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At least 703 records · Page 39

Achieving a high-performance sodium-ion pouch cell by regulating intergrowth structures in a layered oxide cathode with anionic redox

In P2-type layered transition metal (TM) oxides, which are typical cathode materials for Na-ion batteries, the presence of Li within the TM layer could lead to the formation of specific Na–O–Li configurations that trigger additional oxygen redox at high charging voltages. However, the prismatic-type (P-type) to octahedral-type (O-type) phase transition and irreversible TM migration could be simultaneously aggravated in high state of charge, resulting in structural distortion. Here we demonstrate that excessive desodiation of P2-Na 0.67 Li 0.1 Fe 0.37 Mn 0.53 O 2 (NLFMO) induces the formation of neighbouring O-type stacking faults with an intergrowth structure (that is, interlacing of O- and P-type layers), which leads to out-of-lattice Li migration and irreversible oxygen loss. We show that, by controlling the depth of charge to tailor the intergrowth structure, a P-type stacking state can be uniformly interspersed between the O-type stacking state, thereby avoiding neighbouring O-type stacking faults. Adjusting the O/P intergrowth structure leads to both reversible migration of Li/TM ions and reversible anionic redox in the NLFMO cathode. In conclusion, we thereby achieve a high-performance pouch cell (with an energy density of 165 W h kg −1 based on the entire weight of the cell) with both cationic and anionic redox activities.

25 ENERGY STORAGE↗

Dissecting Disorder: Defect-Driven Structural Complexity in Layered Li3InCl6 Solid Electrolyte

Halide solid electrolytes have emerged as promising candidates for solid-state batteries owing to their high oxidative stability and ionic conductivity. Among them, Li3InCl6 (LIC) has attracted significant attention. However, diffraction patterns of LIC synthesized via different methods exhibit distinct differences particularly at low-angle reflectionsindicative of underlying structural disorder. These variations are attributed to deviations from ideal crystallographic order, especially stacking faults, whose impact on structure and ion transport remains poorly understood. Here, we identify and quantify stacking faults in LIC samples prepared under different synthetic conditions. Using X-ray diffraction and time-of-flight neutron diffraction, we construct and refine stacking fault models that accurately reproduce the experimental diffraction features. LIC samples with higher degrees of stacking faults exhibit only negligible differences in ionic conductivities and activation energies. This indicates that stacking faults have a limited impact on altering the Li+ diffusion pathway along the c-axis, likely due to the high concentration of vacancies in the In layers, while Li+ diffusion remains nearly unchanged in the ab-plane. Our results account for the observed differences in diffraction patterns across samples and provide a quantitative assessment of faulting probabilities and stacking sequences. The insights gained from this study are expected to be broadly applicable to other layered halide solid electrolytes and contribute to a deeper understanding of the role of structural disorder in ion transport.

Liu, Jue [ORNL] (ORCID:000000024453910X)↗

The Impact of Catalyst Layer Composition and Structure on Performance and Durability of PEMWE Anodes

A study of various compositions of anodes for proton exchange membrane water electrolysis aimed at reducing precious metal content and system costs without compromising performance and durability is presented. A key challenge in current water electrolysis technologies is the reliance on high iridium loadings to ensure sufficient catalytic activity, electronic conductivity, and durability for the oxygen evolution reaction. To address this, catalyst layers based on the stable but kinetically limited rutile phase of iridium oxide are combined with platinum nanoparticles and carbon-based additives to improve structural properties and ink processability. By systematically varying the volume ratios of carbon to precious metals and ionomer to solids, compositional trends have been identified, and significant performance improvements have been achieved. Structural and elemental analysis confirms improved dispersion of platinum and iridium can be achieved, as well as electronic conductivity improvements within the catalyst layer. Polarization curve analysis has shown the ability of added Pt and C to significantly increase catalytic activity. These results highlight the potential positive impact of Pt and C on anode structure, composition, and cell performance.

