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NASA NTRS1981

Characterization of the physico-chemical properties of polymeric materials for aerospace flight

Electrodes and electrolytes of nickel cadmium sealed batteries were analyzed. Different thermal analysis of negative and positive battery electrodes was conducted and the temperature ranges of occurrence of endotherms indicating decomposition of cadmium hydroxide and nickel hydroxide are identified. Atomic absorption spectroscopy was used to analyze electrodes and electrolytes for traces of nickel, cadmium, cobalt, and potassium. Calibration curves and data are given for each sample analyzed. Instrumentation and analytical procedures used for each method are described.

Rock, M.↗

NASA NTRS2009

Room-Temperature Ionic Liquids for Electrochemical Capacitors

A document discusses room-temperature ionic liquids (RTILs) used as electrolytes in carbon-nanotube-based, electrochemical, double-layer capacitors. Unlike the previous electrolyte (EtNB4 in acetonitrile), the RTIL used here does not produce cyanide upon thermal decomposition and does not have a moisture sensitivity.

Fireman, Heather↗

NASA NTRS1985

Study of high performance alloy electroforming

The nickel-manganese experimental electrolyte was hydrogen peroxide treated and carbon purified for removal of residual sodium saccharin and related organic decomposition products from the plating of previous test panels. The saccharin additive was used to reduce stress where high concentrations of manganese and high pulse peak current densities were used. A large quantity of nickel-manganese alloy plates containing 0.35 to 0.40 percent by weight manganese was electroformed for testing to supply data for a mechanical property data table. The aluminum billet required for the machining of the subscale SSME main combustion chamber was acquired.

Malone, G. A.↗

NASA NTRS2011

Sol-Gel Synthesis of La(0.6)Sr(0.4)CoO(3-x) and Sm(0.5)Sr(0.5)CoO(3-x) Cathode Nanopowders for Solid Oxide Fuel Cells

Nanopowders of La(0.6)Sr(0.4)CoO(3-x) (LSC) and Sm(0.5)Sr(0.5)CoO(3-x) (SSC) compositions, which are being investigated as cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFC) with La(Sr)Ga(Mg)O(3-x) (LSGM) as the electrolyte, were synthesized by low-temperature sol-gel method using metal nitrates and citric acid. Thermal decomposition of the citrate gels was followed by simultaneous DSC/TGA methods. Development of phases in the gels, on heat treatments at various temperatures, was monitored by x-ray diffraction. Solgel powders calcined at 550 to 1000 C consisted of a number of phases. Single perovskite phase La(0.6)Sr(0.4)CoO(3-x) or Sm(0.5)Sr(0.5)CoO(3-x) powders were obtained at 1200 and 1300 C, respectively. Morphological analysis of the powders calcined at various temperatures was done by scanning electron microscopy. The average particle size of the powders was approx.15 nm after 700 C calcinations and slowly increased to 70 to 100 nm after heat treatments at 1300 to 1400 C.

Bansal, Narottam P.↗

NASA NTRS1976

Electrochemical performance investigations on the hydrogen depolarized CO2 concentrator

An extensive investigation of anode and cathode polarization in complete cells and half cells was conducted to determine the factors affecting HDC electrode polarization and the nature of this polarization. Matrix-electrolyte-electrode interactions and cell electrolyte composition were also investigated. The electrodes were found to have normal performance capabilities. The HDC anode polarization characteristics were correlated with a theoretical kinetic analysis; and, except for some quantitative details, a rather complete understanding of the causes for HDC electrode polarization was formulated. One of the important finding resulting from the kinetic analysis was that platinum appears to catalyze the decomposition of carbonic acid to carbon dioxide and water. It was concluded that the abnormal voltage performance of the One Man ARS HDC cells was caused by insufficient cell electrolyte volume under normal operating conditions due to deficiencies in the reservoir to cell interfacing.

Aylward, J. R.↗

NASA NTRS1981

Recent work in advanced hydrogen production concepts

The hydrogen photoelectrolytic conversion activity investigated the practicability of semiconductor electrolytic devises that use solar energy to decompose water into hydrogen and oxygen in an apparent single step process. The photocatalytic decomposition of inorganic hydrogen compounds; i.e., hydrobromic and hydriodic acids using rhodium organic bridge complexes were also studied. The feasibility of direct high temperature thermal decompositions of water with diffusion processes for separation of the equilibrium mixture of hydrogen and oxygen into usable energy sources was examined.

