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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
NASA NTRSDate not supplied

Mixed-Domain Charge Transport in S-Se Alloys as a Li-S Battery Cathode Material

Lithium-sulfur batteries are emerging candidate systems for the next-generation long-range electric aircraft application owing to their potential to deliver high energy density per weight. Their cathodes are to be made primarily with sulfur, but sulfur by itself has much too low electron conductivity to serve as a useful cathode. An idea that has been suggested to overcome this bottleneck is to alloy sulfur with selenium in the hope that electron mobility, which is thought to improve charge transport at some expense of increased weight and reduced energy density. However, understanding of these alloy structures and their transport mechanism is insufficient, and electron mobility at varying degrees of selenium content is not well charted, which are critical for determining the optimum selenium content and testing whether this strategy is generally feasible. The difficulty of computationally characterizing these alloy systems is rooted in the structure. The structures of both sulfur and selenium exhibit eight-atom rings that pack together in various orientations to form their respective crystals. For one, because these crystals (and presumably their alloys as well) feature multiple polymorphs such that their structural coherence is rather unclear. Secondly, these are also relatively large systems (32 atoms per cell) with low-symmetry, which complicate computation both in terms of accuracy and efficiency. Thirdly, such semi-molecular, semi-crystalline structures lead to a combination of band-transport characteristics and hopping-transport characteristics, each of which is a domain with its own physics and set of computational, theoretical challenges. In addition, there is a general dearth of experimental transport data for sulfur-selenium alloys. In this study, we make a comprehensive attempt to tackle this problem using a wide array of first-principles methods. We generate special quasirandom structures to simulate alloy structures, and compute their first-principles Raman spectra for comparison with experimental data to ensure their structural soundness. We then proceed to use recently developed, state-of-the-art tool (AMSET) in order to efficiently compute electronic mobilities under band transport of pure sulfur, pure selenium, as well as their alloys of various compositions at a reasonable accuracy. We then sample numerous dimer configurations of nearest-neighbor eight-atom-ring-pairs and compute electronic hopping rates between them, which yields hopping mobility. A combination of these efforts lead to a general mapping of electron transport behaviors throughout the alloy range. Preliminary results show that introduction of selenium into sulfur initially damages electron mobility due to disorder but eventually improves it beyond that of pure sulfur with additional selenium content, ultimately peaking at the pure-selenium limit. Band transport dominates for holes in sulfur and electrons in selenium, but in all other cases, hopping transport is dominant. Ongoing efforts include determination of charge concentration and conductivity, as well as performing multiphysics modeling to determine the optimum selenium content for best tradeoff between conductivity and energy density for aircraft range.

Junsoo Park↗
NASA NTRS1973

Anode power deposition in quasi-steady MPD arcs

The power deposited in the anode of a quasi-steady MPD accelerator has been measured directly by thermocouples attached to the inside surface of a shell anode which provide a local measurement of anode heat flux. The results over a range of arc currents from 5.5 to 44 kiloamperes and argon mass flows from 1 g/sec to 48 g/sec show that the fraction of the total input power deposited in the anode decreases drastically from 50% at an arc power of 200 kW to 10% at 20 MW, and that anode power is not uniformly deposited in the anode. A theoretical model of the anode heat transfer, including effects of anode work function, electron thermal energy, and anode sheath, can be brought into reasonable agreement with the measurements, provided the effective range of the conduction electrons from within the discharge plasma to the anode surface is properly acknowledged.

Saber, A. J.↗
NASA NTRS1972

Positive ions and the winter anomaly.

A coordinated rocket program to study winter variability in D-region ionization was conducted at White Sands Missile Range, New Mexico, during the winter of 1970-1971. Parachute-borne blunt probes that measure positive-ion and electron conductivities were flown, in conjunction with other experiments, on Jan. 22 and 26 and Feb. 1, 1971. Both A1 and A3 radiowave absorption techniques were used to indicate anomalous winter days. The two rocket shots in January occurred on such days of high absorption. The first of these was one of quiet solar activity, whereas the second was preceded by a major solar proton event on January 24. The third flight occurred on a normal winter day. We tentatively conclude that we have observed two days of 'anomalous' winter absorption of very different character, one possibly related to a solar disturbance, and one probably entirely induced by meteorological effects. The former day was probably characterized by inhibition of the formation of negative ions due to increased detachment and the latter by decreased ionization loss rate.

