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All sourcesNASA NTRSDOE OSTI
NASA NTRS2014

Determining the Source of Water Vapor in a Cerium Oxide Electrochemical Oxygen Separator to Achieve Aviator Grade Oxygen

More than a metric ton of water is transported to the International Space Station (ISS) each year to provide breathing oxygen for the astronauts. Water is a safe and compact form of stored oxygen. The water is electrolyzed on ISS and ambient pressure oxygen is delivered to the cabin. A much smaller amount of oxygen is used each year in spacesuits to conduct Extra Vehicular Activities (EVAs). Space suits need high pressure (>1000 psia) high purity oxygen (must meet Aviator Breathing Oxygen "ABO" specifications, >99.5% O2). The water / water electrolysis system cannot directly provide high pressure, high purity oxygen, so oxygen for EVAs is transported to ISS in high pressure gas tanks. The tanks are relatively large and heavy, and the majority of the system launch weight is for the tanks and not the oxygen. Extracting high purity oxygen from cabin air and mechanically compressing the oxygen might enable on-board production of EVA grade oxygen using the existing water / water electrolysis system. This capability might also benefit human spaceflight missions, where oxygen for EVAs could be stored in the form of water, and converted into high pressure oxygen on-demand. Cerium oxide solid electrolyte-based ion transport membranes have been shown to separate oxygen from air, and a supported monolithic wafer form of the CeO2 electrolyte membrane has been shown to deliver oxygen at pressures greater than 300 psia. These supported monolithic wafers can withstand high pressure differentials even though the membrane is very thin, because the ion transport membrane is supported on both sides (Fig 1). The monolithic supported wafers have six distinct layers, each with matched coefficients of thermal expansion. The wafers are assembled into a cell stack which allows easy air flow across the wafers, uniform current distribution, and uniform current density (Fig 2). The oxygen separation is reported to be "infinitely selective" to oxygen [1] with reported purity of 99.99% [2]. Combined with a mechanical compressor, a Solid Electrolyte Oxygen Separator (SEOS) should be capable of producing ABO grade oxygen at pressures >2400 psia, on the space station. Feasibility tests using a SEOS integrated with a mechanical compressor identified an unexpected contaminant in the oxygen: water vapour was found in the oxygen product, sometimes at concentrations higher than 40 ppm (the ABO limit for water vapour is 7 ppm). If solid electrolyte membranes are really "infinitely selective" to oxygen as they are reported to be, where did the water come from? If water is getting into the oxygen, what other contaminants might get into the oxygen? Microscopic analyses of wafers, welds, and oxygen delivery tubes were performed in an attempt to find the source of the water vapour contamination. Hot and cold pressure decay tests were performed. Measurements of water vapour as a function of O2 delivery rate, O2 delivery pressure, and process air humidity levels were the most instructive in finding the source of water contamination (Fig 3). Water contamination was directly affected by oxygen delivery rate (doubling the oxygen production rate cut the water level in half). Water was affected by process air humidity levels and delivery pressure in a way that indicates the water was diffusing into the oxygen delivery system.

Graf, John↗
NASA NTRS1993

Composite Solid Electrolyte for Li Battery Applications

The electrochemical, bulk and interfacial properties of the polyethylene oxide (PEO) based composite solid electrolyte (CSE) comprising LiI, PEO, and Al2O3 have been evaluated for Li battery applications. The bulk interfacial and transport properties of the CSEs seem to strongly depend on the alumina particle size. For the CSE films with 0.05 micron alumina while the bulk conductivity is around 10(exp -4) (mho/cm) at 103 C, the Li ion transport number seems to be close to unity at the same temperature. Compared to the PEO electrolyte this polymer composite electrolyte seems to exhibit robust mechanical and interfacial properties. We have studied three different films with three different alumina sizes in the range 0.01-0.3 micron. Effects of Al2O3 particle size on the electrochemical performance of polymer composite electrolyte is discussed. With TiS2 as cathode a 10 mAh small capacity cell was charged and discharged at C/40 and C/20 rates respectively.

