Development of a CO2-H2O solid oxide electrolysis system Annual report, 1 Apr. - 31 Dec. 1970
Performance tests of CO2-H2O solid oxide electrolyte electrolysis system for generation of oxygen for life support systems
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Performance tests of CO2-H2O solid oxide electrolyte electrolysis system for generation of oxygen for life support systems
Carbon dioxide-water solid oxide electrolyte electrolysis system
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.
Development of aerospace life support system for oxygen production from carbon dioxide
The design, fabrication, breadboard testing, and the data base obtained for solid oxide electrolysis systems that have applications for planetary manned missions and habitats are reviewed. The breadboard tested contains sixteen tubular cells in a closely packed bundle for the electrolysis of carbon dioxide and water vapor. The discussion covers energy requirements, volume, weight, and operational characteristics related to the measurement of the reactant and product gas compositions, temperature distribution along the electrolyzer tubular cells and through the bundle, and thermal energy losses. The reliability of individual cell performance in the bundle configuration is assessed.
A unitary layered ceramic structure is disclosed which comprises co-sintered layers. The co-sintered structure comprises a sintered central layer of yttria stabilized zirconia (YSZ) which is about 8 mole percent yttria and having a density of at least about 95% of theoretical, and sintered outer layers of strontium lanthanum manganite (LSM) having the approximate molecular composition La.sub.0.8 Sr.sub.0.2 MnO.sub.3, having a density from about 50 to about 60% of theoretical, and having interconnected porosity from about 40 to 50% with an interconnected pore diameter from about one micron to about five microns. The sintered central layer is sandwiched by and bonded and sintered to the outer layers and is essentially free of significant amounts of manganese. A process for making the unitary composition-of-matter is also disclosed which involves tape casting a LSM tape and then on top thereof casting a YSZ tape. The process comprises presintering LSM powder at 1250.degree. F., crushing the presintered commercially available LSM powder, forming a slurry with the crushed LSM, a binder and solvent, tape casting the slurry and allowing the slurry to air dry. A mixture of commercially available submicron size particle YSZ powder is milled with a dispersant and solvent to disperse the YSZ particles thereby forming a dispersed YSZ slurry. The YSZ slurry is then tape cast on the dried LSM tape. If desired, a third layer of LSM can be cast on top of the dried YSZ layer. After drying the composite LSM/YSZ and LSM/YSZ/LSM tapes are fired at 1300.degree. C. No migration of manganese into the YSZ layer was observed with scanning electron microscope/edax in the sintered multilayer tape.
An unitary layered ceramic structure is disclosed which comprises co-sintered layers. The co-sintered structure comprises a sintered central layer of yttria stabilized zirconia (YSZ) which is about 8 mole percent yttria and having a density of at least about 95% of theoretical, and sintered outer layers of strontium lanthanum manganite (LSM) having the approximate molecular composition La.sub.0.8 Sr.sub.0.2 MnO.sub.3, having a density from about 50 to about 60% of theoretical, and having interconnected porosity from about 40 to 50% with an interconnected pore diameter from about one micron to about five microns. The sintered central layer is sandwiched by and bonded and sintered to the outer layers and is essentially free of significant amounts of manganese. A process for making the unitary composition-of-matter is also disclosed which involves tape casting a LSM tape and then on top thereof casting a YSZ tape. The process comprises presintering LSM powder at 1250.degree. F., crushing the presintered commercially available LSM powder, forming a slurry with the crushed LSM, a binder and solvent, tape casting the slurry and allowing the slurry to air dry. A mixture of commercially available submicron size particle YSZ powder is milled with a dispersant and solvent to disperse the YSZ particles thereby forming a dispersed YSZ slurry. The YSZ slurry is then tape cast on the dried LSM tape. If desired, a third layer of LSM can be cast on top of the dried YSZ layer. After drying the composite LSM/YSZ and LSM/YSZ/LSM tapes are fired at 1300.degree. C. No migration of manganese into the YSZ layer was observed with scanning electron microscope/edax in the sintered multilayer tape.
