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At least 199 records · Page 11

Multiscale Cryo Electron Microscopy Reveals Interfacial Degradation and Stabilization in Battery Electrodes

Electrochemical interfaces are dynamic systems, evolving based on their local environment and reactant surface structures. The electrode-electrolyte interface in Li-ion batteries can be protective, limiting parasitic reactions with the electrolyte to passivate the surface [1]. Additionally, this interphase has an impact on the Li-ion transport through that layer based on its composition, bonding environment, and thickness. These parameters are challenging to collect and may vary depending on the electrode surface site investigated relative to its spatial position in a coin cell. This study will detail a multiscale cryogenic electron microscopy approach where millimeter-scale cross-sections through the coin cell batteries were made using a cryogenic stage within a fs-laser plasma focused ion beam (laser PFIB) with complementary energy dispersive X-ray spectroscopy able to detect variations in the composition at electrode interfaces [2]. Microscale cross-sectioning and lamella sample preparation of battery electrodes was conducted at the Center for Integrated Nanotechnologies using a Ga-ion focused ion beam (FIB) with air-free and cryo-transfer [3], followed by nanoscale mapping of composition and bonding within the CEI through cryo-scanning transmission electron microscopy (cryo-STEM) electron energy loss spectroscopy [4]. This multiscale approach enabled identification of millimeter-scale features of a battery stack with visualization of degradation in electrodes such as cracks in cathode particles, gas evolution, and SEI evolution; microscale interfacial characteristics, such as heterogeneity in the SEI or barrier layer and identification of electrolyte networks to the electrode surfaces; and nanoscale measurement of the CEI thickness, mapping of transition metal bonding within the cathode particles to identify loss of active materials, and identification of beneficial electrolyte additives incorporated into the CEI structure. This multiscale approach allows for a statistical understanding of the primary mechanisms and parasitic degradation pathways that impact performance by limiting the ion transport pathways within Li+ batteries.

36 MATERIALS SCIENCE↗

Vapor deposited emittance/catalysis coatings for superalloys in heatshield applications

Statically oxidized Inconel 617 and MA 956 superalloys were prepared with vapor deposited aluminosilicate layers and exposed to temperatures which simulated reentry conditions. The aluminosilicate layers were 1-2 microns thick. The trials consisted of exposures to 1500-2300 F heat while surface temperatures were monitored with pyrometers. Analyses were then performed of the catalytic activity, oxidation phenomena, and radiative properties after thermal cycling the specimens for 8 hr. Both alloys were found to be catalytic to the recombination processes of dissociated species in the reentry environment. The coatings reduced the catalytic activity by 40 percent for both alloys but did not change the emittance. An enhanced Cr depletion zone was detected in the Inconel samples, implying that the coating did not prevent diffusion loss of Cr. The coated MA 956, on the other hand, gained weight over the course of the trials.

Clark, R. K.↗

Theoretical Study of Response of InGaAs Metal-Semiconductor-Metal Photodetectors

We present a theoretical investigation of the response of metal-semiconductor-metal (MSM) photodetectors made of InGaAs lattice-matched to InP using a two-dimensional drift-diffusion model with a thermionic-field emission boundary condition for the heterojunctions. The effect of including a top InAlAs layer to increase the effective barrier height of the metal fingers on the InGaAs active layer is thoroughly examined and found to limit the collection of the photocurrent signal due to the electron and hole barriers that it forms with InGaAs. Due to the thickness and height of the InAlAs barrier layer in existing designs, the tunneling current obtained from the model is found to be negligibly small to significantly affect the output signal current. In an attempt to obtain a better response, different design structures including one where a quasi-Schottky contact is utilized are studied and their speed of response, breakdown voltage, and dark current are compared to that of the usual InGaAs device.