Lawson, D. D.↗

NASA NTRS1980

Characterization of the physico-chemical properties of polymeric materials for aerospace flight

Factors contributing to the final failure of Ni-Cd batteries are listed. A differential thermal analyzer was used to study several positive and negative battery electrodes. The negative plates show a very large peak (endotherm) between 245 C and 250C. The second endotherm occurs at 300C indicating the decomposition of Cd(OH)2. In positive plates, a first weak endotherm occurs at 100C, which indicates loss of H2O from Ni(OH)2(H2O)n molecules. A second large endotherm occurs in the range of 290C to 300C, indicating the decomposition of Ni(OH2) to NiO and H2O. Atomic absorption spectroscopy was used to determine nickel, cobalt, cadmium, and potassium content in battery electrolytes and electrodes. Results are presented in tables.

Rock, M.↗

NASA NTRS1990

The improvement of rechargeable lithium battery electrolyte performance with additives

The deliberate introduction of additives like 2-methylfuran (2-MeF) is known to improve Li cycleability in cyclic ether electrolytes. The authors found that the proclivity of 2-MeF to polymerize in the bulk electrolyte or on a TiS2 cathode was inhibited by the addition of reduced oxygen species, such as O2- and OH-. Additionally, the polymerization of tetrahydrofuran and dioxolane and the destructive processes initiated by AsF6- decomposition to AsF5 and AsF3 were inhibited by the introduction of reduced oxygen species, particularly OH- at the 10-ppm to 100-ppm level.

Dominey, L. A.↗

NASA NTRS1989

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.↗

NASA NTRS1991

Issues on the production and electrochemical separation of oxygen from carbon dioxide

There is considerable interest in in-situ propellant manufacturing on the moon and Mars. One of the concepts of oxygen production that is being actively pursued is the processing of atmospheric carbon dioxide on Mars to produce oxygen by means of thermal decomposition and electrochemical separation. The key component of such a production facility is the electrochemical separation cell that filters out the oxygen from the gas mixture of carbon dioxide, carbon monoxide, and oxygen. Efficient design of the separation cell and the selection of electrolyte and electrode materials of superior performance for the cell would translate to significant reduction in the power requirement and the mass of the production facility. The objective is to develop the technology required to produce the cells in-house and test various electrolyte and electrode materials systematically until the optimal combination is found. An effective technique was developed for the fabrication of disk shaped cells. Zirconia and Ceria cells were made in-house. Complete modules of the electrochemical cell and housings were designed, fabricated, and tested.

Kaloupis, P.↗

NASA NTRS2010

Lithium-Ion Electrolytes Containing Phosphorous-Based, Flame-Retardant Additives

Future NASA missions aimed at exploring Mars, the Moon, and the outer planets require rechargeable batteries that can operate over a wide temperature range (-60 to +60 C) to satisfy the requirements of various applications. In addition, many of these applications will require improved safety, due to their use by humans. Currently, the state-of-the-art lithium-ion (Li-ion) system has been demonstrated to operate over a wide range of temperatures (-40 to +40 C); however, abuse conditions can often lead to cell rupture and fire. The nature of the electrolyte can greatly affect the propensity of the cell/battery to catch fire, given the flammability of the organic solvents used within. Li-ion electrolytes have been developed that contain a flame-retardant additive in conjunction with fluorinated co-solvents to provide a safe system with a wide operating temperature range. Previous work incorporated fluorinated esters into multi-component electrolyte formulations, which were demonstrated to cover a temperature range from 60 to +60 C. This work was described in Fluoroester Co-Solvents for Low-Temperature Li+ Cells (NPO-44626), NASA Tech Briefs, Vol. 33, No. 9 (September 2009), p. 37; and Optimized Li-Ion Electrolytes Con tain ing Fluorinated Ester Co-Solvents (NPO-45824), NASA Tech Briefs, Vol. 34, No. 3 (March 2010), p. 48. Other previous work improved the safety characteristics of the electrolytes by adding flame-retardant additives such as triphenyl phosphate (TPhPh), tri-butyl phosphate (TBuPh), triethyl phosphate (TEtPh), and bis(2,2,2-trifluoroethyl) methyl phosphonate (TFMPo). The current work involves further investigation of other types of flame-retardant additives, including tris(2,2,2-trifluoroethyl) phosphate, tris(2,2,2-trifluoroethyl) phosphite, triphenylphosphite, diethyl ethylphosphonate, and diethyl phenylphosphonate added to an electrolyte composition intended for wide operating temperatures. In general, many of the formulations investigated in this study displayed good performance over a wide temperature range, good cycle life characteristics, and are expected to have improved safety characteristics, such as low flammability. Of the electrolytes studied, 1.0 M LiPF6 in EC+EMC+DEP (20:75:5 v/v %) and 1.0 M LiPF6 in EC+EMC+DPP (20:75:5 v/v %) displayed the best operation at low temperatures, whereas the electrolyte containing triphenylphosphite displayed the best cycle life performance compared to the baseline solution. It is anticipated that further improvements can be made to the life characteristics with the incorporation of a SET promoters (such as VC, vinylene carbonate), which will likely inhibit the decomposition of the flame-retardant additives.