36 MATERIALS SCIENCE↗

A Study to Analyze the Permeation of High Density Gases and Propellant Vapors Through Single Layer Teflon or Teflon Structure Materials and Laminations

This report contains the results of a fifteen month analytical and experimental study of the leakage rate of the pressurant gases (N2, He) and the propellant vapors (N2O4,N2H4) through bladder structures consisting of two layers of Teflon separated by a metallic foil diffusion barrier containing microscopic or larger holes. Results were obtained for the steady state leakage rate through circular holes and long rectangular openings in the barrier for arbitrary thicknesses of the two Teflon layers. The effect of hole shape and relative hole position on the leakage rate were studied. The transient problem was analyzed and it was shown that steady state calculations are adequate for estimating the leakage rate. A computer program entitled "Diffusion Analyzer Program" was developed to calculate the leakage rate, both transient and steady state. Finally, the analytical results were compared to experimentally determined values of the leakage rate through a model laminated bladder structure. The results of the analysis are in good agreement with experiment. The experimental effort (Part II of the Bladder Permeation Program) measured the solubility, diffusion coefficient and permeability of helium, nitrogen and nitrogen tetroxide vapor through Teflon TFE and FEP membranes. Data were obtained in the temperature range of 25 to 100 C at pressures ranging from near vacuum to about 20 atmospheres. Results of the experimental effort were compared with the limited data previously reported. As a verification to the applicability of results to actual bladder systems, counter diffusion tests were performed with a laminated sample containing aluminum foil with a selected group of holes.

Johnson, R. L.↗

Thermodynamic structure of the stratocumulus-capped boundary layer on 5 July 1987

The National Center for Atmospheric Research (NCAR) Electra flew a single aircraft mission on July 5 in comparatively uniform stratocumulus cloud (80 to 100 percent cloud coverage). The flight pattern, a series of north-south doglegs centered at (32N, -122W), included 15 full or partial soundings to examine layer vertical structure between altitudes of 150 and 5000 m. The air below the inversion was well-mixed in moist static energy, total water, and ozone. The inversion base measured by the aircraft ranged from 920 to 938 hPa, while the thickness of the cloud layer varied between 30 and 10 hPa. Maximum cloud liquid water contents approached 0.3 g kg(-1) (as measured by the Johnson-Williams and King probes). Comparison of soundings made in the same location show a strengthening of the inversion and increasing shear at cloud top over the observation period (16:50 to 00:22 UT). Typical windspeeds below the inversion were approximately 10 m s(-1) decreasing to 6 m s(-1) 8 hPa above cloud top. A thermodynamic budget for this case is in preparation; it will provide a comparison and contrast with the more complicated July 7 case.

Austin, Philip H.↗

Deriving Lifetime Maps in the Time/Frequency Domain of Coherent Structures in the Turbulent Boundary Layer

The lifetimes of coherent structures are derived from data correlated over a 3 sensor array sampling streamwise sidewall pressure at high Reynolds number (> 10(exp 8)). The data were acquired at subsonic, transonic and supersonic speeds aboard a Tupolev Tu-144. The lifetimes are computed from a variant of the correlation length termed the lifelength. Characteristic lifelengths are estimated by fitting a Gaussian distribution to the sensors cross spectra and are shown to compare favorably with Efimtsov s prediction of correlation space scales. Lifelength distributions are computed in the time/frequency domain using an interval correlation technique on the continuous wavelet transform of the original time data. The median values of the lifelength distributions are found to be very close to the frequency averaged result. The interval correlation technique is shown to allow the retrieval and inspection of the original time data of each event in the lifelength distributions, thus providing a means to locate and study the nature of the coherent structure in the turbulent boundary layer. The lifelength data are converted to lifetimes using the convection velocity. The lifetime of events in the time/frequency domain are displayed in Lifetime Maps. The primary purpose of the paper is to validate these new analysis techniques so that they can be used with confidence to further characterize the behavior of coherent structures in the turbulent boundary layer.

Palumbo, Dan↗

Laser Doppler velocimeter measurements of boundary layer velocity and turbulent intensities in Mach 2.5 flow

In recent years, the interest in developing a high-speed civil transport has increased. This has led to an increase in research activity on compressible supersonic flows, in particular the boundary layer. The structure of subsonic boundary layers has been extensively documented using conditional sampling techniques which exploit the knowledge of both u and v velocities. Researchers using these techniques have been able to explore some of the complex three-dimensional motions which are responsible for Reynolds stress production and transport in the boundary layer. As interest in turbulent structure has grown to include supersonic flows, a need for simultaneous multicomponent velocity measurements in these flows has developed. The success of conditional analysis in determining the characteristics of coherent motions and structures in the boundary layer relies on accurate, simultaneous measurement of two instantaneous velocity components.

Sewell, Jesse↗

The inviscid secondary instability of fully nonlinear longitudinal vortex structures in growing boundary layers

The inviscid instability of a longitudinal vortex structure within a steady boundary layer is investigated. The instability has a wavelength comparable with the boundary layer thickness so that a quasi-parallel approach to the instability problem can be justified. The generalization of the Rayleigh equation to such a flow is obtained and solved for the case when the vortex structure is induced by curvature. Two distinct modes of instability are found; these modes correspond with experimental observations on the breakdown process for Goertler vortices.

