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313 records · Page 18

A Survey of Alternative Oxygen Production Technologies

Utilization of the Martian atmosphere for the production of fuel and oxygen has been extensively studied. The baseline fuel production process is a Sabatier reactor, which produces methane and water from carbon dioxide and hydrogen. The oxygen produced from the electrolysis of the water is only half of that needed for methane-based rocket propellant, and additional oxygen is needed for breathing air, fuel cells and other energy sources. Zirconia electrolysis cells for the direct reduction of CO2 arc being developed as an alternative means of producing oxygen, but present many challenges for a large-scale oxygen production system. The very high operating temperatures and fragile nature of the cells coupled with fairly high operating voltages leave room for improvement. This paper will survey alternative oxygen production technologies, present data on operating characteristics, materials of construction, and some preliminary laboratory results on attempts to implement each. Our goal is to significantly improve upon the characteristics of proposed zirconia cells for oxygen production. To achieve that goal we are looking at electrolytic systems that operate at significantly lower temperatures, preferably below 31C to allow the incorporation of liquid CO2 in the electrolyte. Our preliminary results indicate that such a system will have much higher current densities and have simpler cathode construction than a porous gas feed electrode system. Such a system could be achieved based on nonaqueous electrolytes or ionic liquids. We are focusing our research on the anode reaction that will produce oxygen from a product generated at the cathode using CO2 as the feed. Operation at low temperatures also will open up the full range of polymer and metal materials, allowing a more robust system design to withstand the rigors of flight, landing, and long term unattended operation on the surface of Mars.

Lueck, Dale E.↗

Integrated Pulse Detonation Propulsion and Magnetohydrodynamic Power

The prospects for realizing an integrated pulse detonation propulsion and magnetohydrodynamic (MHD) power system are examined. First, energy requirements for direct detonation initiation of various fuel-oxygen and fuel-air mixtures are deduced from available experimental data and theoretical models. Second, the pumping power requirements for effective chamber scavenging are examined through the introduction of a scavenging ratio parameter and a scavenging efficiency parameter. A series of laboratory experiments were carried out to investigate the basic engineering performance characteristics of a pulse detonation-driven MHD electric power generator. In these experiments, stoichiometric oxy-acetylene mixtures seeded with a cesium hydroxide/methanol spray were detonated at atmospheric pressure in a 1-m-long tube having an i.d. of 2.54 cm. Experiments with a plasma diagnostic channel attached to the end of the tube confirmed the attainment of detonation conditions (p(sub 2)/p(sub 1) approx. 34 and D approx. 2,400 m/sec) and enabled the direct measurement of current density and electrical conductivity (=6 S/m) behind the detonation wave front. In a second set of experiments, a 30-cm-long continuous electrode Faraday channel, having a height of 2.54 cm and a width of 2 cm, was attached to the end of the tube using an area transition duct. The Faraday channel was inserted in applied magnetic fields of 0.6 and 0.95 T. and the electrodes were connected to an active loading circuit to characterize power extraction dependence on load impedance while also simulating higher effective magnetic induction. The experiments indicated peak power extraction at a load impedance between 5 and 10 Ohm. The measured power density was in reasonable agreement with a simple electrodynamic model incorporating a correction for near-electrode potential losses. The time-resolved thrust characteristics of the system were also measured, and it was found that the MHD interaction exerted a negligible influence on system thrust and that the measured I(sub sp) of the system (200 sec) exceeded that computed for an equivalent nozzleless rocket (120 sec).

Litchford, R. J.↗

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.↗

Electrospray Thruster Performance with Microfabricated Emitter Arrays and Indium Propellant

