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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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A method is described for making an alkaline battery electrode plate where the desired active substances are filled into a nickel foam substrate. In this substrate an electrolytic oxidation reduction occurs in an alkaline solution containing lithium hydroxide.
A component screening facility has been established at The NASA Glenn Research Center (GRC) to evaluate candidate materials for next generation, lithium-based, polymer electrolyte batteries for aerospace applications. Procedures have been implemented to provide standardized measurements of critical electrolyte properties. These include ionic conductivity, electronic resistivity, electrochemical stability window, cation transference number, salt diffusion coefficient and lithium plating efficiency. Preliminary results for poly(ethy1ene oxide)-based polymer electrolyte and commercial liquid electrolyte are presented.
Controlling carbon dioxide (CO2) and humidity levels in a spacesuit is critical to ensuring both the safety and comfort of an astronaut during extra-vehicular activity (EVA). Traditionally, this has been accomplished utilizing either non-regenerative lithium hydroxide (LiOH) or regenerative but heavy metal oxide (MetOx) canisters which pose a significant weight burden. Although such technology enables air revitalization, the volume requirements to store the waste canisters as well as the mass to transport multiple units become prohibitive as mission durations increase. Consequently, motivation exists toward developing a fully regenerative technology for spacesuit environmental control. The application of solid amine materials with vacuum swing adsorption technology has shown the capacity to control CO2 while concomitantly managing humidity levels through a fully regenerative cycle eliminating constraints imposed with the traditional technologies. Prototype air revitalization units employing this technology have been fabricated in both a rectangular and cylindrical geometry. Experimental results for these test articles have been collected and are described herein. In order to accelerate the developmental efforts, an axially-dispersed plug flow model with an accompanying energy balance has been established and correlated with the experimental data. The experimental and simulation results display good agreement for a variety of flow rates (110-170 ALM), replicated metabolic challenges (100-590 Watts), and atmosphere pressures under consideration for the spacesuit (248 and 760 mm Hg). The testing and model results lend insight into the operational capabilities of these devices as well as the influence the geometry of the device has on performance. In addition, variable metabolic profiles were imposed on the test articles in order to assess the ability of the technology to transition to new metabolic conditions. The advent of the model provides the capacity to apply computer-aided engineering practices to support the ongoing efforts to optimize and mature this technology for future application to space exploration.
The upper atmosphere offers a vast photochemical laboratory free from solid surfaces, so all reactions take place in the gaseous phase. At 30 km altitude the pressure has fallen to about one-hundredth of that at ground level, and we shall, rather arbitrarily, regard the upper atmosphere as beginning at that height. By a little less than 100 km the pressure has fallen to 10(exp -3) mm Hg and is decreasing by a power of ten for every 15 km increase in altitude. Essentially we are concerned then with the photochemistry of a nitrogen-oxygen mixture under low-pressure conditions in which photo-ionization, as well as photodissociation, plays an important part. Account must also be taken of the presence of rare constituents, such as water vapour and its decomposition products, including particularly hydroxyl, oxides of carbon, methane and, strangely enough, sodium, lithium and calcium. Many curious and unfamiliar reactions occur in the upper atmosphere. Some of them are luminescent, causing the atmosphere to emit a dim light called the airglow. Others, between gaseous ions and neutral molecules, are almost a complete mystery at this time. Similar interesting phenomena must occur in other planetary atmospheres, and they might be predicted if sufficient chemical information were available.
This paper describes a series of rod-coil block co-polymers that produce easy to fabricate, dimensionally stable films with good ionic conductivity down to room temperature for use as electrolytes for lithium polymer batteries. The polymers consist of short, rigid rod polyimide segments, alternating with flexible, polyalkylene oxide coil segments. The highly incompatible rods and coils should phase separate, especially in the presence of lithium ions. The coil phase would allow for conduction of lithium ions, while the rigid rod phase would provide a high degree of dimensional stability. An optimization study was carried out to study the effect of four variables (degree of branching, formulated molecular weight, polymerization solvent and lithium salt concentration) on ionic conductivity, glass transition temperature and dimensional stability in this system.