Mitchell, J. D.↗
NASA NTRS2011

Composite Thermal Switch

Lithium primary and lithium ion secondary batteries provide high specific energy and energy density. The use of these batteries also helps to reduce launch weight. Both primary and secondary cells can be packaged as high-rate cells, which can present a threat to crew and equipment in the event of external or internal short circuits. Overheating of the cell interior from high current flows induced by short circuits can result in exothermic reactions in lithium primary cells and fully charged lithium ion secondary cells. Venting of the cell case, ejection of cell components, and fire have been reported in both types of cells, resulting from abuse, cell imperfections, or faulty electronic control design. A switch has been developed that consists of a thin layer of composite material made from nanoscale particles of nickel and Teflon that conducts electrons at room temperature and switches to an insulator at an elevated temperature, thus interrupting current flow to prevent thermal runaway caused by internal short circuits. The material is placed within the cell, as a thin layer incorporated within the anode and/or the cathode, to control excess currents from metal-to-metal or metal-to-carbon shorts that might result from cell crush or a manufacturing defect. The safety of high-rate cells is thus improved, preventing serious injury to personnel and sensitive equipment located near the battery. The use of recently available nanoscale particles of nickel and Teflon permits an improved, homogeneous material with the potential to be fine-tuned to a unique switch temperature, sufficiently below the onset of a catastrophic chemical reaction. The smaller particles also permit the formation of a thinner control film layer (<50 m), which can be incorporated into commercial high-rate lithium primary and secondary cells. The innovation permits incorporation in current lithium and lithium-ion cell designs with a minimal impact on cell weight and volume. The composite thermal switch (CTS(TradeMark)) coating can be incorporated in either the anode or cathode or both. The coating can be applied in a variety of different processes that permits incorporation in the cell and electrode manufacturing processes. The CTS responds quickly and halts current flow in the hottest parts of the cell first. The coating can be applied to metal foil and supplied as a cell component onto which the active electrode materials are coated.

McDonald, Robert↗
NASA NTRS2017

Metallic Junction Thermoelectric Device Simulations

Thermoelectric junctions made of semiconductors have existed in radioisotope thermoelectric generators (RTG) for deep space missions, but are currently being adapted for terrestrial energy harvesting. Unfortunately, these devices are inefficient, operating at only 7% efficiency. This low efficiency has driven efforts to make high-figure-of-merit thermoelectric devices, which require a high electrical conductivity but a low thermal conductivity, a combination that is difficult to achieve. Lowered thermal conductivity has increased efficiency, but at the cost of power output. An alternative setup is to use metallic junctions rather than semiconductors as thermoelectric devices. Metals have orders of magnitude more electrons and electronic conductivities higher than semiconductors, but thermal conductivity is higher as well. To evaluate the viability of metallic junction thermoelectrics, a two dimensional heat transfer MATLAB simulation was constructed to calculate efficiency and power output. High Seebeck coefficient alloys, Chromel (90%Ni-10%Cr) and Constantan (55%Cu-45%Ni), produced efficiencies of around 20-30%. Parameters such as the number of layers of junctions, lateral junction density, and junction sizes for both series- and parallel-connected junctions were explored.

Duzik, Adam J.↗
NASA NTRS1973

Selection and preliminary evaluation of three structures as potential solid conductors of alkali ions: Two hollandites, a titanate, and a tungstate

Utilization of crystal-chemical criteria has suggested three structure types in which alkali ions may be mobile: (1)hollandites K(x)Mg(x/2)Ti(8-x/2)O16 and K(x)Al(x)Ti(8-x)O16 for 1.6 less than or equal to x less than or equal to 2.0 tungstate K2W4013; and (3) sodium hexatitante Na2Ti6O13. Each is a tunnel structure. An electrical screening procedure, previously tested on beta-alumina, has indicated high K(+) ion mobility in the hollandites and in the tungstate, but not in the hexatitanate. Specimens were polycrystalline disks near 90 percent of theoretical density. The ac conductivity calculated from dielectric and capacitance measurements has been attributed to ion mobility. This ac conductivity was up to 0.01/ohm-cm for hollandites and about 0.0001/ohm-cm for the tungstate, with approximate activation energies of 21 to 25 and 16 kJ/mole (5 to 6 and 4 kcal/mole), respectively. Electronic conduction and chemical reactivity have eliminated the tungstate from further consideration. The hollandites have been considered worthy of further development and evaluation.

