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Catalysts for ultrahigh current density oxygen cathodes for space fuel cell applications

The objective of this research was to identify promising electrocatalyst/support systems for the oxygen cathode in alkaline fuel cells operating at relatively high temperatures, O2 pressures and current densities. A number of materials were prepared, including Pb-Ru and Pb-Ir pyrochlores, RuO2 and Pt-doped RuO2, and lithiated NiO. Several of these were prepared using techniques that had not been previously used to prepare them. Particularly interesting is the use of the alkaline solution technique to prepare the Pt-doped Pb-Ru pyrochlore in high area form. Well-crystallized Pb(2)Ru(2)O(7-y) was used to fabricate high performance O2 cathodes with relatively good stability in room temperature KOH. This material was also found to be stable over a useful potential range at approximately 140 C in concentrated KOH. Other pyrochlores were found to be either unstable (amorphous samples) or the fabrication of the gas-fed electrodes could not be fully optimized during this project period. Future work may be directed at this problem. High area platinum supported on conductive metal oxide supports produced mixed results: small improvements in O2 reduction performance for Pb(2)Ru(2)O(7-y) but a large improvement for Li-doped NiO at room temperature. Nearly reversible behavior was observed for the O2/OH couple for Li-doped NiO at approximately 200 C.

Tryk, D.

Catalysts for ultrahigh current density oxygen cathodes for space fuel cell applications

The objective was to identify promising electrocatalyst/support systems for oxygen cathodes capable of operating at ultrahigh current densities in alkaline fuel cells. Such cells will require operation at relatively high temperatures and O2 pressures. A number of materials were prepared, including Pb-Ru and Pb-Ir pyrochlores, RuO2 and Pt-doped RuO2, lithiated NiO and La-Ni perovskites. Several of these materials were prepared using techniques that had not been previously used to prepare them. Particularly interesting was the use of the alkaline solution technique to prepare Pt-doped and Pb-Ru pyrochlores in high area form. Also interesting was the use of the fusion (melt) method for preparing the Pb-Ru pyrochlore. Several of the materials were also deposited with platinum. Well-crystallized Pb2Ru2O(7-y) was used to fabricate very high performance O2 cathodes with good stability in room temperature KOH. This material was also found to be stable over a useful potential range at approx. 140 C in concentrated KOH. For some of the samples, fabrication of the gas-fed electrodes could not be fully optimized during this project period. Future work may be directed at this problem. Pyrochlores that were not well-crystallized were found to be unstable in alkaline solution. Very good O2 reduction performance and stability were observed with Pb2RuO(7-y) in a carbon-based gas-fed electrode with an anion-conducting membrane placed on the electrolyte side of the electrode. The performance came within a factor of about two of that observed without carbon. High area platinum and gold supported on several conductive metal oxide supports were examined. Only small improvements in O2 reduction performance at room temperature were observed for Pb2Ru2O(7-y) as a support because of the high intrinsic activity of the pyrochlore. In contrast, a large improvement was observed for Li-doped NiO as a support for Pt. Very poor performance was observed for Au deposited on Li-NiO at approx. 150 C. Nearly reversible behavior was observed for the O2/OH(-) couple for Li-doped NiO at approx. 200 C. The temperature dependence for the O2 reduction was examined.

Tryk, Donald A.

Advanced double layer capacitors

There is a need for large amounts of power to be delivered rapidly in a number of airborne and space systems. Conventional, portable power sources, such as batteries, are not suited to delivering high peak power pulses. The charge stored at the electrode-electrolyte double layer is, however, much more assessible on a short time scale. Devices exploiting this concept were fabricated using carbon and metal oxides (Pinnacle Research) as the electrodes and sulfuric acid as the electrolyte. The approach reported, replaces the liquid sulfuric acid electrolyte with a solid ionomer electrolyte. The challenge is to form a solid electrode-solid ionomer electrolyte composite which has a high capacitance per geometric area. The approach to maximize contact between the electrode particles and the ionomer was to impregnate the electrode particles using a liquid ionomer solution and to bond the solvent-free structure to a solid ionomer membrane. Ruthenium dioxide is the electrode material used. Three strategies are being pursued to provide for a high area electrode-ionomer contact: mixing of the RuOx with a small volume of ionomer solution followed by filtration to remove the solvent, and impregnation of the ionomer into an already formed RuOx electrode. RuOx powder and electrodes were examined by non-electrochemical techniques. X-ray diffraction has shown that the material is almost pure RuO2. The electrode structure depends on the processing technique used to introduce the Nafion. Impregnated electrodes have Nafion concentrated near the surface. Electrodes prepared by the evaporation method show large aggregates of crystals surrounded by Nafion.

Sarangapani, S.

Electrochemical incineration of wastes

The novel technology of waste removal in space vehicles by electrochemical methods is presented to convert wastes into chemicals that can be eventually recycled. The important consideration for waste oxidation is to select a right kind of electrode (anode) material that should be stable under anodic conditions and also a poor electrocatalyst for oxygen and chlorine evolution. On the basis of long term electrolysis experiments on seven different electrodes and on the basis of total organic carbon reduced, two best electrodes were identified. The effect of redox ions on the electrolyte was studied. Though most of the experiments were done in mixtures of urine and waste, the experiments with redox couples involved 2.5 M sulfuric acid in order to avoid the precipitation of redox ions by urea. Two methods for long term electrolysis of waste were investigated: (1) the oxidation on Pt and lead dioxide electrodes using the galvanostatic methods; and (2) potentiostatic method on other electrodes. The advantage of the first method is the faster rate of oxidation. The chlorine evolution in the second method is ten times less then in the first. The accomplished research has shown that urine/feces mixtures can be oxidized to carbon dioxide and water, but current densities are low and must be improved. The perovskite and Ti4O7 coated with RuO2 are the best electrode materials found. Recent experiment with the redox agent improves the current density, however, sulphuric acid is required to keep the redox agent in solution to enhance oxidation effectively. It is desirable to reduce the use of acid and/or find substitutes.

Bhardwaj, R. C.

Sol-gel Technology and Advanced Electrochemical Energy Storage Materials

Advanced materials play an important role in the development of electrochemical energy devices such as batteries, fuel cells, and electrochemical capacitors. The sol-gel process is a versatile solution for use in the fabrication of ceramic materials with tailored stoichiometry, microstructure, and properties. This processing technique is particularly useful in producing porous materials with high surface area and low density, two of the most desirable characteristics for electrode materials. In addition,the porous surface of gels can be modified chemically to create tailored surface properties, and inorganic/organic micro-composites can be prepared for improved material performance device fabrication. Applications of several sol-gel derived electrode materials in different energy storage devices are illustrated in this paper. V2O5 gels are shown to be a promising cathode material for solid state lithium batteries. Carbon aerogels, amorphous RuO2 gels and sol-gel derived hafnium compounds have been studied as electrode materials for high energy density and high power density electrochemical capacitors.

Chung-tse Chu

Space-based bacterial production of hydrogen

This paper deals with the electrochemical production of hydrogen by depolarizing the oxygen evolution reaction using human feces and urine, which contains 30-40% bacteria and yeast. The electroactivity of graphite, tungsten carbide, perovskite and RuO2-coated Ebonex (Ti4O7) as anode materials are compared. The scale-up of the process in a laboratory-scale three-dimensional packed bed cell is discussed.

NASA Discipline Life Support Systems