Advancing beyond current lithium-ion technology is necessary in order to enable energy storage devices for electric airplanes. Electrolyte stability is a key limiting factor, yet the design of improved electrolytes remains a formidable challenge. Molecular dynamics (MD) simulations are a powerful tool for studying electrolytes, since they can be used to evaluate structural, thermodynamic, and transport properties, and can provide molecular-level detail often inaccessible to experimental techniques. Our computational materials groups at the NASA Ames Research Center has developed models and methods to accurately simulate both liquid and polymer electrolytes.We report the results from atomistic MD simulations of several electrolyte materials, with lithium salts dissolved in ionic liquids, dimethoxyethane (DME), and polyethylene oxide (PEO). For improved accuracy, we employ polarizable models, where each atom is given an environment-dependent atomic dipole. The simulations accurately predict bulk transport properties, including viscosity, diffusion, and ionic conductivity, in quantitative agreement with available experimental data. Moreover, the simulations provide important insights into the solvation structure of the lithium ions.We also report the results from coarse-grained MD simulations of polyanion electrolytes. In order to more efficiently capture the longer length- and time-scales of these systems, we employ a generic bead-spring model. These simulations provide important insight into how the polymer chain architecture and ionic interaction strengths affect the ionic aggregation behavior and cation dynamics. Despite the simplicity of the model, the simulations yield qualitative agreement with experimental data for similar systems.
Lithium-based polymer batteries for aerospace applications need to be highly conductive from -70 to 70 C. State-of-the-art polymer electrolytes are based on polyethylene oxide (PEO) because of the ability of its ether linkages to solvate lithium ions. Unfortunately, PEO has a tendency to form crystalline regions below 60 C, dramatically lowering conductivity below this temperature. PEO has acceptable ionic conductivities (10(exp -4) to 10(exp -3) S/cm) above 60 C, but it is not mechanically strong. The room-temperature conductivity of PEO can be increased by adding solvent or plasticizers, but this comes at the expense of thermal and mechanical stability. One of NASA Glenn Research Center s objectives in the Polymer Rechargeable System program (PERS) is to develop novel polymer electrolytes that are highly conductive at and below room temperature without added solvents or plasticizers.
The incorporation of specific metal ions into polyimides is described. Detailed studies have included various compounds of copper, lithium, and palladium as dopants. Addition of the metal during polymerization or after formation of the polyamic acid precedes the thermal imidization step. With many dianhydride-diamine-dopant combinations high quality variously colored films are produced. Many metal doped films exhibit (1) improved high temperature adhesive properties, (2) increased electrical conductivity, (3) excellent thermal stability, (4) improved acid/base resistance, (5) increased modulus in flexible films and (6) excellent high temperature tensile strength. X-ray photo-electron spectroscopic study of these films suggests that many of the additives undergo chemical modification during thermal imidization. Palladium dopants appear to be partially reduced to the metallic state, while lithium and copper dopants are probably converted to their oxides. Ion etching experiments with Auger electron spectroscopy monitoring are discussed.
The incorporation of specific metal ions into polyimides is described. Detailed studies have included various compounds of copper, lithium, and palladium as dopants. Addition of the metal during polymermzation or after formation of the polyamic acid precedes the thermal imidization step. With many dianhydride-diamine-dopant combinations high quality variously colored films are produced. Many metal doped films exhibit (1) improved high temperature adhesive properties, (2) increased electrical conductivity, (3) excellent thermal stability, (4) improved acid/base resistance, (5) increased modulus in flexible films and (6) excellent high temperature tensile strength. X-ray photo-electron spectroscopic study of these films suggests that many of the additives undergo chemical modification during thermal imidization. Palladium dopants appear to be partially reduced to the metallic state, while lithium and copper dopants are probably converted to their oxides. Ion etching experiments with Auger electron spectroscopy monitoring are discussed.