Salem, Ali F.↗

Micro-Tubular Solid Oxide Fuel Cell Polarization and Impedance Variation With Thin Porous Samarium-Doped Ceria and Gadolinium-Doped Ceria Buffer Layer Thickness

Abstract Porous buffer layers for anode-supported solid oxide fuel cells (SOFCs) have been investigated for many years with different thicknesses of the buffer layer in each study. In this work, micro-tubular SOFCs having samarium-doped ceria (SDC) and gadolinium-doped ceria (GDC) buffer layers are compared using the current–voltage technique, electrochemical impedance spectroscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The thickness of the porous SDC and GDC buffer layer is investigated systematically with the thickness varying between 0.3 and 2.0 μm. The power density varies between 212 and 1004 mW/cm2 for samples having different SDC buffer layer thickness. Comparable changes occur for the SOFCs with a GDC buffer layer, but less variation in polarization losses resulted. Variation in electrochemical performance varies due to changes in ohmic resistance, cathode activation polarization, and interfacial reactions between the cathode and electrolyte materials.

Electrochemistry↗

Experimental Studies of Low-Pressure Turbine Flows and Flow Control. Streamwise Pressure Profiles and Velocity Profiles

This report summarizes research performed in support of the NASA Glenn Research Center (GRC) Low-Pressure Turbine (LPT) Flow Physics Program. The work was performed experimentally at the U.S. Naval Academy faculties. The geometry corresponded to "Pak B" LPT airfoil. The test section simulated LPT flow in a passage. Three experimental studies were performed: (a) Boundary layer measurements for ten baseline cases under high and low freestream turbulence conditions at five Reynolds numbers of 25,000, 50,000, 100,000, 200,000, and 300,000, based on passage exit velocity and suction surface wetted length; (b) Passive flow control studies with three thicknesses of two-dimensional bars, and two heights of three-dimensional circular cylinders with different spanwise separations, at same flow conditions as the 10 baseline cases; (c) Active flow control with oscillating synthetic (zero net mass flow) vortex generator jets, for one case with low freestream turbulence and a low Reynolds number of 25,000. The Passive flow control was successful at controlling the separation problem at low Reynolds numbers, with varying degrees of success from case to case and varying levels of impact at higher Reynolds numbers. The active flow control successfully eliminated the large separation problem for the low Reynolds number case. Very detailed data was acquired using hot-wire anemometry, including single and two velocity components, integral boundary layer quantities, turbulence statistics and spectra, turbulent shear stresses and their spectra, and intermittency, documenting transition, separation and reattachment. Models were constructed to correlate the results. The report includes a summary of the work performed and reprints of the publications describing the various studies.This report summarizes research performed in support of the NASA Glenn Research Center (GRC) Low-Pressure Turbine (LPT) Flow Physics Program. The work was performed experimentally at the U.S. Naval Academy faculties. The geometry corresponded to "Pak B" LPT airfoil. The test section simulated LPT flow in a passage. Three experimental studies were performed: (a) Boundary layer measurements for ten baseline cases under high and low freestream turbulence conditions at five Reynolds numbers of 25,000, 50,000, 100,000, 200,000, and 300,000, based on passage exit velocity and suction surface wetted length; (b) Passive flow control studies with three thicknesses of two-dimensional bars, and two heights of three-dimensional circular cylinders with different spanwise separations, at same flow conditions as the 10 baseline cases; (c) Active flow control with oscillating synthetic (zero net mass flow) vortex generator jets, for one case with low freestream turbulence and a low Reynolds number of 25,000. The Passive flow control was successful at controlling the separation problem at low Reynolds numbers, with varying degrees of success from case to case and varying levels of impact at higher Reynolds numbers. The active flow control successfully eliminated the large separation problem for the low Reynolds number case. Very detailed data was acquired using hot-wire anemometry, including single and two velocity components, integral boundary layer quantities, turbulence statistics and spectra, turbulent shear stresses and their spectra, and intermittency, documenting transition, separation and reattachment. Models were constructed to correlate the results. The report includes a summary of the work performed and reprints of the publications describing the various studies. The folders in this supplement contain processed data in ASCII format. Streamwise pressure profiles and velocity profiles are included. The velocity profiles were acquired using single sensor and cross sensor hot-wire probes which were traversed from the wall to the freestream at various streamwise locations. In some of the flow control cases (3D Trips and Jets) profiles were acquired at multiple spanwise locations.