Singer, J.↗
NASA NTRS1989

The solid state photomultiplier: Status of photon counting beyond the near-infrared

Rockwell International's Solid State Photomultiplier (SSPM) is an impurity-band avalanche device which can count individual photons with wavelengths between 0.4 and 28 micrometers. Its response to a photon is a pulse of between 10(exp 4) and 10(exp 5) conduction electrons, making it an important device for use in phenomenology. The characteristics of the SSPM make it a potentially important device for use in astronomical applications. Contract NAS2-12400 was initiated in June 1986 to conduct modeling and characterization studies of the SSPM to provide a basis for assessing its use in astronomical systems. Some SSPM models and results of measurements which characterize the group of SSPMs recently fabricated on this contract are discussed.

Hays, K. M.↗
NASA NTRS1993

Correlated petrographic, electron microprobe, and ion microprobe studies of selected primitive and processed phase assemblages in meteorites

During the past three years we have received support to continue our research in elucidating the formation and alteration histories of selected meteoritic materials by a combination of petrographic, trace element, and isotopic analyses employing optical and scanning electron microscopes and electron and ion microprobes. The awarded research funds enabled the P.I. to attend the annual LPSC, the co-I to devote approximately 15 percent of his time to the research proposed in the grant, and partial support for a visiting summer post-doctoral fellow to conduct electron microprobe analyses of meteoritic samples in our laboratory. The research funds, along with support from the NASA Education Initiative awarded to P.I. G. Wasserburg, enabled the co-I to continue a mentoring program with inner-city minority youth. The support enabled us to achieve significant results in the five projects that we proposed (in addition to the Education Initiative), namely: studies of the accretional and post-accretional alteration and thermal histories in CV meteorites, characterization of periclase-bearing Fremdlinge in CV meteorites, characterization of Ni-Pt-Ge-Te-rich Fremdlinge in CV meteorites in an attempt to determine the constraints they place on the petrogenetic and thermal histories of their host CAI's, correlated electron and ion microprobe studies of silicate and phosphate inclusions in the Colomera meteorite in an attempt to determine the petrogenesis of the IE iron meteorites, and development of improved instrumental and correction procedures for improved accuracy of analysis of meteoritic materials with the electron microprobe. This grant supported, in part or whole, 18 publications so far by our research team, with at least three more papers anticipated. The list of these publications is included. The details of the research results are briefly summarized.

Albee, Arden L.↗
NASA NTRS1990

Applications of high thermal conductivity composites to electronics and spacecraft thermal design

Recently, high thermal conductivity graphite fiber-reinforced metal matrix composites (MMCs) have become available that can save weight over present methods of heat conduction. Another significant advantage is that these materials can be used without the plumbing and testing complexities that accompany the use of liquid heat pipes. A spinoff of this research was the development of other MMCs as electronic device heat sinks. These use particulates rather than fibers and are formulated to match the coefficient of thermal expansion of electronic substrates in order to alleviate thermally induced stresses. The development of both types of these materials as viable weight-saving substitutes for the traditional methods of thermal control for electronics packaging and also for spacecraft thermal control applications are the subjects of this report.

Sharp, G. Richard↗
NASA NTRS1990

Applications of high thermal conductivity composites to electronics and spacecraft thermal design

Recently, high thermal conductivity continuous graphite fiber reinforced metal matrix composites (MMC's) have become available that can save much weight over present methods of heat conduction. These materials have two or three times higher thermal conductivity in the fiber direction than the pure metals when compared on a thermal conductivity to weight basis. Use of these materials for heat conduction purposes can result in weight savings of from 50 to 70 percent over structural aluminum. Another significant advantage is that these materials can be used without the plumbing and testing complexities that accompany the use of liquid heat pipes. A spinoff of this research was the development of other MMC's as electronic device heat sinks. These use particulates rather than fibers and are formulated to match the coefficient of thermal expansion of electronic substrates in order to alleviate thermally induced stresses. The development of both types of these materials as viable weight saving substitutes for traditional methods of thermal control for electronics packaging and also for spacecraft thermal control applications are the subject of this report.

