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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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35 records · Page 2

Near-ambient solid polymer fuel cell

Fuel cells are extremely attractive for extraterrestrial and terrestrial applications because of their high energy conversion efficiency without noise or environmental pollution. Among the various fuel cell systems the advanced polymer electrolyte membrane fuel cells based on sulfonated fluoropolymers (e.g., Nafion) are particularly attractive because they are fairly rugged, solid state, quite conductive, of good chemical and thermal stability and show good oxygen reduction kinetics due to the low specific adsorption of the electrolyte on the platinum catalyst. The objective of this program is to develop a solid polymer fuel cell which can efficiently operate at near ambient temperatures without ancillary components for humidification and/or pressurization of the fuel or oxidant gases. During the Phase 1 effort we fabricated novel integral electrode-membrane structures where the dispersed platinum catalyst is precipitated within the Nafion ionomer. This resulted in electrode-membrane units without interfacial barriers permitting unhindered water diffusion from cathode to anode. The integral electrode-membrane structures were tested as fuel cells operating on H2 and O2 or air at 1 to 2 atm and 10 to 50 C without gas humidification. We demonstrated that cells with completely dry membranes could be self started at room temperature and subsequently operated on dry gas for extended time. Typical room temperature low pressure operation with unoptimized electrodes yielded 100 mA/cm(exp 2) at 0.5V and maximum currents over 300 mA/cm(exp 2) with low platinum loadings. Our results clearly demonstrate that operation of proton exchange membrane fuel cells at ambient conditions is feasible. Optimization of the electrode-membrane structure is necessary to assess the full performance potential but we expect significant gains in weight and volume power density for the system. The reduced complexity will make fuel cells also attractive for smaller and portable power supplies and as replacement for batteries.

Holleck, G. L.↗

(abstract) Fundamental Mechanisms of Electrode Kinetics and Alkali Metal Atom Transport at the Alkali Beta'-Alumina/Porous Electrode/Alkali Metal Vapor Three Phase Boundary

The mechanisms of electrode kinetics and mass transport of alkali metal oxidation and alkali metal cation reduction at the solid electrolyte/porous electrode boundary as well as alkali metal transport through porous metal electrodes has important applications in optimizing device performance in alkali metal thermal to electric converter (AMTEC) cells which are high temperature, high current density electrochemical cells. Basic studies of these processes also affords the opportunity to investigate a very basic electrochemical reaction over a wide range of conditions; and a variety of mass transport modes at high temperatures via electrochemical techniques. The temperature range of these investigations covers 700K to 1240K; the alkali metal vapor pressures range from about 10(sup -2) to 10(sup 2) Pa; and electrodes studied have included Mo, W, Mo/Na(sub 2)MoO(sub 4), W/Na(sub 2)WO(sub 4), WPt(sub x), and WRh(sub x) (1.0 < x < 6.0 ) with Na at Na-beta'-alumina, and Mo with K at K-beta'-alumina. Both liquid metal/solid electrolyte/alkali metal vapor and alkali metal vapor/solid electrolyte/vapor cells have been used to characterize the reaction and transport processes. We have previously reported evidence of ionic, free molecular flow, and surface transport of sodium in several types of AMTEC electrodes.