Volino, Ralph↗

Modeling and Analysis of Polarization Losses in Solid Oxide Fuel Cells with Siloxane Contamination

In this study, the degradation of the solid-oxide fuel cell (SOFC) nickel-yttria stabilized zirconia anode under decamethyltetrasiloxane (L4) contamination is examined with experiments and modeling. A model is developed for the polarization losses based on the charge transfer coefficient,α, and diffusion layer thickness,δ, and fitted to the experimental data to understand how the siloxane degrades the SOFC performance with time. The results of the model indicate that the total polarization losses increase approximately 44% over the course of the 180 min experiment at 350 mA cm −2 . Activation losses dominate the polarization losses initially but decrease in their total contribution while concentration losses increase. Scanning electron microscopy (SEM) with wavelength dispersive X-ray spectroscopy (WDS) elemental mapping indicates that silicon deposition is highest at the outer edge of the anode and forms a barrier layer to fuel diffusion, increasing concentration losses. When the model is applied to other previous D4 and L4 siloxane experiments conducted over a period of 40 h, similar trends in polarization losses are observed. Polarization losses increase more rapidly with D4 compared to L4 siloxane contamination, with concentration losses increasing the fastest with both types of siloxane.

Electrochemistry↗

Superlattice-Structured Films by Magnetron Sputtering as New Era Electrodes for Advanced Lithium-ion Batteries

Sustaining sound structures in Si-based anodes is extremely challenging because of the high volumetric expansion that occurs upon cycling. To maintain high capacities over cycles, new designs rely on engineering-specific hierarchical geometries and/or optimized composite compositions such that at least one of the multiple elements serves as buffer and/or electron conductive pathways in the electrodes. In this paper, we report an innovative design in which alternating layers of periodic atomic structures involving multiple elements form a new anode material for lithium-ion batteries. In this work, a superlattice-structured amorphous film made using Si, Mo, and Cu is fabricated by a simple and scalable magnetron sputtering process for the first time. This continuous and repetitive superlattice formation along the film thickness provides a homogeneous stress-strain distribution. The Mo-Cu layer in the superlattice acts as an inactive-conductive layer and as a backbone to handle the volume expansion of active Si upon cycling. This nano-functional superlattice approach enables harnessing the high energy density of Si while maintaining its structural stability. As a result, the electrode exhibits high specific capacity and capacity retention even at high cycling rates. The possible use of the film in a full cell is also evaluated by cycling it vs. the LiMn 1.5 Ni 0.5 O 4 cathode. The full cell maintains a stable capacity of about 900 mAh g anode -1 over 150 cycles, at ~600 mA g -1 rate. The remarkable performance of this nano-functional superlattice film is found to be promising as anodes for applications that require high energy, long calendar life, and excellent abuse tolerance such as electric vehicle batteries.

25 ENERGY STORAGE↗

A solid-state framework for terrestrial upper mantles

A framework is proposed for understanding the upper mantle structure of the terrestrial planets which is based on solid state dislocation processes. It is proposed that the base of the lithosphere on any planet with a Mg-Fe silicate rich upper mantle is defined by the threshold temperatures of low energy dislocation glide systems in olivine and the pyroxenes. This threshold temperature is approximately 1100 to 1200 K and is directly tied to the mobility of olivine and pyroxene dislocations. Using this definition, all terrestrial planets of the Inner Solar System are expected to have mantle lithospheres. Second, the anomalous properties of the asthenosphere in the Earth are related to the rheological properties of an olivine rich differentiate approximately 220 km thick. All of these properties can be the result of the abundant low energy glide systems in olivine which are mobile at temperatures above approximately 1200 K. It is proposed that a true planetary asthenosphere must be both olivine rich and at temperatures above approximately 1200 K. This mode for the asthenosphere does not require partial melting and is therefore less sensitive to the constraints of volatile content in the upper mantle. The thickness of planetary lithospheres is estimated as is maximum thickness of the olivine rich differentiate on each planet. The cooling of the olivine rich layer on Mars (and hence disappearance of the asthenosphere) may coincide with the cessation of global tectonic activity approximately 1 Gyr ago.

