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A device for electrolysis of an aqueous solution of an organic fuel. The electrolyte is a solid-state polymer membrane with anode and cathode catalysts on both surfaces for electro-oxidization and electro-reduction. A low-cost and portable hydrogen generator can be made based on the device with organic fuels such as methanol.
A device for electrolysis of an aqueous solution of an organic fuel. The electrolyte is a solid-state polymer membrane with anode and cathode catalysts on both surfaces for electro-oxidization and electro-reduction. A low-cost and portable hydrogen generator can be made based on the device with organic fuels such as methanol.
An automatic-control system has been devised for a process in which carbon nanotubes are produced in an arc between a catalyst-filled carbon anode and a graphite cathode. The control system includes a motor-driven screw that adjusts the distance between the electrodes. The system also includes a bridge circuit that puts out a voltage proportional to the difference between (1) the actual value of potential drop across the arc and (2) a reference value between 38 and 40 V (corresponding to a current of about 100 A) at which the yield of carbon nanotubes is maximized. Utilizing the fact that the potential drop across the arc increases with the interelectrode gap, the output of the bridge circuit is fed to a motor-control circuit that causes the motor to move the anode toward or away from the cathode if the actual potential drop is more or less, respectively, than the reference potential. Thus, the system regulates the interelectrode gap to maintain the optimum potential drop. The system also includes circuitry that records the potential drop across the arc and the relative position of the anode holder as function of time.
A simple optical setup has been devised to enable safe viewing of the arc and measurement of the interelectrode gap in a process in which carbon nanotubes are produced in an arc between a catalyst-filled carbon anode and a graphite cathode. This setup can be used for visually guided manual positioning of the anode to maintain the interelectrode gap at a desired constant value, possibly as a low-technology alternative to the automatic position/voltage control described in Automatic Control of Arc Process for Making Carbon Nanotubes (MSC-23134), NASA Tech Briefs, Vol. 28, No. 3 (March 2004), page 51. The optical setup consists mainly of lenses for projecting an image of the arc onto a wall, plus a calibrated grid that is mounted on the wall so that one can measure the superimposed image of the arc. To facilitate determination of the end point of the process, the anode is notched, by use of a file, at the end of the filled portion that is meant to be consumed in the process. As the anode is consumed and the notch comes into view in the scene projected onto the wall, the process operator switches off the arc current.
In certain embodiments of the present disclosure, a solid oxide fuel cell is described. The solid oxide fuel cell includes a hierarchically porous cathode support having an impregnated cobaltite cathode deposited thereon, an electrolyte, and an anode support. The anode support includes hydrocarbon oxidation catalyst deposited thereon, wherein the cathode support, electrolyte, and anode support are joined together and wherein the solid oxide fuel cell operates a temperature of 600.degree. C. or less.
One of the primary obstacles to the widespread use of the direct methanol fuel cell (DMFC) is the high cost of the catalyst. Therefore, reducing the catalyst loading well below the current level of 8-12 mg/cm 2 would be important to commercialization. The current methods for preparation of catalyst layers consisting of catalyst, ionomer and sometimes a hydrophobic additive are applied by either painting, spraying, decal transfer or screen printing processes. Sputter deposition is a coating technique widely used in manufacturing and therefore particularly attractive. In this study we have begun to explore sputtering as a method for catalyst deposition. Present experiments focus on Pt-Ru catalyst layers for the anode.
The oxygen (O2) recovery system for the International Space Station (ISS) can recover approximately 50 percent of O2 from metabolic carbon dioxide (CO2). Increasing the O2 recovery rate and closing the open loop for future long duration crewed missions in space beyond Low Earth Orbit (LEO) is essential. There are several developmental efforts underway to increase the recovery rate. However, most of these technologies result in a complex, heavy, and power consuming system. The desired exploration O2 recovery system would be reliable and efficient with maximum O2 recovery. Marshall Space Flight Center (MSFC) is currently investigating an electrolytic O2 recovery approach that will increase the O2 recovery to greater than 70 percent as well as lowering the complexity, mass, and power consumption than most other technologies currently under development. The electrolytic O2 recovery system consists of a Microfluidic Electrochemical Reactor (MFECR) that is based on the electrochemical reduction of CO2 to O2 and ethylene (C2H4) using water (H2O) as precursor and operates at standard condition with a theoretical recovery rate of 73 percent. In 2016, NASA’s Game Changing Development Program awarded the University of Texas Arlington (UTA) a grant to initiate the development of the MFECR. Since 2019, MSFC and UTA have been collaborating with the current goals of increasing the O2 recovery efficiency, advancing the technology readiness to a Technology Readiness Level (TRL) 4, and maturing the system to process CO2 of one crew-member. Based on the results from UTA’s initial efforts, the following were identified as key areas of improvement in order to maximize O2 recovery for the system: further development of the anode material and cathode catalyst, model-based cell design optimization, and the addition of a separation system and fuel cell. This paper will present the current developmental efforts of the electrolytic system including MFECR design and overall system enhancements as well as results from single cell stack testing.