electrode kinetics thermal to electric conversion ↗

The TMI Regenerative Solid Oxide Fuel Cell

Energy storage and production in space requires rugged, reliable hardware which minimizes weight, volume, and maintenance while maximizing power output and usable energy storage. Systems generally consist of photovoltaic solar arrays which operate (during sunlight cycles) to provide system power and regenerate fuel (hydrogen) via water electrolysis and (during dark cycles) fuel cells convert hydrogen into electricity. Common configurations use two separate systems (fuel cell and electrolyzer) in conjunction with photovoltaic cells. Reliability, power to weight and power to volume ratios could be greatly improved if both power production (fuel cells) and power storage (electrolysis) functions can be integrated into a single unit. The solid oxide fuel cell (SOFC) based design integrates fuel cell and electrolyzer functions and potentially simplifies system requirements. The integrated fuel cell/electrolyzer design also utilizes innovative gas storage concepts and operates like a rechargeable 'hydrogen-oxygen battery'. Preliminary research has been completed on improved H2/H20 electrode (SOFC anode/electrolyzer cathode) materials for regenerative fuel cells. Tests have shown improved cell performance in both fuel and electrolysis modes in reversible fuel cell tests. Regenerative fuel cell efficiencies, ratio of power out (fuel cell mode) to power in (electrolyzer mode), improved from 50 percent using conventional electrode materials to over 80 percent. The new materials will allow a single SOFC system to operate as both the electolyzer and fuel cell. Preliminary system designs have also been developed to show the technical feasibility of using the design for space applications requiring high energy storage efficiencies and high specific energy. Small space systems also have potential for dual-use, terrestrial applications.

Cable, Thomas L.↗

The MSP 2001 Mars Environmental Compatibility Assessment (MECA)

A chemical analysis of soil-water mixtures and the first microscopic images of martian soil will be among the results to be returned by the Mars Environmental Compatibility Assessment (MECA) payload on the Mars Surveyor Program 2001 Lander. Sponsored by the Human Exploration and Development of Space (HEDS) enterprise, MECA's primary goal is to evaluate potential geochemical and environmental hazards that may confront future martian explorers, and to guide HEDS scientists in the development of high fidelity Mars soil simulants. As a survey of soil properties, the MECA data set will also be rich in information relevant to basic geology, paleoclimate, and exobiology. The integrated MECA payload contains a wet-chemistry laboratory, a microscopy station, an electrometer to characterize the electrostatics of the soil and its environment, and arrays of material patches to study the abrasive and adhesive properties of soil grains. MECA is allocated a mass of 10 kg and a peak power usage of 15 W within an enclosure of 35 x 25 x 15 cm. The Wet Chemistry Laboratory (WCL) consists of four identical cells that will accept samples from surface and subsurface regions accessible to the Lander's robotic arm, mix them with water, and perform extensive analysis of the solution. Ion-selective electrodes and related sensors will evaluate total dissolved solids, redox potential, pH, and the concentration of many soluble ions and gases. Cyclic voltammetry will address oxidants, and anodic stripping voltammetry will probe potentially hazardous trace metals. MECA's microscopy station combines optical and atomic-force microscopy (AFM) in a controlled illumination environment to image dust and soil particles from millimeters to nanometers in size. Careful selection of substrates and an abrasion tool allows experimental study of size distribution, adhesion, abrasion, hardness, color, shape, aggregation, magnetic and other properties. Mounted on the end of the robot arm, MECA's electrometer consists of four types of sensors: an electric field meter, several triboelectricity monitors, an ion gauge, and a thermometer. Tempered only by ultra-violet- light-induced ions and a low-voltage break-down threshold, the dry, cold, dusty martian environment presents an imposing electrostatic hazard to both robots and humans. In addition, the electrostatic environment is key to transport of dust and, consequently, martian meteorology. MECA will also observe natural dust accumulation on engineering materials. Viewed with the robot arm camera, the abrasion and adhesion plates are strategically placed to allow direct observation of the inter-action between materials and soils on a macroscopic scale. Materials of graded hardness are placed directly under the robot arm scoop to sense wear and soil hardness. A second array, placed on the lander deck, is deployed after the dust plume of landing has settled. It can be manipulated in a primitive fashion by the arm, first having dirt deposited on it from the scoop and subsequently shaken clean. Dust accumulation as a function of conductivity, magnetic field strength, and other parameters will be explored. The MECA instruments described above will assess potential hazards that the Martian soil might present to human explorers and their equipment. In addition, MECA will provide information on the composition of ancient surface water environments, observing microscopic evidence of geological (and biological?) processes, inferring soil and dust transport, comminution and weathering mechanisms, and characterizing soil horizons that might be encountered during excavation. Additional information is contained in the original extended abstract.

