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This presentation discusses where the solid oxide fuel cell and electrolysis technologies could address the In Situ Resource Utilization (ISRU) and Sustainable Power needs in NASA Exploration activities.
Life support systems can take advantage of elements in the atmosphere of Mars to provide for necessary consumables such as oxygen and buffer gas for makeup of leakage. In situ consumables production (ISCP) can be performed effectively in conjunction with in situ propellant production, in which oxygen and methane are manufactured for rocket fuel. This project considers ways of achieving the optimal system objectives from the two sometimes competing objectives of ISPP and ISCP. In previous years we worked on production of a nitrogen-argon buffer gas as a by- product of the CO2 acquisition and compression system. Recently we have been focusing on combined electrolysis of water vapor and carbon dioxide. Combined electrolysis of water vapor and carbon dioxide is essential for reducin,o the complexity of a combined ISPP/ISCP plant. Using a solid oxide electrolysis cell (SOEC) for this combined process would be most advantageous for it allows mainly gas phase reactions, O2 gas delivered from the electrolyzer is free of any H2O vapor, and SOE is already a proven technology for pure CO2 electrolysis. Combined SOEC testing is conducted at The University of Arizona in the Space Technologies Laboratory (STL) of the Aerospace and Mechanical Engineering Department.
Gadolinia-doped ceria, or GDC, (Gd(0.4)Ce(0.6)O(2-delta), where the value of delta in this material varies, depending on the temperature and oxygen concentration in the atmosphere in which it is being used) has shown promise as a cathode material for high-temperature electrolysis of carbon dioxide in solid oxide electrolysis cells. The polarization resistance of a GDC electrode is significantly less than that of an otherwise equivalent electrode made of any of several other materials that are now in use or under consideration for use as cathodes for reduction of carbon dioxide. In addition, GDC shows no sign of deterioration under typical temperature and gas-mixture operating conditions of a high-temperature electrolyzer. Electrolysis of CO2 is of interest to NASA as a way of generating O2 from the CO2 in the Martian atmosphere. On Earth, a combination of electrolysis of CO2 and electrolysis of H2O might prove useful as a means of generating synthesis gas (syngas) from the exhaust gas of a coal- or natural-gas-fired power plant, thereby reducing the emission of CO2 into the atmosphere. The syngas a mixture of CO and H2 could be used as a raw material in the manufacture, via the Fisher-Tropsch process, of synthetic fuels, lubrication oils, and other hydrocarbon prod
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.
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.
Solid oxide electrolyzers, such as electrolysis cells utilizing yttria-stabilized zirconia, can produce oxygen from Mars atmospheric carbon dioxide and reject carbon monoxide and unreacted carbon dioxide in a separate stream. The oxygen-production process has been shown to be far more efficient if the high-pressure, unreacted carbon dioxide can be separated and recycled back into the feed stream. Additionally, the mass of the adsorption compressor can be reduced. Also, the carbon monoxide by-product is a valuable fuel for space exploration and habitation, with applications from fuel cells to production of hydrocarbons and plastics. In our research, we will design, construct, and test an innovative, robust, low mass, low power separation device that can recover carbon dioxide and carbon monoxide for Mars ISRU. Such fundamental process technology, involving gas-solid phase separation in a reduced gravitational environment, will help to enable Human Exploration and Development of Space. The separation device will be scaled to operate with a CO2 sorption compressor and a zirconia electrolysis device built at the NASA Ames Research Center and the University of Arizona, respectively. In our research, we will design, construct, and test an innovative, robust, low mass, low power separation device that can recover carbon dioxide and carbon monoxide for Mars ISRU, Such fundamental process technology, involving gas-solid phase separation in a reduced gravitational environment, will help to enable Human Exploration and Development of Space. The separation device will be scaled to operate with a CO2 sorption compressor and a zirconia electrolysis device built at the NASA Ames Research Center and the University of Arizona, The separation device will be scaled to operate with a CO2 sorption compressor and a zirconia electrolysis device built at the NASA Ames Research Center and the University of Arizona, Research needs for the design shown are as follows: (1) The best adsorbent for the process must be determined. (2) Adsorption isotherms must be measured, both for pure components and mixtures. (3) Mathematical modeling must be performed to provide a solid framework for design. (4) The separation system must be constructed and tested. (5) System integration must be studied.