The feasibility of a microfabricated indium-fueled electrospray thruster with excellent performance was demonstrated. High efficiency electrospray thrusters with microfabricated components are under development for very compact, distributable propulsion systems that can be employed on both very small and large spacecraft with 10X improvement over SOA in mass, volume and specific impulse The critical components of this technology are the microfabricated emitter arrays and the capillary force driven indium feed system. Grey scale electron-beam lithography patterning and reactive ion dry etching provided the required micron-scale etch precision and uniformity across an array of 400 emitters in 1 cm2. Initial tests of single microfabricated silicon emitters demonstrated better performance than industry standard single emitters and the performance required to achieve 200 micronewtons when scaled up to a thruster with 400 emitters in 1 cm2. Arrays of emitters tested in a preliminary prototype Microfluidic Electrospray Propulsion (MEP) thruster assembly demonstrated stable performance at estimated thrust levels of 5, 50, and 120 µN at extraction voltages less than 4 kV. Current stability was within 0.15 % at 120 µN with only 1.5% of the emitter current collected by the extractor electrode. Post-test inspections revealed that more than 99% of the 400 emitters were electrospraying during the test. Specific impulse was estimated to be >3100 s from measurements of total charge and consumed indium mass at an emitter voltage of 1470 V. The results of this investigation suggest that microfabricated indium electrospray thruster technology is both feasible and capable of excellent performance as a highly compact microthruster.

Marrese-Reading, Colleen M.↗

Substituted Quaternary Ammonium Salts Improve Low-Temperature Performance of Double-Layer Capacitors

Double-layer capacitors are unique energy storage devices, capable of supporting large current pulses as well as a very high number of charging and discharging cycles. The performance of doublelayer capacitors is highly dependent on the nature of the electrolyte system used. Many applications, including for electric and fuel cell vehicles, back-up diesel generators, wind generator pitch control back-up power systems, environmental and structural distributed sensors, and spacecraft avionics, can potentially benefit from the use of double-layer capacitors with lower equivalent series resistances (ESRs) over wider temperature limits. Higher ESRs result in decreased power output, which is a particular problem at lower temperatures. Commercially available cells are typically rated for operation down to only 40 C. Previous briefs [for example, Low Temperature Supercapacitors (NPO-44386), NASA Tech Briefs, Vol. 32, No. 7 (July 2008), p. 32, and Supercapacitor Electrolyte Solvents With Liquid Range Below 80 C (NPO-44855), NASA Tech Briefs, Vol. 34, No. 1 (January 2010), p. 44] discussed the use of electrolytes that employed low-melting-point co-solvents to depress the freezing point of traditional acetonitrile-based electrolytes. Using these modified electrolyte formulations can extend the low-temperature operational limit of double-layer capacitors beyond that of commercially available cells. This previous work has shown that although the measured capacitance is relatively insensitive to temperature, the ESR can rise rapidly at low temperatures, due to decreased electrolyte conductance within the pores of the high surface- area carbon electrodes. Most of these advanced electrolyte systems featured tetraethylammonium tetrafluoroborate (TEATFB) as the salt. More recent work at JPL indicates the use of the asymmetric quaternary ammonium salt triethylmethylammonium tetrafluoroborate (TEMATFB) or spiro-(l,l')-bipyrrolidium tetrafluoroborate (SBPBF4) in a 1:1 by volume solvent mixture of acetonitrile (AN) and methyl formate (MF) enables double-layer capacitor cells to operate well below -40 C with a relatively low ESR. Typically, a less than twofold increase in ESR is observed at -65 C relative to room-temperature values, when these modified electrolyte blends are used in prototype cells. Double-layer capacitor coin cells filled with these electrolytes have displayed the lowest measured ESR for an organic electrolyte to date at low temperature (based on a wide range of electrolyte screening studies at JPL). The cells featured high-surface-area (approximately equal to 2,500 m/g) carbon electrodes that were 0.50 mm thick and 1.6 cm in diameter, and coated with a thin layer of platinum to reduce cell resistance. A polyethylene separator was used to electrically isolate the electrodes.