Hecht, M. H.↗

Mixed Conducting Electrodes for Better AMTEC Cells

Electrode materials that exhibit mixed conductivity (that is, both electronic and ionic conductivity) have been investigated in a continuing effort to improve the performance of the alkali metal thermal-to-electric converter (AMTEC). These electrode materials are intended primarily for use on the cathode side of the sodium-ion-conducting solid electrolyte of a sodium-based AMTEC cell. They may also prove useful in sodium-sulfur batteries, which are under study for use in electric vehicles. An understanding of the roles played by the two types of conduction in the cathode of a sodium-based AMTEC cell is prerequisite to understanding the advantages afforded by these materials. In a sodium-based AMTEC cell, the anode face of an anode/solid-electrolyte/cathode sandwich is exposed to Na vapor at a suitable pressure. Upon making contact with the solid electrolyte on the anode side, Na atoms oxidize to form Na+ ions and electrons. Na+ ions then travel through the electrolyte to the cathode. Na+ ions leave the electrolyte at the cathode/electrolyte interface and are reduced by electrons that have been conducted through an external electrical load from the anode to the cathode. Once the Na+ ions have been reduced to Na atoms, they travel through the cathode to vaporize into a volume where the Na vapor pressure is much lower than it is on the anode side. Thus, the cathode design is subject to competing requirements to be thin enough to allow transport of sodium to the low-pressure side, yet thick enough to afford adequate electronic conductivity. The concept underlying the development of the present mixed conducting electrode materials is the following: The constraint on the thickness of the cathode can be eased by incorporating Na+ -ionconducting material to facilitate transport of sodium through the cathode in ionic form. At the same time, by virtue of the electronically conducting material mixed with the ionically conducting material, reduction of Na+ ions to Na atoms can take place throughout the thickness of the cathode. The net effect is to reduce the diffusion and flow resistance to sodium through the electrode while reducing the electronic resistance by providing shorter conduction paths for electrons. Reduced resistance to both sodium transport and electronic conductivity results in an increase in electric power output.

Ryan, Margaret↗

Space Electrochemical Research and Technology

Individual papers presented at the conference address the following topics: development of a micro-fiber nickel electrode for nickel-hydrogen cell, high performance nickel electrodes for space power application, bending properties of nickel electrodes for nickel-hydrogen batteries, effect of KOH concentration and anions on the performance of a Ni-H2 battery positive plate, advanced dependent pressure vessel nickel hydrogen spacecraft cell and battery design, electrolyte management considerations in modern nickel hydrogen and nickel cadmium cell and battery design, a novel unitized regenerative proton exchange membrane fuel cell, fuel cell systems for first lunar outpost - reactant storage options, the TMI regenerable solid oxide fuel cell, engineering development program of a closed aluminum-oxygen semi-cell system for an unmanned underwater vehicle, SPE OBOGS on-board oxygen generating system, hermetically sealed aluminum electrolytic capacitor, sol-gel technology and advanced electrochemical energy storage materials, development of electrochemical supercapacitors for EMA applications, and high energy density electrolytic capacitor.

Richard M Wilson↗

Factors Limiting Li+ Charge Transfer Kinetics in Li-ion Batteries

Understanding the factors limiting Li+ charge transfer kinetics in Li-ion batteries is essential in improving the rate performance, especially at lower temperatures. The Li+ charge transfer process involved in the lithium intercalation of graphite anode includes the step of de-solvation of the solvated Li+ in the liquid electrolyte and the step of transport of Li+ in the preformed solid electrolyte interphase (SEI) on electrodes until the Li+ accepts an electron at the electrode and becomes a Li in the electrode. Whether the de-solvation process or the Li+ transport through the SEI is a limiting step depends on the nature of the interphases at the electrode and electrolyte interfaces. Several examples involving the electrode materials such as graphite, lithium titanate (LTO), lithium iron phosphate (LFP), lithium nickel cobalt aluminum oxide (NCA) and solid Li+ conductor such as lithium lanthanum titanate or Li-Al-Ti-phosphate are reviewed and discussed to clarify the conditions at which either the de-solvation or the transport of Li+ in SEI is dominating and how the electrolyte components affect the activation energy of Li+ charge transfer kinetics. How the electrolyte additives impact the Li+ charge transfer kinetics at both the anode and the cathode has been examined at the same time in 3-electrode full cells. The resulting impact on Li+ charge transfer resistance, Rct, and activation energy, Ea, at both electrodes are reported and discussed.