Smart, Marshall C.↗

NASA NTRS1976

Hydrogen as an energy medium

Coal, though abundant in certain geographical locations of the USA poses environmental problems associated with its mining and combustion. Also, nuclear fission energy appears to have problems regarding safety and radioactive waste disposal that are as yet unresolved. The paper discusses hydrogen use and market projection along with energy sources for hydrogen production. Particular attention is given to hydrogen production technology as related to electrolysis and thermochemical water decomposition. Economics of hydrogen will ultimately be determined by the price and availability of future energy carriers such as electricity and synthetic natural gas. Thermochemical methods of hydrogen production appear to offer promise largely in the efficiency of energy conversion and in capital costs over electrolytic methods.

Cox, K. E.↗

NASA NTRS1988

Carbon dioxide electrolysis with solid oxide electrolyte cells for oxygen recovery in life support systems

The direct electrochemical reduction of carbon dioxide (CO2) is achieved without catalysts and at sufficiently high temperatures to avoid carbon formation. The tubular electrolysis cell consists of thin layers of anode, electrolyte, cathode and cell interconnection. The electrolyte is made from yttria-stabilized zirconia which is an oxygen ion conductor at elevated temperatures. Anode and cell interconnection materials are complex oxides and are electronic conductors. The cathode material is a composite metal-ceramic structure. Cell performance characteristics have been determined using varying feed gas compositions and degrees of electrochemical decomposition. Cell test data are used to project the performance of a three-person CO2-electrolysis breadboard system.

Isenberg, Arnold O.↗

NASA NTRS1987

Perovskite oxides: Oxygen electrocatalysis and bulk structure

Perovskite type oxides were considered for use as oxygen reduction and generation electrocatalysts in alkaline electrolytes. Perovskite stability and electrocatalytic activity are studied along with possible relationships of the latter with the bulk solid state properties. A series of compounds of the type LaFe(x)Ni1(-x)O3 was used as a model system to gain information on the possible relationships between surface catalytic activity and bulk structure. Hydrogen peroxide decomposition rate constants were measured for these compounds. Ex situ Mossbauer effect spectroscopy (MES), and magnetic susceptibility measurements were used to study the solid state properties. X ray photoelectron spectroscopy (XPS) was used to examine the surface. MES has indicated the presence of a paramagnetic to magnetically ordered phase transition for values of x between 0.4 and 0.5. A correlation was found between the values of the MES isomer shift and the catalytic activity for peroxide decomposition. Thus, the catalytic activity can be correlated to the d-electron density for the transition metal cations.

Carbonio, R. E.↗

NASA NTRS1988

Perovskite-type oxides - Oxygen electrocatalysis and bulk structure

Carbonio, R. E.↗

NASA NTRS1976

Evaluation of selected chemical processes for production of low-cost silicon

Plant construction costs and manufacturing costs were estimated for the production of solar-grade silicon by the reduction of silicon tetrachloride in a fluidized bed of seed particles, and several modifications of the iodide process using either thermal decomposition on heated filaments (rods) or hydrogen reduction in a fluidized bed of seed particles. Energy consumption data for the zinc reduction process and each of the iodide process options are given and all appear to be acceptable from the standpoint of energy pay back. Information is presented on the experimental zinc reduction of SiCl4 and electrolytic recovery of zinc from ZnCl2. All of the experimental work performed thus far has supported the initial assumption as to technical feasibility of producing semiconductor silicon by the zinc reduction or iodide processes proposed. The results of a more thorough thermodynamic evaluation of the iodination of silicon oxide/carbon mixtures are presented which explain apparent inconsistencies in an earlier cursory examination of the system.