Estey, L.↗

Fabrication of thin-film electronic devices with non-destructive wafer reuse

Thin-film electronic devices such as LED devices and field effect transistor devices are fabricated using a non-destructive epitaxial lift-off technique that allows indefinite reuse of a growth substrate. The method includes providing an epitaxial protective layer on the growth substrate and a sacrificial release layer between the protective layer and an active device layer. After the device layer is released from the growth substrate, the protective layer is selectively etched to provide a newly exposed surface suitable for epitaxial growth of another device layer. The entire thickness of the growth substrate is preserved, enabling continued reuse. Inorganic thin-film device layers can be transferred to a flexible secondary substrate, enabling formation of curved inorganic optoelectronic devices.

Forrest, Stephen R.↗

1.1 eV GaInAs Cell Development for Dual-Use Solar and 1070 nm Laser Power Converters

Dual-use power converter cells can receive solar and laser power simultaneously to generate current, an application relevant to space and terrestrial industries. This study investigates two concepts of solar cells optimized for dual-use 1070 nm laser and solar power conversion, a single-junction and triple-junction cell. Because it is bandgap-tuned for a 1070 nm laser, the 1.1 eV junction is incorporated into each of the two designs, making its development key to the success of both concepts. Efficiency data for a one junction GaInAs cell demonstrates a laser conversion efficiency of 38% at 1070nm wavelength without an anti-reflection coating. However, the single-junction device requires optimization to reduce short wavelength absorption of the broad solar spectrum. In both devices, the graded buffer layers in the GaInAs cell affects the cell's performance by reducing threading dislocations in the active junction. However, the buffer in the three-junction device also acts as a lateral transport layer and so affects the fill factor depending on its sheet resistance. By varying the buffer thickness, we demonstrate a direct relationship between buffer thickness and sheet resistance reduction, while considering implications to open-circuit voltages. We also performed resistance modeling to determine the optimal grid spacing and thickness of the grid fingers to minimize losses due to sheet resistance and grid shading.

junctions↗

1.1 eV GaInAs Cell Development for Dual-Use Solar and 1070 nm Laser Power Converters

Dual-use photovoltaic cells can receive solar and laser power simultaneously to generate current, an application relevant to space and terrestrial industries. This study investigates two concepts of solar cells optimized for dual-use 1070 nm laser and solar power conversion, a single-junction and triple-junction cell. The cell designs are based upon the 3- junction inverted metamorphic solar cell, previously shown highly efficient for solar conversion. Because it is closely bandgap-tuned for a 1070 nm laser, the 1 eV bottom junction is incorporated into each of the two designs, making its development key to the success of both concepts. However, each design requires some modification for efficient dual use. The single-junction device requires optimization to reduce short wavelength absorption of the broad solar spectrum. In both devices, the graded buffer layers in the GaInAs cell affect the cell's performance by reducing threading dislocations in the active junction. However, the buffer in the three-junction device also acts as a lateral transport layer and so affects the fill factor depending on its sheet resistance. By varying the buffer thickness, we demonstrate a direct relationship between buffer thickness and sheet resistance reduction, while considering implications to open-circuit voltages. We also performed resistance modeling to determine the optimal grid spacing and thickness of the grid fingers to minimize losses due to sheet resistance and grid shading. Efficiency data for a one junction GaInAs cell demonstrates a laser conversion efficiency of 38% at 1070 nm wavelength without an anti-reflection coating.