Delp, Samuel A.↗

Fabrication of advanced electrochemical energy materials using sol-gel processing techniques

Advanced materials play an important role in electrochemical energy devices such as batteries, fuel cells, and electrochemical capacitors. They are being used as both electrodes and electrolytes. Sol-gel processing is a versatile solution technique used in fabrication of ceramic materials with tailored stoichiometry, microstructure, and properties. The application of sol-gel processing in the fabrication of advanced electrochemical energy materials will be presented. The potentials of sol-gel derived materials for electrochemical energy applications will be discussed along with some examples of successful applications. Sol-gel derived metal oxide electrode materials such as V2O5 cathodes have been demonstrated in solid-slate thin film batteries; solid electrolytes materials such as beta-alumina for advanced secondary batteries had been prepared by the sol-gel technique long time ago; and high surface area transition metal compounds for capacitive energy storage applications can also be synthesized with this method.

Chu, C. T.↗

Some studies on a solid state sulfur probe for coal gasification systems

Measurements on the solid electrolyte cell (Ar + H(2) + H(2)S/CaS + CaF(2) + (Pt)//CaF(2)//(Pt) + CaF(2) + CaS/H(2) + H(2)+Ar) show that the emf of the cell is directly related to the difference in sulfur potentials established at the Ar + H(2) + H(2)S/electrode interfaces. The electrodes convert the sulfur potential gradient across the calcium fluoride electrolyte into an equivalent fluorine potential gradient. Response time of the probe varies from approximately 9 hr at 990 K to 2.5 hr at 1225 K. The conversion of calcium sulfide and/or calcium fluoride into calcium oxide is not a problem anticipated in commercial coal gasification systems. Suggestions are presented for improving the cell for such commercial applications.

Jacob, K. T.↗

Novel Materials, Processing and Device Technologies for Space Exploration with Potential Dual-Use Applications

We highlight results of a broad spectrum of efforts on lower-temperature processing of nanomaterials, novel approaches to energy conversion, and environmentally rugged devices. Solution-processed quantum dots of copper indium chalcogenide semiconductors and multiwalled carbon nanotubes from lower-temperature spray pyrolysis are enabled by novel (precursor) chemistry. Metal-doped zinc oxide (ZnO) nanostructured components of photovoltaic cells have been grown in solution at low temperature on a conductive indium tin oxide substrate. Arrays of ZnO nanorods can be templated and decorated with various semiconductor and metallic nanoparticles. Utilizing ZnO in a more broadly defined energy conversion sense as photocatalysts, unwanted organic waste materials can potentially be repurposed. Current efforts on charge carrier dynamics in nanoscale electrode architectures used in photoelectrochemical cells for generating solar electricity and fuels are described. The objective is to develop oxide nanowire-based electrode architectures that exhibit improved charge separation, charge collection and allow for efficient light absorption. Investigation of the charge carrier transport and recombination properties of the electrodes will aid in the understanding of how nanowire architectures improve performance of electrodes for dye-sensitized solar cells. Nanomaterials can be incorporated in a number of advanced higher-performance (i.e. mass specific power) photovoltaic arrays. Advanced technologies for the deposition of 4H-silicon carbide are described. The use of novel precursors, advanced processing, and process studies, including modeling are discussed from the perspective of enhancing the performance of this promising material for enabling technologies such as solar electric propulsion. Potential impact(s) of these technologies for a variety of aerospace applications are highlighted throughout. Finally, examples are given of technologies with potential spin-offs for dual-use or terrestrial applications.