Metal-coated graphite fibers are being considered as a thermal conductivity enhancement filler material for molten salts in solar dynamic thermal energy storage systems. The successful metal coating chosen for this application must exhibit acceptable wettability and must be compatible with the molten salt environment. Contact angle values between molten lithium fluoride and several metal, metal fluoride, and metal oxide substrates have been determined at 892 C using a modification of the Wilhelmy plate technique. Reproducible contact angles with repeated exposure to the molten LiF indicated compatibility.
Metabolically produced carbon dioxide (CO2) removal in spacesuit applications has traditionally been accomplished utilizing non-regenerative Lithium Hydroxide (LiOH) canisters. In recent years, regenerative Metal Oxide (MetOx) has been developed to replace the Extravehicular Mobility Unity (EMU) LiOH canister for extravehicular activity (EVA) missions in micro-gravity, however, MetOx may carry a significant weight burden for potential use in future Lunar or planetary EVA exploration missions. Additionally, both of these methods of CO2 removal have a finite capacity sized for the particular mission profile. Metabolically produced water vapor removal in spacesuits has historically been accomplished by a condensing heat exchanger within the ventilation process loop of the suit life support system. Advancements in solid amine technology employed in a pressure swing adsorption system have led to the possibility of combining both the CO2 and humidity control requirements into a single, lightweight device. Because the pressure swing adsorption system is regenerated to space vacuum or by an inert purge stream, the duration of an EVA mission may be extended significantly over currently employed technologies, while markedly reducing the overall subsystem weight compared to the combined weight of the condensing heat exchanger and current regenerative CO2 removal technology. This paper will provide and overview of ongoing development efforts evaluating the subsystem size required to manage anticipated metabolic CO2 and water vapor generation rates in a spacesuit environment.
The present invention comprises an improved electrolyte for secondary lithium-based cells as well as batteries fabricated using this electrolyte. The electrolyte is a lithium containing salt dissolved in a non-aqueous solvent, which is made from a mixture of ethylene carbonate, ethylene propylene diene terpolymer, 2-methylfuran, and 2-methyltetrahydrofuran. This improved, mixed solvent electrolyte is more conductive than prior electrolytes and much less corrosive to lithium anodes. Batteries constructed with this improved electrolyte utilize lithium or lithium alloy anodes and cathodes made of metal chalcogenides or oxides, such as TiS.sub.2, NbSe.sub.3, V.sub.6 O.sub.13, V.sub.2 O.sub.5, MoS.sub.2, MoS.sub.3, CoO.sub.2, or CrO.sub.2, dissolved in a supporting polymer matrix, like EPDM. The preferred non-aqueous solvent mixture comprises approximately 5 to 30 volume percent ethylene carbonate, approximately 0.01 to 0.1 weight percent ethylene propylene diene terpolymer, and approximately 0.2 to 2 percent 2-methylfuran, with the balance being 2-methyltetrahydrofuran. The most preferred solvent comprises approximately 10 to 20 volume percent ethylene carbonate, about 0.05 weight percent ethylene propylene diene terpolymer, and about 1.0 percent 2-methylfuran, with the balance being 2-methyltetrahydrofuran. The concentration of lithium arsenic hexafluoride can range from about 1.0 to 1.8 M; a concentration 1.5 M is most preferred. Secondary batteries made with the improved electrolyte of this invention have lower internal impedance, longer cycle life, higher energy density, low self-discharge, and longer shelf life.
The trace contaminant control system (TCCS) located in the International Space Station s (ISS) U.S. laboratory module employs physical adsorption, thermal catalytic oxidation, and chemical adsorption to remove trace chemical contamination produced by equipment offgassing and anthropogenic sources from the cabin atmosphere. The chemical adsorption stage, consisting of a packed bed of granular lithium hydroxide (LiOH), is located after the thermal catalytic oxidation stage and is designed to remove acid gas byproducts that may be formed in the upstream oxidation stage. While in service on board the ISS, the LiOH bed exhibited a change in flow resistance that leading to flow control difficulties in the TCCS. Post flight evaluation revealed LiOH granule size attrition among other changes. An experimental program was employed to investigate mechanisms hypothesized to contribute to the change in the packed bed s flow resistance. Background on the problem is summarized, including a discussion of likely mechanisms. The experimental program is described, results are presented, and implications for the future are discussed.