dual-use↗

Large area space qualified thermoelectrically (TE) cooled HgCdTe MW photovoltaic detectors for the Halogen Occultation Experiment (HALOE)

Large-area, HgCdTe MW photovoltaic detectors have been developed for the NASA-HALOE instrument scheduled for operation on the Upper Atmospheric Research Satellite. The photodiodes will be TE-cooled and were designed to operate in the 5.1-5.4 micron band at 185 K to measure nitric oxide concentrations in the atmosphere. The active area required 15 micron thick devices and a full backside common contact. Reflections from the backside contact doubled the effective thickness of the detectors. Optical interference from reflections was eliminated with a dual layer front surface A/R coating. Bakeout reliability was optimized by having Au metallization for both n and p interconnects. Detailed performance data and a model for the optical stack are presented.

Norton, P. W.↗

1.1 eV GaInAs Cell Development for Dual-Use Solar and 1075 nm Laser Power Converters

Dual-use power converter cells can receive solar and laser power simultaneously to generate current, an application relevant to space and terrestrial industries. This study investigates two concepts of solar cells optimized for dual- use 1070 nm laser and solar power conversion, a single-junction and triple-junction cell. Because it is bandgap-tuned for a 1070 nm laser, the 1.1 eV junction is incorporated into each of the two designs, making its development key to the success of both concepts. Efficiency data for a one junction GaInAs cell demonstrates a laser conversion efficiency of 38% at 1070nm wavelength without an anti-reflection coating. However, the single-junction device requires optimization to reduce short wavelength absorption of the broad solar spectrum. In both devices, the graded buffer layers in the GaInAs cell affects the cell's performance by reducing threading dislocations in the active junction. However, the buffer in the three-junction device also acts as a lateral transport layer and so affects the fill factor depending on its sheet resistance. By varying the buffer thickness, we demonstrate a direct relationship between buffer thickness and sheet resistance reduction, while considering implications to open-circuit voltages. We also performed resistance modeling to determine the optimal grid spacing and thickness of the grid fingers to minimize losses due to sheet resistance and grid shading.

dual-use↗

UCGretina geant4 simulation of the GRETINA Gamma-Ray Energy Tracking Array

UCGretina, a geant4 simulation of the GRETINA gamma-ray tracking array of highly-segmented high-purity germanium detectors is described. We have developed a model of the array, in particular of the Quad Module and the capsules, that gives good agreement between simulated and measured photopeak efficiencies over a broad range of gamma-ray energies and reproduces the shape of the measured Compton continuum. Both of these features are needed in order to accurately extract gamma-ray yields from spectra collected in in-beam gamma-ray spectroscopy measurements with beams traveling at v / c ≳0.3 at the National Superconducting Cyclotron Laboratory and the Facility for Rare Isotope Beams. In the process of developing the model, we determined that millimeter-scale layers of passive germanium surrounding the active volumes of the simulated crystals must be included in order to reproduce measured photopeak efficiencies. In conclusion, we adopted a simple model of effective passive layers and developed heuristic methods of determining passive-layer thicknesses by comparison of simulations and measurements for a single crystal and for the full array. Prospects for future development of the model are discussed.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Enhanced long-term cyclability in Li-Rich layered oxides by electrochemically constructing a Li x TM 3-x O 4 -type spinel shell

The poor long-term cycling stability, including the fast capacity fade and the severe voltage decay, has become the main concern hindering the practical application of Li-rich layered oxides, a promising cathode for high- energy-density Li-ion battery. Herein, we design and electrochemically construct a ~10 nm-thick Li x TM 3-x O 4 - type (TM ¼Ni, Co, Mn, 0 3 O 4 -type spinel phase and the good Liþconductivity of LiMn 2 O 4 -type spinel phase. Systemic structural and electrochemical analysis demonstrate that, it slows down the activation rate of Li 2 MnO 3 component and efficiently alleviates the lattice O loss at high voltage (>4.5 V) and Mn dissolution, thereby suppressing the structural degradation from the layered phase to the spinel phase in the bulk, eventually significantly enhancing the long-term cycling stability. This study adds richness into the Mn-based spinel phase system and provides a new heterostructure design strategy to improve the electrochemical performance of Li-rich layered cathodes and beyond.