solid state devices↗

Electrochemical cell for obtaining oxygen from carbon dioxide atmospheres

For manned missions to Mars to become a reality, an efficient and reliable means of obtaining oxygen from the carbon dioxide-rich atmosphere will be required. Otherwise, the high cost of transporting the oxygen needed to sustain the astronauts will severely restrict the expedition to the martian surface. Recently, the use of electrochemical devices has been explored as a means of obtaining oxygen from the carbon dioxide-rich atmosphere. In these devices, oxygen ions diffuse through solid oxide membranes, thus, separating oxygen from the other gases presented. This phenomenon has only recently been explored as a means of obtaining large quantities of oxygen from toxic atmospheres, although first observed by Walter nernst in 1899. Nernst observed that stabilized zirconia will conduct oxygen ions when an electrical potential is applied across metallic electrodes applied to the ceramic membrane. Diatomic oxygen molecules are dissociated at the positive electrode/electrolyte interface. The oxygen ions enter the ceramic body due to the ion density gradient which is produced by the electrical potential across the electrolytic membrane. Once the ions have diffused through the membrane, they reform diatomic oxygen molecules at the anode. The separation of oxygen from carbon dioxide is achieved by the combination of thermal and electrochemical processes. The thermal decomposition of carbon dioxide (at 1000 C) results in the production of carbon monoxide and oxygen by the reaction.

Hooker, M. W.↗

The MSP 2001 Mars Environmental Compatibility Assessment (MECA)

The Mars Environmental Compatibility Assessment (MECA) will evaluate the Martian environment for soil and dust-related hazards to human exploration as part of the Mars Surveyor Program 2001 Lander. Sponsored by the Human Exploration and Development of Space (HEDS) enterprise, MECA's goal is to evaluate potential geochemical and environmental hazards that may confront future Martian explorers, and to guide HEDS scientists in the development of high fidelity Mars soil simulants. The integrated MECA payload contains a wet-chemistry laboratory, a microscopy station, an electrometer to characterize the electrostatics of the soil and its environment, and arrays of material patches to study the abrasive and adhesive properties of soil grains. The instrument will acquire soil samples with a robotic arm equipped with a camera. MECA will examine surface and subsurface soil and dust in order to characterize particle size, shape, hardness, and also physical characteristics that may provide clues to mineralogy. MECA will characterize soil/water mixtures with respect to pH, redox potential, total dissolved ions, and trace toxins. MECA will determine the nature of electrostatic charging associated with excavation of soil, and the influence of ionizing radiation on material properties. It will also observe natural dust accumulation on engineering materials. To accomplish these objectives, MECA is allocated a mass of 10 kg within an enclosure of 35 x 25 x 15 cm. The Wet Chemistry Laboratory (WCL) consists of four identical cells that will accept samples from surface and subsurface regions accessible to the Lander's robotic arm, mix them with water, and perform extensive analysis of the solution. Ion-selective electrodes and related sensors will evaluate total dissolved solids, redox potential, pH, and the concentration of many soluble ions and gases in wet Martian soil. These electrodes can detect potentially dangerous heavy-metal ions, emitted pathogenic gases, and the soil's corrosive potential. Experiments will include cyclic voltammetry and anodic stripping voltammetry. Complementary to the Viking experiments, the chemical laboratory will characterize the water-soil solution rather than emitted gases. Nonetheless, through analysis of dissolved gases it will be able to replicate many of the Viking observations related to oxidants. MECA's microscopy station combines optical and atomic-force microscopy (AFM) in an actively focused, controlled illumination environment to image particles from millimeters to nanometers in size. Careful selection of substrates allows controlled experiments in adhesion, abrasion, hardness, aggregation, magnetic and other properties. Special tools allow primitive manipulation (brushing and scraping) of samples. Soil particle properties including size, shape, color, hardness, adhesive potential (electrostatic and magnetic), will be determined using an array of sample receptacles and collection substrates. The simple, rugged atomic-force microscope will image in the submicron size range and has the capability of performing a particle-by-particle analysis of the dust and soil. On Earth, the earliest forms of life are preserved as microfossils. The atomic-force microscope will have the required resolution to image down to the scale of terrestrial microfossils and beyond. Mounted on the end of the robot arm, MECA's electrometer actually consists of four types of sensors: an electric field meter, several triboelectricity monitors, an ion gauge, and a thermometer. Tempered only by ultraviolet-light-induced ions and a low-voltage breakdown threshold, the dry, cold, dusty martian environment presents an imposing electrostatic hazard to both robots and humans. The field meter will measure the ambient field on nearby objects while the triboelectric sensors, using identical circuitry, will measure the charge accumulated on test substances as they are dragged through the soil by the arm. The ion chamber, open to the environment, will sense both charged dust and free ions in the air. Over and above the potential threat to electronics, the electrostatic environment holds one of the keys to transport of dust and, consequently, Martian meteorology. Viewed with the robot arm camera, the abrasion and adhesion plates are strategically placed to allow direct observation of the interaction between materials and soils on a macroscopic scale. Materials of graded hardness are placed directly under the robot arm scoop to sense wear and soil hardness. A second array, placed on the lander deck, is deployed after the dust plume of landing has settled. It can be manipulated in a primitive fashion by the arm, first having dirt deposited on it from the scoop and subsequently shaken clean. A third array will passively collect dust from the atmosphere. In addition to objectives related to human exploration, the MECA data set will be rich in information relevant to basic geology, paleoclimate, and exobiology issues. To understand both contemporaneous and ancient processes on Mars, the mineralogy, petrology, and reactivity of Martian surface materials should be constrained. The MECA experiment will shed light on these quantities through its combination of chemistry and microscopy. MECA will be capable of measuring the composition of ancient surface water environments, observing microscopic evidence of geological (and biological?) processes, inferring soil and dust transport, comminution and weathering mechanisms, and characterizing soil horizons that might be encountered during excavation.

