bys was essentially limited to an estimate of the mean density being intermediate between pure ice and pure rock. Here we report measurements of Callisto's gravitational field which reveal that, in contrast to Io and Ganymede, this galilean satellite is most probably a homogeneous object consisting of a solar mixture of 40% compressed ice and 60% rock (including iron and iron sulphide). Callisto's undifferentiated state is consistent with the apparent lack of an intrinsic magnetic field, and indicates that the outermost galilean satellite has not experienced a heating phase sufficiently high to separate its rock and metal components from the lighter ices.

unmanned↗

Hybrid Dion–Jacobson 2D Lead Iodide Perovskites

The three-dimensional hybrid organic–inorganic perovskites have shown huge potential for use in solar cells and other optoelectronic devices. Although these materials are under intense investigation, derivative materials with lower dimensionality are emerging, offering higher tunability of physical properties and new capabilities. Here, we present two new series of hybrid two-dimensional (2D) perovskites that adopt the Dion–Jacobson (DJ) structure type, which are the first complete homologous series reported in halide perovskite chemistry. Lead iodide DJ perovskites adopt a general formula A'A n–1 PbnI 3 n +1 (A' = 3-(aminomethyl)piperidinium (3AMP) or 4-(aminomethyl)piperidinium (4AMP), A = methylammonium (MA)). These materials have layered structures where the stacking of inorganic layers is unique as they lay exactly on top of another. With a slightly different position of the functional group in the templating cation 3AMP and 4AMP, the as-formed DJ perovskites show different optical properties, with the 3AMP series having smaller band gaps than the 4AMP series. Analysis on the crystal structures and density functional theory (DFT) calculations suggest that the origin of the systematic band gap shift is the strong but indirect influence of the organic cation on the inorganic framework. Fabrication of photovoltaic devices utilizing these materials as light absorbers reveals that (3AMP)(MA) 3 Pb 4 I 13 has the best power conversion efficiency (PCE) of 7.32%, which is much higher than that of the corresponding (4AMP)(MA) 3 Pb 4 I 13 .

14 SOLAR ENERGY↗

Applying Configurational Complexity to the 2D Ruddlesden–Popper Crystal Structure

The layered Ruddlesden–Popper crystal structure can host a broad range of functionally important behaviors. In this work, we establish extraordinary configurational disorder in a layered Ruddlesden–Popper (RP) structure using entropy stabilization assisted synthesis. A protype A 2 CuO 4 RP cuprate oxide with five cations on the A-site sublattice is designed and fabricated into epitaxial single crystal films using pulsed laser deposition. When grown on a near lattice matched substrate, the (La 0.2 Pr 0.2 Nd 0.2 Sm 0.2 Eu 0.2 ) 2 CuO 4 film features a T'-type RP structure with uniform A-site cation mixing and square-planar CuO4 units. These observations are made with a range of combined characterizations using X-ray diffraction, atomic-resolution scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray absorption spectroscopy measurements. It is further found that heteroepitaxial strain plays an important role in crystal phase formation during synthesis. Compressive strain over ~1.5% results in the formation of a non-RP cubic phase consistent with a Cu X 2O 4 spinel structure. The ability to manipulate configurational complexity and move between 2D layered RP and 3D cubic crystal structures in cuprate and related materials promises to enable flexible design strategies for a range of functionalities, such as magnetoresistance, unconventional superconductivity, ferroelectricity, catalysis, and ion transport.

36 MATERIALS SCIENCE↗

Model-Based Reconstruction for Collimated Beam Ultrasound Systems

Collimated beam ultrasound systems are a novel technology for imaging inside multi-layered structures such as geothermal wells. Such systems include a transmitter and multiple receivers to capture reflected signals. Common algorithms for ultrasound reconstruction use delay-and-sum (DAS) approaches; these have low computational complexity but produce inaccurate images in the presence of complex structures and specialized geometries such as collimated beams.In this paper, we propose a multi-layer, ultrasonic, model-based iterative reconstruction algorithm designed for collimated beam systems. We introduce a physics-based forward model to accurately ac-count for the propagation of a collimated ultrasonic beam in multi-layer media and describe an efficient implementation using binary search. We model direct arrival signals, detector noise, and a spatially varying image prior, then cast the reconstruction as a maximum a posteriori estimation problem. Using simulated and experimental data we obtain significantly fewer artifacts relative to DAS while running in near real time using commodity compute resources.

Alanazi, Abdulrahman M.↗