Hall, Philip↗

Navier-Stokes structure of merged layer flow on the spherical nose of a space vehicle

Hypersonic merged layer flow on the forepart of a spherical surface of a space vehicle has been investigated on the basis of the full steady-state Navier-Stokes equations using slip and temperature jump boundary conditions at the surface and free-stream conditions far from the surface. The shockwave-like structure was determined as part of the computations. Using an equivalent body concept, computations were carried out under conditions that the Aeroassist Flight Experiment (AFE) Vehicle would encounter at 15 and 20 seconds in its flight path. Emphasis was placed on understanding the basic nature of the flow structure under low density conditions. Particular attention was paid to the understanding of the structure of the outer shockwave-like region as the fluid expands around the sphere. Plots were drawn for flow profiles and surface characteristics to understand the role of dissipation processes in the merged layer of the spherical nose of the vehicle.

Jain, A. C.↗

A New View of the Dynamics of Reynolds Stress Generation in Turbulent Boundary Layers

The structure of a numerically simulated turbulent boundary layer over a flat plate at Re(theta) = 670 was studied using the invariants of the velocity gradient tensor (Q and R) and a related scalar quantity, the cubic discriminant (D = 27R(exp 2)/4 + Q(exp 3)). These invariants have previously been used to study the properties of the small-scale motions responsible for the dissipation of turbulent kinetic energy. In addition, these scalar quantities allow the local flow patterns to be unambiguously classified according to the terminology proposed by Chong et al. The use of the discriminant as a marker of coherent motions reveals complex, large-scale flow structures that are shown to be associated with the generation of Reynolds shear stress -u'v'(bar). These motions are characterized by high spatial gradients of the discriminant and are believed to be an important part of the mechanism that sustains turbulence in the near-wall region.

Cantwell, Brian J.↗

Highly Asymmetric Graphene Layer Doping and Band Structure Manipulation in Rare Earth–Graphene Heterostructure by Targeted Bonding of the Intercalated Gadolinium

Heterostructures consisting of vertically stacked two-dimensional (2D) materials have recently gained large attention due to their highly controllable electronic properties and resulting quantum phases. In contrast to the mechanically stacked multilayered systems, which offer exceptional control over a stacking sequence or interlayer twist angles, the epitaxially grown 2D materials express unprecedented quality and stability over wafer-scale lengths. However, controlling the growth conditions remains a major obstacle toward the formation of complex, epitaxial heterostructures with well-defined electronic properties. Here, we synthesized a trilayer graphene heterostructure on the SiC(0001) substrate with two specific interlayer locations occupied by gadolinium. We applied multitechnique methodology based on low-temperature scanning tunneling microscopy/spectroscopy (STM/S) and angle-resolved photoelectron spectroscopy (ARPES) to determine the intercalant’s locations in the complex, epitaxial graphene heterostructure. Our approach relies on very high quality and large, micrometer-scale homogeneity of the synthesized system. The experimentally determined electronic structure is dominated by the two topmost graphene layers. Overall, our spectroscopic results show quantitative agreement between global ARPES, local STM/S, and density functional theory predictions. The characterized electronic properties primarily reflect highly anisotropic doping levels between the two corresponding graphene layers, which significantly affect the band structure topology. Two pairs of hybridized massive Dirac bands from our initial synthesis–the bilayer graphene on the SiC(0001) substrate–are transformed upon Gd intercalation into two pairs of massless Dirac bands with a new hybridization region in between. Our results open perspectives in the realization of exotic 2D quantum materials via atomically precise synthesis of epitaxial, multilayered graphene–rare earth heterostructures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Turbulent boundary-layer flow and structure on a convex wall and its redeveloment on a flat wall

Although the number of data sets which show the effects of convex curvature on turbulence has increased in the last 10 years, the development of really good calculational models is being held back by a lack of reliable data. The pesent investigation is concerned with a set of experiments which provide a litle more information regarding the response of a boundary-layer flow to convex curvature. Careful measurements were conducted to show the response of the boudnary layer to a sudden change from flat wall to curvature, and from curvature to flat wall. It was found that curvature effects were clearly apparent one or two boundary-layer thicknesses downstream of the start of curvature, while the disappearance of the curvature effects on a flat wall was an extremely slow process.

Gillis, J. C.↗

Effects of precipitation on the thermodynamic structure of the trade wind boundary layer

A model of the thermodynamic structure of the trade wind boundary layer is formulated to include the parameterization of precipitation in relatively shallow clouds. Although the area-averaged simulated precipitation rates are relatively small (less than 1 mm/day), the inclusion of precipitation has an appreciable effect on the predicted thermodynamic structure. The cloud layer structure simulated with precipitation is warmer, drier, and more stable than that simulated without precipitation. The simulated inversion height is lowered by as much as 60 mbar when precipitation is included.