Hecht, M. H.↗

A Symmetrical, Planar SOFC Design for NASA's High Specific Power Density Requirements

Solid oxide fuel cell (SOFC) systems for aircraft applications require an order of magnitude increase in specific power density (1.0 kW/kg) and long life. While significant research is underway to develop anode supported cells which operate at temperatures in the range of 650-800 C, concerns about Cr-contamination from the metal interconnect may drive the operating temperature down further, to 750 C and lower. Higher temperatures, 900-1000 C, are more favorable for SOFC stacks to achieve specific power densities of 1.0 kW/kg. Since metal interconnects are not practical at these high temperatures and can account for up to 75% of the weight of the stack, NASA is pursuing a design that uses a thin, LaCrO3-based ceramic interconnect that incorporates gas channels into the electrodes. The bi-electrode supported cell (BSC) uses porous YSZ scaffolds, on either side of a 10-20 microns electrolyte. The porous support regions are fabricated with graded porosity using the freeze-tape casting process which can be tailored for fuel and air flow. Removing gas channels from the interconnect simplifies the stack design and allows the ceramic interconnect to be kept thin, on the order of 50 -100 microns. The YSZ electrode scaffolds are infiltrated with active electrode materials following the high temperature sintering step. The NASA-BSC is symmetrical and CTE matched, providing balanced stresses and favorable mechanical properties for vibration and thermal cycling.