Nagasubramanian, G.↗
NASA NTRS2003

Creep Resistance of ZrO2 Ceramic Improved by the Addition of a Small Amount of Er2O3

Zirconia (ZrO2) has great technological importance in structural, electrical, and chemical applications. It is the crucial component for state-of-the art thermal barrier coatings and an enabling component as a solid electrolyte for solid-oxide fuel cell systems. Pure ZrO2 is of limited use for industrial applications because of the phase transformations that occur. Upon the addition of stabilizers, cubic (c-ZrO2) and tetragonal (t-ZrO2) forms can be preserved. It is the stabilized and partially stabilized forms of zirconia that function as thermal barrier coatings, solid electrolytes, and oxygen sensors and that have numerous applications in the electrochemical industry. The cubic form of ZrO2 is typically stabilized through Y2O3 additions. However, Y2O3-stabilized zirconia is susceptible to deformation at high temperatures (greater than 900 C) because of the large number of slip systems and the high oxygen diffusion rates, which result in high creep rates at high temperatures. Successful use of ZrO2 at high temperatures requires that new dopant additives be found that will retain or enhance the desirable properties of cubic ZrO2 and yet produce a material with lower creep rates. At the NASA Glenn Research Center, erbium oxide (Er2O3) was identified as a promising dopant for improving the creep resistance of. ZrO2. The selection of Er2O3 was based on the strong interactions of point defects and dislocations. Single crystals of 5 mol% Er2O3- doped ZrO2 rods (4 mm in diameter) and monofilaments (200 to 300 mm in diameter and 30 cm long) were grown using the laser-heated float zone technique, and their creep behavior was measured as a function of temperature. The addition of 5 mol% Er2O3 to single-crystal ZrO2 improved its creep resistance at high temperatures by 2 to 3 orders of magnitude over state-of-the-art Y2O3-doped crystals. Detailed microstructural characterization of ZrO2-Er2O3 single crystals has identified new mechanisms for improving the creep resistance of this class of materials. Adding Er2O3 to ZrO2 results in microstructure of stable and metastable tetragonal precipitates that with thermal treatment evolve to a tweed structure of nanosize tetragonal lamellae. The superior high-temperature creep resistance of Er2O3-doped ZrO2 is attributed to nanoscale precipitation hardening. Doping with Er2O3 will significantly increase the upper-use temperature limit of ZrO2. Potential applications include using Er2O3-doped ZrO2 as a high-temperature fiber for structural applications and adding Er2O3 to reduce the sintering rates of ZrO2 thermal barrier coatings. This work was conducted at Dpto. de F sica de la Materia Condensada, Universidad de Sevilla, Spain, and at NASA Glenn.

Martinez-Fernandez, Julian↗
NASA NTRS1992

Secondary Li battery incorporating 12-Crown-4 ether

A rechargeable lithium battery which utilizes a polyethylene oxide (PEO) solid polymeric electrolyte complexed with a lithium salt is disclosed. The conductivity is increased an order of magnitude and interfacial charge transfer resistance is substantially decreased by incorporating a minor amount of 12-Crown-4 ether in the PEO-lithium salt solid electrolyte film. Batteries containing the improved electrolyte permit operation at a lower temperature with improved efficiency.

Nagasubramanian, Ganesan↗
NASA NTRS2002

Processing and Mechanical Properties of Various Zirconia/Alumina Composites for Fuel Cell Applications

Various electrolyte materials for solid oxide fuel cells were fabricated by hot pressing 10 mol% yttria-stabilized zirconia (10-YSZ) reinforced with two different forms of alumina, particulates and platelets, each containing 0 to 30 mol% alumina. Flexure strength and fracture toughness of both particulate and platelet composites at ambient temperature increased with increasing alumina content, reaching a maximum at 30 mot% alumina. For a given alumina content, strength of particulate composites was greater than that of platelet composites, whereas, the difference in fracture toughness between the two composite systems was negligible. No virtual difference in elastic modulus and density was observed for a given alumina content between particulate and platelet composites. Thermal cycling up to 10 cycles between 200 to 1000 C did not show any effect on strength degradation of the 30 mol% platelet composites, indicative of negligible influence of CTE mismatches between YSZ matrix and alumina grains.