Blocher, J. M., Jr.↗

NASA NTRS2004

Increasing the Thermal Stability of Aluminum Titanate for Solid Oxide Fuel Cell Anodes

Solid-oxide fuel cells (SOFCs) show great potential as a power source for future space exploration missions. Because SOFCs operate at temperatures significantly higher than other types of fuel cells, they can reach overall efficiencies of up to 60% and are able to utilize fossil fuels. The SOFC team at GRC is leading NASA's effort to develop a solid oxide fuel cell with a power density high enough to be used for aeronautics and space applications, which is approximately ten times higher than ground transport targets. layers must be able to operate as a single unit at temperatures upwards of 900'C for at least 40,000 hours with less than ten percent degradation. One key challenge to meeting this goal arises from the thermal expansion mismatch between different layers. The amount a material expands upon heating is expressed by its coefficient of thermal expansion (CTE). If the CTEs of adjacent layers are substantially different, thermal stresses will arise during the cell's fabrication and operation. These stresses, accompanied by thermal cycling, can fracture and destroy the cell. While this is not an issue at the electrolyte-cathode interface, it is a major concern at the electrolyte-anode interface, especially in high power anode-supported systems. electrolyte are nearly identical. Conventionally, this has been accomplished by varying the composition of the anode to match the CTE of the yittria-stabilized zirconia (YSZ) electrolyte (approx.10.8x10(exp -6/degC). A Ni/YSZ composite is typically used as a base material for the anode due to its excellent electrochemical properties, but its CTE is about 13.4x10(exp -6/degC). One potential way to lower the CTE of this anode is to add a small percentage of polycrystalline Al2TiO5, with a CTE of 0.68x10(exp -6/degC, to the Ni/YSZ base. However, Al2TiO5 is thermally unstable and loses its effectiveness as it decomposes to Al2O3 and TiO2 between 750 C and 1280 C. be used as additives to increase the thermal stability of Al2TiO5 in SOFC operating conditions without adversely affecting the electrochemical properties of the SOFC anode. Three candidate materials were chosen through an extensive literature review: MgO, Fe2O3, and ZrTiO4. Although all three have been shown to prevent Al2TiO5 decomposition under various conditions, their effectiveness in the temperature range and atmosphere of the SOFC has not yet been evaluated. Several batches of Al2TiO5 with varying amounts of additives were prepared, exposed to reducing and oxidizing atmospheres at elevated temperatures, and the resulting decomposition of Al2TiO5 was measured. The most promising additives were further evaluated with the goal of ultimately preparing low CTE anodes that are chemically compatible to current systems. Adding minor constituents to stabilize Al2TiO5 could ultimately preserve its low CTE for the life of the fuel cell and improve the cell's long-term performance without a drop in anode conductivity. Further, these low CTE filler additions could allow the use of new sulfur tolerant anode materials, improving the viability of SOFCs for future aeronautics and space applications. Every SOFC consists of a cathode and an anode separated by an electrolyte, These three One way to avoid this problem is to design the cell such that the CTEs of the anode and The objective of this summer research project was to evaluate several materials that could

Bender, Jeffrey B.↗

NASA NTRS1988

Decomposition of hydrazine by high frequency glow electrical discharges

Originally, de Groot et al. examined electrical conductivity phenomena in terms of the thermodynamics of irreversible processes. They considered the system to be discontinuous and calculated only the differences between the opposing ends of the process. Thus these theories are phenomenological. In the present work, thermodynamics is developed as a continuous system based on hydrodynamics and the entropy production for a thin capillary. It is shown that electroconductivity can be interpreted without difficulty. For the electric double layer, the effects of electrolytes and surface conductivity and the gap width were calculated for the Gouy model.

Suzuki, M.↗