Cable, Thomas L.↗

Li-Ion Batteries for Space Applications: High Specific Energy and Wide-Operating Temperature

Compared to the conventional Ni-Co oxides (with or without AI additions), the NMC (1/3:1/3:1/3) cathode provides marginal improvement in specific capacity. However, some of the formulations based on the solid solutions of layered Li2Mn03 and LiM02 (M = Mn0.5Ni0.5} have shown capacities as high as 250 mAh/g, combined with high cell voltages (4.5 V) and with the likelihood of enhanced thermal stability. Multi-component electrolytes with low EC-proportions and selected co-solvents provide significant improvement in the low temperature performance, down to -60 C, combined with the non-flammable attribute from the co-solvents. The NMC cathode shows good compatibility with the carbonate-based low temperature electrolytes. Impressive performances have been realized at low temperatures of <= 30 C. Electrolytes with high salt concentration and high EC content fare well at room temperatures, while the formulations with low EC content and low salt concentration are preferred at low temperatures. DPA studies reveal increased SEI growth on the electrodes, especially anode, upon irradiation. Performance of low temperature electrolytes in prototype cells corroborate the findings from laboratory cells.

storage↗

Assessment of Lithium-based Battery Electrolytes Developed under the NASA PERS Program

Recently, NASA formally completed the Polymer Energy Rechargeable System (PERS) Program, which was established in 2000 in collaboration with the Air Force Research Laboratory (AFRL) to support the development of polymer-based, lithium-based cell chemistries and battery technologies to address the next generation of aerospace applications and mission needs. The goal of this program was to ultimately develop an advanced, space-qualified battery technology, which embodied a solid polymer electrolyte (SPE) and complementary components, with improved performance characteristics that would address future aerospace battery requirements. Programmatically, the PERS initiative exploited both interagency collaborations to address common technology and engineering issues and the active participation of academia and private industry. The initial program phases focused on R&D activities to address the critical technical issues and challenges at the cell level. A variety of cell and polymeric electrolyte concepts were pursued as part of the development efforts undertaken at numerous governmental, industrial and academic laboratories. Numerous candidate electrolyte materials were developed, synthesized and optimized for evaluation. Utilizing the component screening facility and the "standardized" test procedures developed at the NASA Glenn Research Center, electrochemical screening and performance evaluations of promising candidate materials were completed. This overview summarizes test results for a variety of candidate electrolyte materials that were developed under the PERS Program. Electrolyte properties are contrasted and compared to the original project goals, and the strengths and weaknesses of the electrolyte chemistries are discussed. Limited cycling data for full-cells using lithium metal and vanadium oxide electrodes are also presented. Based on measured electrolyte properties, the projected performance characteristics and temperature limitations of batteries utilizing the advanced electrolytes and components have been estimated. Limitations for the achievement of practical performance levels are also discussed, as well as needs for future research and development.

Bennett, William R.↗

Electrocatalysts for oxygen electrodes in fuel cells and water electrolyzers for space applications

In most instances separate electrocatalysts are needed to promote the reduction of O2 in the fuel cell mode and to generate O2 in the energy storage-water electrolysis mode in aqueous electrochemical systems operating at low and moderate temperatures (T greater than or equal to 200 C). Interesting exceptions are the lead and bismuth ruthenate pyrochlores in alkaline electrolytes. These catalysts on high area carbon supports have high catalytic activity for both O2 reduction and generation (1,2). Rotating ring-disk electrode measurements provide evidence that the O2 reduction proceeds by a parallel four-electron pathway. The ruthenates can also be used as self-supported catalysts to avoid the problems associated with carbon oxidation, but the electrode performance so far achieved in the research at Case Western Reserve University (CWRU) is considerably less. At the potentials involved in the anodic mode the ruthenate pyrochlores have substantial equilibrium solubility in concentrated alkaline electrolyte. This results in the loss of catalyst into the bulk solution and a decline in catalytic activity. Furthermore, the hydrogen generation counter electrode may become contaminated with reduction products from the pyrochlores (lead, ruthenium). A possible approach to this problem is to immobilize the pyrochlore catalyst within an ionic-conducting solid polymer, which would replace the fluid electrolyte within the porous gas diffusion O2 electrode. For bulk alkaline electrolyte, an anion-exchange polymer is needed with a transference number close to unity for the Oh(-) ion. Preliminary short-term measurements with lead ruthenates using a commercially available partially-fluorinated anion-exchange membrane as an overlayer on the porous gas-fed electrode indicate lower anodic polarization and virtually unchanged cathodic polarization.