Choi, Sung R.↗
NASA NTRS2003

Strength, Fracture Toughness, and Slow Crack Growth of Zirconia/alumina Composites at Elevated Temperature

Various electrolyte materials for solid oxide fuel cells were fabricated by hot pressing 10 mol% yttria-stabilized zirconia (10-YSZ) reinforced with two different forms of alumina particulates and platelets each containing 0 to 30 mol% alumina. Flexure strength and fracture toughness of platelet composites were determined as a function of alumina content at 1000 C in air and compared with those of particulate composites determined previously. In general, elevated-temperature strength and fracture toughness of both composite systems increased with increasing alumina content. For a given alumina content, flexure strength of particulate composites was greater than that of platelet composites at higher alumina contents (greater than or equal to 20 mol%), whereas, fracture toughness was greater in platelet composites than in particulate composites, regardless of alumina content. The results of slow crack growth (SCG) testing, determined at 1000 C via dynamic fatigue testing for three different composites including 0 mol% (10-YSZ matrix), 30 mol % particulate and 30 mol% platelet composites, showed that susceptibility to SCG was greatest with SCG parameter n = 6 to 8 for both 0 and 30 mol% particulate composites and was least with n = 33 for the 30 mol% platelet composite.

Choi, Sung R.↗
NASA NTRS2003

Alumina-Reinforced Zirconia Composites

Alumina-reinforced zirconia composites, used as electrolyte materials for solid oxide fuel cells, were fabricated by hot pressing 10 mol percent yttria-stabilized zirconia (10-YSZ) reinforced with two different forms of alumina particulates and platelets each containing 0 to 30 mol percent alumina. Major mechanical and physical properties of both particulate and platelet composites including flexure strength, fracture toughness, slow crack growth, elastic modulus, density, Vickers microhardness, thermal conductivity, and microstructures were determined as a function of alumina content either at 25 C or at both 25 and 1000 C. Flexure strength and fracture toughness at 1000 C were maximized with 30 particulate and 30 mol percent platelet composites, respectively, while resistance to slow crack growth at 1000 C in air was greater for 30 mol percent platelet composite than for 30 mol percent particulate composites.

Choi, Sung R.↗
NASA NTRS1992

Polymeric Electrolyte Containing 12-Crown-4 Ether

Experiments show incorporation of 12-crown-4 ether into solid electrolytes based on polyethylene oxide enhances their electrochemical properties. More specifically, 12-crown-4 ether increases Faradaic efficiency for Li+ ions in low-power secondary Li cells and enables operation of these cells at lower temperatures with higher efficiencies.