Electrolyte operated at an elevated temperature in an electrolysis cell regenerates oxygen from metabolic carbon dioxide found in closed-cycle cabin atmospheres.
A low temperature electrolysis process has been developed for the treatment of solid waste material and urine. Experiments are described in which organic materials are oxidized directly at the surface of an electrode. Also, hypochlorite is generated electrochemically from chloride component of urine. Hypochlorite can act as a strong oxidizing agent in solution. The oxidation takes place at 30-60 C and the gaseous products from the anodic reaction are carbon dioxide, nitrogen, oxygen. Hydrogen is formed at the cathode. Carbon monoxide, and nitrogen oxides and methane were not detected in the off gases. Chlorine was evolved at the anode in relatively low amounts.
The investigation into electrolysis as a means of waste treatment and recycling on manned space missions is described. The electrochemical reactions of an artificial fecal waste mixture was examined. Waste electrolysis experiments were performed in a single compartment reactor, on platinum electrodes, to determine conditions likely to maximize the efficiency of oxidation of fecal waste material to CO2. The maximum current efficiencies for artificial fecal waste electrolysis to CO2 was found to be around 50 percent in the test apparatus. Experiments involving fecal waste oxidation on platinum indicates that electrodes with a higher overvoltage for oxygen evolution such as lead dioxide will give a larger effective potential range for organic oxidation reactions. An electrochemical packed column reactor was constructed with lead dioxide as electrode material. Preliminary experiments were performed using a packed-bed reactor and continuous flow techniques showing this system may be effective in complete oxidation of fecal material. The addition of redox mediator Ce(3+)/Ce(4+) enhances the oxidation process of biomass components. Scientific literature relevant to biomass and fecal waste electrolysis were reviewed.
A solid electrolyte cell with improved sealing characteristics was examined. A tube cell was designed, developed, fabricated, and tested. Design concepts incorporated in the tube cell to improve its sealing capability included minimizing the number of seals per cell and moving seals to lower temperature regions. The advanced tube cell design consists of one high temperature ceramic cement seal, one high temperature gasket seal, and three low temperature silicone elastomer seals. The two high temperature seals in the tube cell design represent a significant improvement over the ten high temperature precious metal seals required by the electrolyzer drum design. For the tube cell design the solid electrolyte was 8 mole percent yttria stabilized zirconium oxide slip cast into the shape of a tube with electrodes applied on the inside and outside surfaces.
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.
Mining and processing of lunar material could possibly lead to more cost-efficient scenarios for permanent presence of man in space and on the Moon. Production of oxygen for use as propellant seems especially important. Different candidate processes for oxygen-extraction from lunar soil were proposed, of which the reduction of ilmenite by hydrogen was studied most. This process, however, needs the concentration of ilmenite from lunar regolith to a large extent and releases oxygen only with low efficiency. Another possibility - the fluorination method - which works with lunar bulk material as feedstock is discussed. Liberation of oxygen from silicate or oxide materials by fluorination methods has been applied in geoscience since the early sixties. The fact that even at moderate temperatures 98 to 100 percent yields can be attained, suggests that fluorination of lunar regolith could be an effective way of propellant production. Lunar soil contains about 50 percent oxygen by weight which is gained nearly completely through this process as O2 gas. The second-most element Si is liberated as gaseous SiF4. It could be used for production of Si-metal and fluorine-recycling. All other main elements of lunar soil will be converted into solid fluorides which also can be used for metal-production and fluorine-recycling. Preliminary results of small scale experiments with different materials are discussed, giving information on specific oxygen-yields and amounts of by-products as functions of temperature. These experiments were performed with an already existing fluorine extraction and collection device at the University of Bonn, normally used for determination of oxygen-isotopic abundances. Optimum conditions, especially concerning energy consumption, are investigated. Extrapolation of the experimental results to large industrial-type plants on the Moon is tried and seems to be promising at first sight. The recycling of the fluorine is, however, crucial for the process. It might be achieved by means of electrolysis. This needs further investigation. The technical problem of transport and handling of the toxic and corrosive fluorine seems to be solvable and could be done by inert storage vessels.