A regenerable metal oxide carbon dioxide (CO2) removal system was developed to replace the current means of a nonreusable chemical, lithium hydroxide, for removing the metabolic CO2 of an astronaut in a space suit. Testing indicates that a viable low-volume metal oxide concept can be used in the portable life support system for CO2 removal during Space Station extravehicular activity (EVA). A canister of nearly the same volume as that used for the Space Shuttle, containing 0.10 cu ft of silver-oxide-based pellets, was tested; test data analysis indicates that 0.18 cu ft of the metal oxide will result in an 8-hour EVA capability. The testing suggests that the metal oxide technology offers a low-volume approach for a reusable CO2 removal concept applicable for at least 40 EVA missions. The development and testing of the breadboard regeneration package is also described.
An assessment is made of the potential effectiveness, designs, and technological difficulties involved in the construction of space nuclear reactors coupled to thermionic energy converters (TEC). The TECs can be positioned either inside or outside of the reactor core. The out-of-core design lowers the reactor shielding requirements, as well as removing the need for mechanically pumped coolant for the reactor. R&D is still needed for the heat pipes for the reactor and the collectors, electrical insulation, and to reduce the potential losses in the interelectrode space. A cylindrical converter for the out-of-core configuration consists of a tungsten emitter heated by a tungsten-lithium heat pipe. The collector is a layer of tungsten oxide deposited on a Nb-1%Zr alloy, and has been tested at emitter temperatures of 1300-1850 K and a collector temperature range of 700-850 K. A design of a superheated thermionic converter is described, noting that a prototype has been operated at 1730 K for 12,000 hr.
Polymer-clay nanocomposites have exhibited superior strength and thermo- oxidative properties as compared to pure polymers for use in air and space craft; however, there has often been difficulty completely dispersing the clay within the matrices of the polymer. In order to improve this process, the cation exchange capacity of lithium clay is first lowered using twenty-four hour heat treatments of no heat, 130 C, 150 C, or 170 C to fixate the lithium ions within the clay layers so that they are unexchangeable. Generally, higher temperatures have generated lower cation exchange capacities. An ion exchange involving dodecylamine, octadecylamine, or dimethyl benzidine (DMBZ) is then employed to actually expand the clay galleries. X-ray diffraction and transmission electron microscopy can be used to determine whether the clay has been successfully exfoliated. Finally, resins of DMBZ with clay are then pressed into disks for characterization using dynamic mechanical analyzer and oven- aging techniques in order to evaluate their glass transition, modulus strength, and thermal-oxidative stability in comparison to neat DMBZ. In the future, they may also be tested as composites for flexural and laminar shear strength.
The RS-PM aluminum alloys which show less than anticipated toughness properties were studied. After eliminating negative variables such as sodium and potassium in lithium containing alloys, hydrogen in all Al alloys, and trapped impurities from the atomization processing the data pointed to fine oxides, as the primary cause of poor toughness properties. The oxide content of aluminum powders increases with: decreasing powder size, deviations from spherical powder shapes, exposure to moist atmospheres either during atomization or in subsequent powder handling, and alloy compositions which contain significant amounts of lithium, magnesium, cerium, and other reactive elements.
Advanced high power density rechargeable batteries are currently under development. These batteries have the potential of greatly increasing the power and energy densities available for space applications. Depending on whether the system is optimized for high power or high energy, values up to 150 Wh/kg and 2100 W/kg (including hardware) are projected. This is due to the fact that the system uses a high conductivity molten salt electrolyte. The electrolyte also serves as a separator layer with unlimited freeze thaw capabilities. Life of 1000 cycles and ten calendar years is projected. The electrochemistry consists of a lithium aluminum alloy negative electrode, iron disulfide positive electrode, and magnesium oxide powder immobilized molten salt electrolyte. Processed powders are cold compacted into circular discs which are assembled into bipolar cell hardware with peripheral ceramic salts. The culmination of the work will be a high energy battery of 40 kWh and a high power battery of 28 kWh.