Nagasubramanian, Ganesa↗
NASA NTRS2004

NASA Tech Briefs, February 2004

Topics include: Simulation Testing of Embedded Flight Software; Improved Indentation Test for Measuring Nonlinear Elasticity; Ultraviolet-Absorption Spectroscopic Biofilm Monitor; Electronic Tongue for Quantitation of Contaminants in Water; Radar for Measuring Soil Moisture Under Vegetation; Modular Wireless Data-Acquisition and Control System; Microwave System for Detecting Ice on Aircraft; Routing Algorithm Exploits Spatial Relations; Two-Finger EKG Method of Detecting Evasive Responses; Updated System-Availability and Resource-Allocation Program; Routines for Computing Pressure Drops in Venturis; Software for Fault-Tolerant Matrix Multiplication; Reproducible Growth of High-Quality Cubic-SiC Layers; Nonlinear Thermoelastic Model for SMAs and SMA Hybrid Composites; Liquid-Crystal Thermosets, a New Generation of High-Performance Liquid-Crystal Polymers; Formulations for Stronger Solid Oxide Fuel-Cell Electrolytes; Simulation of Hazards and Poses for a Rocker-Bogie Rover; Autonomous Formation Flight; Expandable Purge Chambers Would Protect Cryogenic Fittings; Wavy-Planform Helicopter Blades Make Less Noise; Miniature Robotic Spacecraft for Inspecting Other Spacecraft; Miniature Ring-Shaped Peristaltic Pump; Compact Plasma Accelerator; Improved Electrohydraulic Linear Actuators; A Software Architecture for Semiautonomous Robot Control; Fabrication of Channels for Nanobiotechnological Devices; Improved Thin, Flexible Heat Pipes; Miniature Radioisotope Thermoelectric Power Cubes; Permanent Sequestration of Emitted Gases in the Form of Clathrate Hydrates; Electrochemical, H2O2-Boosted Catalytic Oxidation System; Electrokinetic In Situ Treatment of Metal-Contaminated Soil; Pumping Liquid Oxygen by Use of Pulsed Magnetic Fields; Magnetocaloric Pumping of Liquid Oxygen; Tailoring Ion-Thruster Grid Apertures for Greater Efficiency; and Lidar for Guidance of a Spacecraft or Exploratory Robot.

Source record↗
NASA NTRS1995

Superacid-Based Lithium Salts For Polymer Electrolytes

Solid polymer electrolytes exhibiting high lithium-ion conductivities made by incorporating salts of superacids into thin films of polyethylene oxide (PEO). These and other solid-polymer electrolytes candidates for use in rechargeable lithium-based electrochemical cells. Increases in room-temperature lithium-ion conductivities of solid electrolytes desirable because they increase achievable power and energy densities.

Nagasubramanian, Ganesan↗
NASA NTRS2015

Electrode Design for Low Temperature Direct-Hydrocarbon Solid Oxide Fuel Cells

In certain embodiments of the present disclosure, a solid oxide fuel cell is described. The solid oxide fuel cell includes a hierarchically porous cathode support having an impregnated cobaltite cathode deposited thereon, an electrolyte, and an anode support. The anode support includes hydrocarbon oxidation catalyst deposited thereon, wherein the cathode support, electrolyte, and anode support are joined together and wherein the solid oxide fuel cell operates a temperature of 600.degree. C. or less.

Chen, Fanglin↗
NASA NTRS2002

Novel Molecular Architectures Developed for Improved Solid Polymer Electrolytes for Lithium Polymer Batteries

Lithium-based polymer batteries for aerospace applications need the ability to operate in temperatures ranging from -70 to 70 C. Current state-of-the-art solid polymer electrolytes (based on amorphous polyethylene oxide, PEO) have acceptable ionic conductivities (10-4 to 10-3 S/cm) only above 60 C. Higher conductivity can be achieved in the current systems by adding solvent or plasticizers to the solid polymer to improve ion transport. However, this can compromise the dimensional and thermal stability of the electrolyte, as well as compatibility with electrode materials. One of NASA Glenn Research Center's objectives in the PERS program is to develop new electrolytes having unique molecular architectures and/or novel ion transport mechanisms, leading to good ionic conductivity at room temperature and below without solvents or plasticizers.