Prakash, Jai↗

Thermocapillary Flow and Aggregation of Bubbles on a Solid Wall

During the electrolytic evolution of oxygen bubbles forming on a vertically oriented transparent tin oxide electrode, bubbles were found to be mutually attractive. The mechanism of the aggregation had never been explained satisfactorily until Guelcher et al. attributed it to thermocapillary flow. The gradient of surface tension of the liquid at the bubble's surface, which was established because of reaction heat and ohmic heat loss at the electrode wall, drives flow of the liquid adjacent to each bubble; the bubble "pumps" fluid along its surface away from the wall. Fluid flows toward the bubble to conserve mass and entrains nearby bubbles in the flow pattern. The same logic would apply when two bubbles of equal size are adjacent to each other on a warm wall. Each bubble drives thermocapillary flow and hence entrains the other in its flow pattern, which drives the aggregation. Our objective here is to perform experiments where the temperature gradient at the wall is well known and controlled. The theory can be quantitatively tested by studying aggregation of bubble pairs of equal size, and by varying system parameters such as temperature gradient, bubble size and fluid viscosity. The results are then compared with the theory in a quantitatively rigorous manner. We demonstrate that the theory without adjustable parameters is capable of quantitatively modeling the rate of aggregation of two bubbles. The equations governing the thermocapillary flow around a single stationary bubble on a heated or cooled wall in a semi-infinite domain were solved. Both Reynolds number and Marangoni number were much less than unity. The critical result is that liquid in the vicinity of a warm wall flows toward a stationary collector bubble. Consequently the thermocapillary flow around the stationary bubble entrains another bubble toward itself. The bubbles undergo hindered translation parallel to the wall with velocity U while the fluid flow field is described with u. Two velocities were equated by using a wall hindrance parameter q: U = qu [1] which shows the velocity of bubble is proportional to the entraining velocity. The hindrance parameter q can experimentally be measured independently. q can also be calculated by solving the equations of motion for a bubble translating parallel to a solid wall. The experimental cell is cylindrical with an ID of 10 cm and consists of a 1 cm deep main cell filled with silicone oil and flanked by two thermal reservoirs. The upper thermal reservoir was heated and the lower thermal reservoir was cooled so that the bubbles aggregate. Two types of silicone oil (eta = 0.02 and 0.50 Pa s) were used. Two equal sized air bubbles were injected into the cell with a syringe. The center-to-center distance of bubbles was observed through a microscope. Bubble radius ranged from 0.40 mm to 0.65 mm and the temperature gradients along with the cell ranged from 1400 to 5000 K/m. The bubbles aggregated when heat flows from the wall to the fluid. The velocities of bubbles were in the range of 1 - 10 microns/s. The separation r decreased more quickly when the temperature gradient was higher, bubble size was larger, and the oil viscosity was lower. r decreased more rapidly as the bubbles approached each other. Dimensionless time was arbitrarily set to be zero when the dimensionless center-to-center distance between the bubbles was 4. All the bubble trajectories fall onto one line, especially in the range of dimensionless distance from 4 to 3. This means the relative movement of the bubble pair is proportional to the temperature gradient and bubble size and it is inversely proportional to the viscosity of the oil. This result strongly suggests that the thermocapillary flow-based aggregation mechanism is correct. A value of q can be estimated by fitting the scaled data to Eq. [1]. A best fit value of q was obtained as q = 0.26 with a standard deviation of 0.03. Independent experimental results for q for a 0.5 mm radius bubble, give values of q in the range 0.11 to 0.23. The value of q obtained from solving the equations of motion reveals q has values in the range 0.23 - 0.30. Since the full scale of possible values of q is zero to one, the maximum deviation of independently determined values of q from the best fit value was 15% of this full scale. Thus reasonable quantitative agreement between theory and experiment has been obtained.

Kasumi, Hiroki↗