Brandon, Erik J.↗

Fuel-Cell-Powered Vehicle with Hybrid Power Management

Figure 1 depicts a hybrid electric utility vehicle that is powered by hydrogenburning proton-exchange-membrane (PEM) fuel cells operating in conjunction with a metal hydride hydrogen-storage unit. Unlike conventional hybrid electric vehicles, this vehicle utilizes ultracapacitors, rather than batteries, for storing electric energy. This vehicle is a product of continuing efforts to develop the technological discipline known as hybrid power management (HPM), which is oriented toward integration of diverse electric energy-generating, energy-storing, and energy- consuming devices in optimal configurations. Instances of HPM were reported in five prior NASA Tech Briefs articles, though not explicitly labeled as HPM in the first three articles: "Ultracapacitors Store Energy in a Hybrid Electric Vehicle" (LEW-16876), Vol. 24, No. 4 (April 2000), page 63; "Photovoltaic Power Station With Ultracapacitors for Storage" (LEW- 17177), Vol. 27, No. 8 (August 2003), page 38; "Flasher Powered by Photovoltaic Cells and Ultracapacitors" (LEW-17246), Vol. 27, No. 10 (October 2003), page 37; "Hybrid Power Management" (LEW-17520), Vol. 29, No. 12 (December 2005), page 35; and "Ultracapacitor-Powered Cordless Drill" (LEW-18116-1), Vol. 31, No. 8 (August 2007), page 34. To recapitulate from the cited prior articles: The use of ultracapacitors as energy- storage devices lies at the heart of HPM. An ultracapacitor is an electrochemical energy-storage device, but unlike in a conventional rechargeable electrochemical cell or battery, chemical reactions do not take place during operation. Instead, energy is stored electrostatically at an electrode/electrolyte interface. The capacitance per unit volume of an ultracapacitor is much greater than that of a conventional capacitor because its electrodes have much greater surface area per unit volume and the separation between the electrodes is much smaller.

Eichenberg, Dennis J.↗

Electrochemical Hydrogen Peroxide Generator

Two-electron reduction of oxygen to produce hydrogen peroxide is a much researched topic. Most of the work has been done in the production of hydrogen peroxide in basic media, in order to address the needs of the pulp and paper industry. However, peroxides under alkaline conditions show poor stabilities and are not useful in disinfection applications. There is a need to design electrocatalysts that are stable and provide good current and energy efficiencies to produce hydrogen peroxide under acidic conditions. The innovation focuses on the in situ generation of hydrogen peroxide using an electrochemical cell having a gas diffusion electrode as the cathode (electrode connected to the negative pole of the power supply) and a platinized titanium anode. The cathode and anode compartments are separated by a readily available cation-exchange membrane (Nafion 117). The anode compartment is fed with deionized water. Generation of oxygen is the anode reaction. Protons from the anode compartment are transferred across the cation-exchange membrane to the cathode compartment by electrostatic attraction towards the negatively charged electrode. The cathode compartment is fed with oxygen. Here, hydrogen peroxide is generated by the reduction of oxygen. Water may also be generated in the cathode. A small amount of water is also transported across the membrane along with hydrated protons transported across the membrane. Generally, each proton is hydrated with 3-5 molecules. The process is unique because hydrogen peroxide is formed as a high-purity aqueous solution. Since there are no hazardous chemicals or liquids used in the process, the disinfection product can be applied directly to water, before entering a water filtration unit to disinfect the incoming water and to prevent the build up of heterotrophic bacteria, for example, in carbon based filters. The competitive advantages of this process are: 1. No consumable chemicals are needed in the process. The only raw materials needed are water and oxygen or air. 2. The product is pure and can therefore be used in disinfection applications directly or after proper dilution with water. 3. Oxygen generated in the anode compartment is used in the electrochemical reduction process; in addition, external oxygen is used to establish a high flow rate in the cathode compartment to remove the desired product efficiently. Exiting oxygen can be recycled after separation of liquid hydrogen peroxide product, if so desired. 4. The process can be designed for peroxide generation under microgravity conditions. 5. High concentrations of the order of 6-7 wt% can be generated by this method. This method at the time of this reporting is superior to what other researchers have reported. 6. The cell design allows for stacking of cells to increase the hydrogen peroxide production. 7. The catalyst mix containing a diquaternary ammonium compound enabled not only higher concentration of hydrogen peroxide but also higher current efficiency, improved energy efficiency, and catalyst stability. 8. The activity of the catalyst is maintained even after repeated periods of system shutdown. 9. The catalyst system can be extended for fuel-cell cathodes with suitable modifications.

Tennakoon, Charles L. K.↗