Meador, Mary Ann B.↗
NASA NTRS2009

Hydrogen Fuel System Design Trades for High-Altitude Long-Endurance Remotely- Operated Aircraft

Preliminary design trades are presented for liquid hydrogen fuel systems for remotely-operated, high-altitude aircraft that accommodate three different propulsion options: internal combustion engines, and electric motors powered by either polymer electrolyte membrane fuel cells or solid oxide fuel cells. Mission goal is sustained cruise at 60,000 ft altitude, with duration-aloft a key parameter. The subject aircraft specifies an engine power of 143 to 148 hp, gross liftoff weight of 9270 to 9450 lb, payload of 440 lb, and a hydrogen fuel capacity of 2650 to 2755 lb stored in two spherical tanks (8.5 ft inside diameter), each with a dry mass goal of 316 lb. Hydrogen schematics for all three propulsion options are provided. Each employs vacuum-jacketed tanks with multilayer insulation, augmented with a helium pressurant system, and using electric motor driven hydrogen pumps. The most significant schematic differences involve the heat exchangers and hydrogen reclamation equipment. Heat balances indicate that mission durations of 10 to 16 days appear achievable. The dry mass for the hydrogen system is estimated to be 1900 lb, including 645 lb for each tank. This tank mass is roughly twice that of the advanced tanks assumed in the initial conceptual vehicle. Control strategies are not addressed, nor are procedures for filling and draining the tanks.

Millis, Marc G.↗
NASA NTRS2006

Miniature Oxidizer Ionizer for a Fuel Cell

A proposed miniature device for ionizing the oxygen (or other oxidizing gas) in a fuel cell would consist mostly of a membrane ionizer using the same principles as those of the device described in the earlier article, Miniature Bipolar Electrostatic Ion Thruster (NPO-21057). The oxidizing gas would be completely ionized upon passage through the holes in the membrane ionizer. The resulting positively charged atoms or molecules of oxidizing gas could then, under the influence of the fringe fields of the ionizer, move toward the fuel-cell cathode that would be part of a membrane/electrode assembly comprising the cathode, a solid-electrolyte membrane, and an anode. The electro-oxidized state of the oxidizer atoms and molecules would enhance transfer of them through the cathode, thereby reducing the partial pressure of the oxidizer gas between the ionizer and the fuel-cell cathode, thereby, in turn, causing further inflow of oxidizer gas through the holes in the membrane ionizer. Optionally the ionizer could be maintained at a positive electric potential with respect to the cathode, in which case the resulting electric field would accelerate the ions toward the cathode.

Hartley, Frank↗
NASA NTRS1978

Long-lasting solid-polymer electrolytic hygrometer

Device consists of hollow tube node of oxidation-resistant sulfonated fluorocarbon polymer. Tube absorbs moisture from air passing across inner and outer surfaces, causing change in polymer conductance. Change is related to change in water content in gas sample.

Lawson, D. D.↗
NASA NTRS2003

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↗
NASA NTRS2017

Thermal Design for Extra-Terrestrial Regenerative Fuel Cell System

The Advanced Exploration Systems (AES) Advanced Modular Power Systems (AMPS) Project is investigating different power systems for various lunar and Martian mission concepts. The AMPS Fuel Cell (FC) team has created two system-level models to evaluate the performance of regenerative fuel cell (RFC) systems employing different fuel cell chemistries. Proton Exchange Membrane fuel cells PEMFCs contain a polymer electrolyte membrane that separates the hydrogen and oxygen cavities and conducts hydrogen cations (protons) across the cell. Solid Oxide fuel cells (SOFCs) operate at high temperatures, using a zirconia-based solid ceramic electrolyte to conduct oxygen anions across the cell. The purpose of the modeling effort is to down select one fuel cell chemistry for a more detailed design effort. Figures of merit include the system mass, volume, round trip efficiency, and electrolyzer charge power required. PEMFCs operate at around 60 C versus SOFCs which operate at temperatures greater than 700 C. Due to the drastically different operating temperatures of the two chemistries the thermal control systems (TCS) differ. The PEM TCS is less complex and is characterized by a single pump cooling loop that uses deionized water coolant and rejects heat generated by the system to the environment via a radiator. The solid oxide TCS has its own unique challenges including the requirement to reject high quality heat and to condense the steam produced in the reaction. This paper discusses the modeling of thermal control systems for an extraterrestrial RFC that utilizes either a PEM or solid oxide fuel cell.

thermal modeling↗