Sharp, G. Richard↗
NASA NTRS2008

Oxide Fiber Cathode Materials for Rechargeable Lithium Cells

LiCoO2 and LiNiO2 fibers have been investigated as alternatives to LiCoO2 and LiNiO2 powders used as lithium-intercalation compounds in cathodes of rechargeable lithium-ion electrochemical cells. In making such a cathode, LiCoO2 or LiNiO2 powder is mixed with a binder [e.g., poly(vinylidene fluoride)] and an electrically conductive additive (usually carbon) and the mixture is pressed to form a disk. The binder and conductive additive contribute weight and volume, reducing the specific energy and energy density, respectively. In contrast, LiCoO2 or LiNiO2 fibers can be pressed and sintered to form a cathode, without need for a binder or a conductive additive. The inter-grain contacts of the fibers are stronger and have fewer defects than do those of powder particles. These characteristics translate to increased flexibility and greater resilience on cycling and, consequently, to reduced loss of capacity from cycle to cycle. Moreover, in comparison with a powder-based cathode, a fiber-based cathode is expected to exhibit significantly greater ionic and electronic conduction along the axes of the fibers. Results of preliminary charge/discharge-cycling tests suggest that energy densities of LiCoO2- and LiNiO2-fiber cathodes are approximately double those of the corresponding powder-based cathodes.

Rice, Catherine E.↗
NASA NTRS1999

Stable powders made from photosensitive polycrystalline complexes of heterocyclic monomers and their polymers

The present invention relates to a low electronic conductivity polymer composition having well dispersed metal granules, a stable powder made from photosensitive polycrystalline complexes of pyrrole, or its substituted derivatives and silver cations for making the polymer composition, and methods of forming the stable powder and polymer composition, respectively. A polycrystalline complex of silver and a monomer, such as pyrrole, its substituted derivatives or combinations thereof, is precipitated in the form of a stable photosensitive powder upon addition of the monomer to a solvent solution, such as toluene containing an electron acceptor. The photosensitive powder can be stored in the dark until needed. The powder may be dissolved in a solvent, cast onto a substrate and photopolymerized.

Hodko, Dalibor↗
NASA NTRS1992

Electrolytic smelting of lunar rock for oxygen, iron, and silicon

Preliminary studies of the electrochemical properties of silicate melts such as those available from heating of lunar mare soils indicate that conductivities are high enough for design of a practical electrolytic cell. The nature and kinetics of the electrode reactions, which involve reduction of Fe(++) and Si(IV) and oxidation of silicate anions as the primary, product-forming reactions, are also satisfactory. A survey of the efficiencies for production (amount of product for a given current) of O2, Fe(sup 0), and Si(sup 0) as functions of potential and of electrolyte composition indicate that conditions can be chosen to yield high production efficiencies. We also conclude that electronic conductivity does not occur to a significant extent. Based on these data, a cell with electrodes of 30 sq m in area operating between 1 and 5V with a current between 1.6 and 3.5(10)(exp 5) A for a mean power requirement of 0.54 MW and total energy use of approximately 13 MWhr per 24-hr day would produce 1 ton of O2, 0.81 ton of Fe(sup 0), 0.65 ton of Si(sup 0) (as Fe(sup 0)-Si(sup 0) alloy), and about 3.5 tons of silicate melt of altered composition per 24 hr. Adjustable distance between electrodes could offer flexibility with respect to feedstock and power source.

Haskin, Larry A.↗
NASA NTRS2020

Structural evolution, electrochemical kinetic properties, and stability of A-site doped perovskite Sr(1-x)Yb(x)CoO(3-δ)

Mixed ionic and electronic conducting (MIEC) perovskite SrCoO(3-δ) is a widely studied (electro)catalyst for the oxygen reduction reaction (ORR) and possesses different crystal structures at different temperatures. These temperature dependent phase transitions significantly impact the ordering of oxygen vacancies and electrochemical kinetic properties as well as the reliability of the related devices. Some of the crystal structures formed, e.g. hexagonal phases, turn out to be almost impermeable to oxygen gas. Therefore, it is important to stabilize the crystal structure of SrCoO(3-δ) that favors the ORR over a wide temperature range. Herein, the partial substitution of the A-site Sr with Yb is systematically studied, including synthesis, characterization and analysis of structural evolution, electrochemical kinetic properties, thermal stability, and stability in a CO2-containing atmosphere. The results indicate that Sr(0.90)Yb(0.10)CoO(3-δ) is able to stabilize the tetragonal crystal structure with less ordered oxygen vacancies, leading to polarization resistances of 0.051, 0.115 and 0.272 U sq.cm at 750, 700 and 650 °C, respectively, on symmetrical cells. Sr(0.90)Yb(0.10)CoO(3-δ) demonstrates a very stable surface oxygen vacancy distribution and electronic structure near oxygen vacancies but dissociation of adsorbed oxygen molecules into atomic oxygen is affected by surface Sr segregation, and polarization resistance degradation is mainly induced by surface Sr segregation. Furthermore, Sr(0.90)Yb(0.10)CoO(3-δ) exhibits excellent thermal stability as well as excellent recovery stability and improved polarization performance after a few pure air/CO2-containing air treatment cycles at 700 °C. However, a hysteresis behavior of polarization performance is observed at 650 °C during gas cycling treatment, which may cause long-term degradation of the Sr(0.90)Yb(0.10)CoO(3-δ) electrode. The different polarization behaviors during gas cycling treatment are induced by different sensitivities of the formed surface strontium carbonate and chemisorbed surface oxo-carbonaceous species to different operating temperatures.