Energy storage and production in space requires rugged, reliable hardware which minimizes weight, volume, and maintenance while maximizing power output and usable energy storage. These systems generally consist of photovoltaic solar arrays which operate during sunlight cycles to provide system power and regenerate fuel (hydrogen) via water electrolysis; during dark cycles, hydrogen is converted by the fuel cell into system. The currently preferred configuration uses two separate systems (fuel cell and electrolyzer) in conjunction with photovoltaic cells. Fuel cell/electrolyzer system simplicity, reliability, and power-to-weight and power-to-volume ratios could be greatly improved if both power production (fuel cell) and power storage (electrolysis) functions can be integrated into a single unit. The Technology Management, Inc. (TMI), solid oxide fuel cell-based system offers the opportunity to both integrate fuel cell and electrolyzer functions into one unit and potentially simplify system requirements. Based an the TMI solid oxide fuel cell (SOPC) technology, the TMI integrated fuel cell/electrolyzer utilizes innovative gas storage and operational concepts and operates like a rechargeable 'hydrogen-oxygen battery'. Preliminary research has been completed on improved H2/H2O electrode (SOFC anode/electrolyzer cathode) materials for solid oxide, regenerative fuel cells. Improved H2/H2O electrode materials showed improved cell performance in both fuel cell and electrolysis modes in reversible cell tests. ln reversible fuel cell/electrolyzer mode, regenerative fuel cell efficiencies (ratio of power out (fuel cell mode) to power in (electrolyzer model)) improved from 50 percent (using conventional electrode materials) to over 80 percent. The new materials will allow the TMI SOFC system to operate as both the electrolyzer and fuel cell in a single unit. Preliminary system designs have also been developed which indicate the technical feasibility of using the TMI SOFC technology for space applications with high energy storage efficiencies and high specific energy. Development of small space systems would also have potential dual-use, terrestrial applications.
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.
Electrolyte operated at an elevated temperature in an electrolysis cell regenerates oxygen from metabolic carbon dioxide found in closed-cycle cabin atmospheres.
The NASA Glenn Research Center is developing both a novel cell design (BSC) and a novel ceramic fabrication technique to produce fuel cells predicted to exceed a specific power density of 1.0 kW/kg. The NASA Glenn cell design has taken a completely different approach among planar designs by removing the metal interconnect and returning to the use of a thin, doped LaCrO3 interconnect. The cell is structurally symmetrical. Both electrodes support the thin electrolyte and contain micro-channels for gas flow-- a geometry referred to as a bi-electrode supported cell or BSC. The cell characteristics have been demonstrated under both SOFC and SOE conditions. Electrolysis tests verify that this cell design operates at very high electrochemical voltage efficiencies (EVE) and high H2O conversion percentages, even at the low flow rates predicted for closed loop systems encountered in unmanned aerial vehicle (UAV) applications. For UAVs the volume, weight and the efficiency are critical as they determine the size of the water tank, the solar panel size, and other system requirements. For UAVs, regenerative solid oxide fuel cell stacks (RSOFC) use solar panels during daylight to generate power for electrolysis and then operate in fuel cell mode during the night to power the UAV and electronics. Recent studies, performed by NASA for a more electric commercial aircraft, evaluated SOFCs for auxiliary power units (APUs). System studies were also conducted for regenerative RSOFC systems. One common requirement for aerospace SOFCs and RSOFCs, determined independently in each application study, was the need for high specific power density and volume density, on the order of 1.0 kW/kg and greater than 1.0 kW/L. Until recently the best reported performance for SOFCs was 0.2 kW/kg or less for stacks. NASA Glenn is working to prototype the light weight, low volume BSC design for such high specific power aerospace applications.
This presentation provides a high-level summary of recent fuel cell and electrolysis development activities at NASA for both aeronautic and aerospace applications. It highlights advances in PEM and solid oxide technologies implemented as primary fuel cells. It also includes the results of recent Lunar energy storage trade studies evaluating the feasibility of regenerative fuel cell energy storage.
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 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.
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.
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.
Power production is a key aspect to any Mars mission. One method for providing power throughout the day/night cycle, or to satisfy short-duration high-output power needs, is to utilize a regenerative fuel cell system for providing energy storage and nighttime or supplemental power. This study compares the total system mass for two types of fuel cell systems, proton exchange membrane (PEM) and solid oxide (SO), sized to provide 10 kW of electrical output power in the Mars environment. Two operating locations were examined; one near the equator at 4 °S latitude and one the higher northern latitude of 48°N. The systems were sized to operate throughout the year at these locations, where the radiator was sized for the worst-case warm condition and the insulation was sized for the worst-case cold condition. Using the selected system parameters, the results for both latitudes showed that the lightest system was the SO fuel cell with a PEM electrolyzer. This was mainly due to the higher operational temperature of the SO system enabled a significantly smaller radiator mass compared to that of the PEM fuel cell system. However, there was a significant difference in mass for the PEM system when operated near the equator as compared to the higher northern latitude. For the 10-kW output system this difference in mass was just under 100 kg.