25 ENERGY STORAGE↗

Translational diffusion in supercooled water at and near the glass transition temperature—136 K

The properties of amorphous solid water at and near the calorimetric glass transition temperature, T g , of 136 K have been debated for years. One hypothesis is that water turns into a “true” liquid at T g (i.e., it becomes ergodic) and exhibits all the characteristics of an ergodic liquid, including translational diffusion. A competing hypothesis is that only rotational motion becomes active at T g , while the “real” glass transition in water is at a considerably higher temperature. To address this dispute, we have investigated the diffusive mixing in nanoscale water films, with thicknesses up to ∼100 nm, using infrared (IR) spectroscopy. The experiments used films that were composed of at least 90% H 2 O with D 2 O making up the balance and were conducted under conditions where H/D exchange was essentially eliminated. Because the IR spectra of multilayer D 2 O films (e.g., thicknesses of ∼3–6 nm) embedded within thick H 2 O films are distinct from the spectrum of isolated D 2 O molecules within H 2 O, the diffusive mixing of (initially) isotopically layered water films could be followed as a function of annealing time and temperature. The results show that water films with total thicknesses ranging from ∼20 to 100 nm diffusively mixed prior to crystallization for temperatures between 120 and 144 K. The translational diffusion had an Arrhenius temperature dependence with an activation energy of 40.8 ± 3.5 kJ/mol, which indicates that water at and near T g is a strong liquid. The measured diffusion coefficient at 136 K is 6.25 ± 1.4 × 10 −21 m 2 /s.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Apollo 14 active seismic experiment.

Explosion seismic refraction data indicate that the lunar near-surface rocks at the Apollo 14 site consist of a regolith 8.5 meters thick and characterized by a compressional wave velocity of 104 meters per second. The regolith is underlain by a layer with a compressional wave velocity of 299 meters per second. The thickness of this layer, which we interpret to be the Fra Mauro Formation, is between 16 and 76 meters. The layer immediately beneath this has a velocity greater than 370 meters per second. We found no evidence of permafrost.

Watkins, J. S.↗

Sweep and Compressibility Effects on Active Separation Control at High Reynolds Numbers

This paper explores the effects of compressibility, sweep and excitation location on active separation control at high Reynolds numbers. The model, which was tested in a cryogenic pressurized wind tunnel, simulates the upper surface of a 20% thick GlauertGoldschmied type airfoil at zero angle of attack. The flow is fully turbulent since the tunnel sidewall boundary layer flows over the model. Without control, the flow separates at the highly convex area and a large turbulent separation bubble is formed. Periodic excitation is applied to gradually eliminate the separation bubble. Two alternative blowing slot locations as well as the effect of compressibility, sweep and steady suction or blowing were studied. During the test the Reynolds numbers ranged from 2 to 40 million and Mach numbers ranged from 0.2 to 0.7. Sweep angles were 0 and 30 deg. It was found that excitation must be introduced slightly upstream of the separation region regardless of the sweep angle at low Mach number. Introduction of excitation upstream of the shock wave is more effective than at its foot. Compressibility reduces the ability of steady mass transfer and periodic excitation to control the separation bubble but excitation has an effect on the integral parameters, which is similar to that observed in low Mach numbers. The conventional swept flow scaling is valid for fully and even partially attached flow, but different scaling is required for the separated 3D flow. The effectiveness of the active control is not reduced by sweep. Detailed flow field dynamics are described in the accompanying paper.

Seifert, Avi↗