electrochemical kinetic↗
NASA NTRSDate not supplied

Apollo Sample 64455: Petrologic and Geochemical Characterization of a Glass-Coated Impact Melt Rock

Introduction and Background: Impact melts are a key product of the impact cratering process. Impact melts can turbulently entrain pre-existing rock fragments, and melt part of those entrained materials until thermal equilibrium is achieved [1–3]. Lunar impact melt rocks are valuable for determining the precise ages of basin-forming and cratering events, which anchor the cratering chronology and dynamics of the entire solar system [4, and references therein]. Additionally, entrained clasts can inform on the petrology and age of crustal materials that predate the melt-forming impact. In lithologies where no pristine samples are available, entrained materials may hold the record of endogenous lunar volatiles, provided we can untangle their impact histories as high temperature impact melt can heat the clasts and may alter their native volatiles or isotopic signatures [5–6]. Here, we characterize an Apollo 16 sample, 64455,70B, in an effort to understand the physical, microstructural, and geochemical consequences of impact melt contact metamorphism. We acquired optical light and x-ray maps of the sample, as well as quantitative analyses via electron probe microanalysis (EPMA). These tasks allow us to better understand the interaction between impact melts and entrained clasts, ultimately closing knowledge gaps in high-temperature impact processing on planetary surfaces. Sample Description: Sample 64455 is an oblong crystalline rock encased in glass to form an egg-like shape [7–8]. The impact melt coating has altered the outer (1 to 2 mm) rind of the crystalline rock and has preserved schlieren. The interior crystalline rock is likely a crystalline impact melt rock based on its bulk Ir content of 2.25 parts per billion [9]. The composition of the impact melt glass rind cannot be solely derived from the crystalline interior, the glassy rind is more aluminous and less magnesian [10]. Neither the crystalline interior nor the glassy rind were radiometrically age dated, although several studies investigated its cosmogenic isotopes and exposure ages, which reveal the sample was exposed on the lunar surface for ~1–2 Ma [11–13]. Preliminary Results: The interior crystalline rock consists primarily of plagioclase with interstitial pyroxene and olivine. Plagioclase grains are zoned and compositions range from An97–89, while pyroxene compositions generally range from En68Fs19Wo13 to En82Fs15Wo3 and olivine are Fo77 to Fo85. Minor phases include Fe-Ni metal, Ca-phosphates, a K- and Si-rich phase, sulfides, and Fe-phosphides. The glass rind contains approximately 44 wt.% SiO2, 25 wt.% Al2O3, 6 wt.% FeO, 8 wt.% MgO, and 14 wt.% CaO, with other oxides at <1 wt.% each, although the composition of the glass becomes more variable closest to the crystalline rock. The rind consists of rounded plagioclase, pyroxene, and olivine crystals with interstitial melt. In some locations, the rounded crystals are surrounded by closely-packed, blade-like crystals, <5 µm in width. These results indicate that the crystalline interior has partially melted where in contact with the high-temperature impact melt and while further investigation is needed, pyroxene may have preferentially melted relative to olivine and plagioclase. Future Work: We plan to conduct electron backscatter diffraction (EBSD) mapping in order to determine crystallinity and crystal orientation. Next using transmission electron microscopy (TEM) data in conjunction with EBSD and EPMA information, we will model the diffusion of moderately volatile elements between the melt and remnant crystals.

A C Stadermann↗
NASA NTRS1968

Technique increases storage capacity in camera tube target

Technique increases the signal current, where direct beam readout is used, in Secondary Electron Conduction /SEC/ camera tubes. Increasing the storage capacity and therefore the dynamic range of the SEC target permits satisfactory operation at reduced frame rates.

Boll, K. F.↗