Albrecht, Bruce A.↗

Structural Evolution of Layered Manganese Oxysulfides during Reversible Electrochemical Lithium Insertion and Copper Extrusion

The electrochemical lithiation and delithiation of the layered oxysulfide Sr 2 MnO 2 Cu 4-δ S 3 has been investigated by using a combination of in situ powder X-ray diffraction and ex situ neutron powder diffraction, X-ray absorption and 7 Li NMR spectroscopy, together with a range of electrochemical experiments. Sr 2 MnO 2 Cu 4-δ S 3 consists of [Sr 2 MnO 2 ] perovskite-type cationic layers alternating with highly defective antifluorite-type [Cu 4-δ S 3 ] (δ ≈ 0.5) anionic layers. It undergoes a combined displacement/intercalation (CDI) mechanism on reaction with Li, where the inserted Li replaces Cu, forming Li 4 S 3 slabs and Cu + is reduced and extruded as metallic particles. For the initial 2-3% of the first discharge process, the vacant sites in the sulfide layer are filled by Li; Cu extrusion then accompanies further insertion of Li. Mn 2.5+ is reduced to Mn 2+ during the first half of the discharge. The overall charging process involves the removal of Li and re-insertion of Cu into the sulfide layers with re-oxidation of Mn 2+ to Mn 2.5+ . However, due to the different diffusivities of Li and Cu, the processes operating on charge are quite different from those operating during the first discharge: charging to 2.75 V results in the removal of most of the Li, little reinsertion of Cu, and good capacity retention. A charge to 3.75 V is required to fully reinsert Cu, which results in significant changes to the sulfide sublattice during the following discharge and poor capacity retention. This detailed structure-property investigation will promote the design of new functional electrodes with improved device performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of Eddy Current Techniques for Detection of Deep Fatigue Cracks in Multi-Layer Airframe Components

Thick, multi-layer aluminum structure has been widely used in aircraft design in critical wing splice areas. The multi-layer structure generally consists of three or four aluminum layers with different geometry and varying thickness, which are held together with fasteners. The detection of cracks under fasteners with ultrasonic techniques in subsurface layers away from the skin is impeded primarily by interlayer bonds and faying sealant condition. Further, assessment of such sealant condition is extremely challenging in terms of complexity of structure, limited access, and inspection cost. Although Eddy current techniques can be applied on in-service aircraft from the exterior of the skin without knowing sealant condition, the current eddy current techniques are not able to detect defects with wanted sensitivity. In this work a series of low frequency eddy current probes have been designed, fabricated and tested for this application. A probe design incorporating a shielded magnetic field sensor concentrically located in the interior of a drive coil has been employed to enable a localized deep diffusion of the electromagnetic field into the part under test. Due to the required low frequency inspections, probes have been testing using a variety of magnetic field sensors (pickup coil, giant magneto-resistive, anisotropic magneto-resistive, and spin-dependent tunneling). The probe designs as well as capabilities based upon a target inspection for sub-layer cracking in an airframe wing spar joint is presented.

Wincheski, Russell A.↗

Quasi-Coherent Structures In Turbulent Boundary Layers

Two-part report reviews knowledge of coherent structures in turbulent boundary layers. Part I describes processes and status of cooperative project to summarize data from research on boundary-layer turbulence. Part II presents results of study of numerically simulated flat-plate canonical turbulent boundary layer.

Robinson, S. K.↗

Ceramic Fiber Structures for Cryogenic Load-Bearing Applications

This invention is intended for use as a load-bearing device under cryogenic temperatures and/or abrasive conditions (i.e., during missions to the Moon). The innovation consists of small-diameter, ceramic fibers that are woven or braided into devices like ropes, belts, tracks, or cables. The fibers can be formed from a variety of ceramic materials like silicon carbide, carbon, aluminosilicate, or aluminum oxide. The fiber architecture of the weave or braid is determined by both the fiber properties and the mechanical requirements of the application. A variety of weave or braid architectures is possible for this application. Thickness of load-bearing devices can be achieved by using either a 3D woven structure, or a layered, 2D structure. For the prototype device, a belt approximately 0.10 in. (0.25 cm) thick, and 3.0 in. (7.6 cm) wide was formed by layering and stitching a 2D aluminosilicate fiber weave.

Jaskowiak, Martha H.↗