Corrosion resistance and anode activity data on interstitial compounds for fuel cell catalysts
Although many methods are available for producing single-walled carbon nanotubes (SWNTs), the conventional carbon arc process remains the most popular due to its simplicity and large production rate. In the carbon arc, SWNTs are catalytically synthesized by rapidly evaporating a graphite anode impregnated with NiN metal catalyst from which the nanotubes grow in an inert atmosphere. However, high temperatures inside the carbon arc generate strong buoyancy driven convection, and it is hypothesized that the non-uniform environment created by this flow has a large effect on the growth and morphology of the SWNTs. To study the effect of buoyancy on the arc process, a miniature carbon arc apparatus was developed to synthesize SWNTs in a microgravity environment substantially free from these strong convective flows. The reactor was operated for either 2.2 or 5 seconds during free-fall in the drop towers at the NASA Glenn Research Center. Two apparatus designs differing mainly in their production rate and power capacity were investigated. The first consisted of a miniaturized carbon arc employing a 1 mm diameter graphite anode and powered by a 0.54 F capacitor bank charged to 65 V. The second, larger apparatus employed a 4 mm diameter anode and was powered by a portable battery pack capable of providing in excess of 300 amps at 30 volts to the arc for the duration of a 5 second drop. Initial results indicated that transient heating is a very large effect in the short-duration drop tower carbon arcs, and thermal equilibrium of the arc plasma, buffer gas, and apparatus was not attained during the short microgravity periods. In addition, removal of the buoyant convection by the microgravity now allowed clear observation of large jets of evaporated carbon vapor streaming from the anode and mixing with the inert buffer gas. The initial mixing of these jets with the cold buffer gas combined with the thermal transient made it difficult to establish a uniform high temperature environment around the arc in the 2.1 to 5 second microgravity time interval, and even with a very high-powered arc, the arc region was cooler than in continuously operated arcs. Despite these difficulties, the miniature arc produced SWNTs in microgravity. However, given the large thermal transient to overcome, no dramatic difference in sample yield or composition was noted between normal gravity and q2-,andL%econd long microgravity runs.
An experimental study was conducted with anode limited D size cells to characterize the performance of an active lithium-thionyl chloride (Li/SOCl2) system using the polymeric cobalt phthalocyanine, (CoPC)n, catalyst in carbon cathodes. The author describes the results of this experiment with respect to initial voltage delays, operating voltages, and capacities. The effectiveness of the preconditioning methods evolved to alleviate passivation effects on storage are also discussed. The results clearly demonstrated the superior high rate capability of cells with the catalyst. The catalyst did not adversely impact the performance of cells after active storage for up to 6 months, while retaining its beneficial influences.
Alloy electrocatalysts on carbon supports were developed for hydrogen oxidation in the presence of carbon monoxide. These electrocatalysts match the best platinum on carbon catalysts for performance yet cost half as much. The results demonstrate that a significant reduction in anode electrocatalyst material cost can be achieved by replacing the platinum. Since surface characterization of this catalyst is important to explain its performance, several approaches and pitfalls to the elucidation of the surface characterization are presented.
A modified porous anodic alumina template (PAA) containing a thin CNT catalyst layer directly embedded into the pore walls. CNT synthesis using the template selectively catalyzes SWNTs and DWNTs from the embedded catalyst layer to the top PAA surface, creating a vertical CNT channel within the pores. Subsequent processing allows for easy contact metallization and adaptable functionalization of the CNTs and template for a myriad of applications.
A method for preparing a membrane for use in a fuel cell membrane electrode assembly includes the steps of providing an electrolyte membrane, and sputter-depositing a catalyst onto the electrolyte membrane. The sputter-deposited catalyst may be applied to multiple sides of the electrolyte membrane. A method for forming an electrode for use in a fuel cell membrane electrode assembly includes the steps of obtaining a catalyst, obtaining a backing, and sputter-depositing the catalyst onto the backing. The membranes and electrodes are useful for assembling fuel cells that include an anode electrode, a cathode electrode, a fuel supply, and an electrolyte membrane, wherein the electrolyte membrane includes a sputter-deposited catalyst, and the sputter-deposited catalyst is effective for sustaining a voltage across a membrane electrode assembly in the fuel cell.
Platinum-silver, palladium-gold, and platinum-gold alloys serve as oxygen reduction catalysts in high-current-density cells. Catalysts were tested on polytetrafluoroethylene-bonded cathodes and a hydrogen anode at an operating cell temperature of 80 degrees C.
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.
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. 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).
NASA Glenn Research Center (GRC) is currently working on polymers for fuel cell and lithium battery applications. The desire for more efficient, higher power density, and a lower environmental impact power sources has led to interest in proton exchanges membrane fuels cells (PEMFC) and lithium batteries. A PEMFC has many advantages as a power source. The fuel cell uses oxygen and hydrogen as reactants. The resulting products are electricity, heat, and water. The PEMFC consists of electrodes with a catalyst, and an electrolyte. The electrolyte is an ion-conducting polymer that transports protons from the anode to the cathode. Typically, a PEMFC is operated at a temperature of about 80 C. There is intense interest in developing a fuel cell membrane that can operate at higher temperatures in the range of 80 C- 120 C. Operating the he1 cell at higher temperatures increases the kinetics of the fuel cell reaction as well as decreasing the susceptibility of the catalyst to be poisoned by impurities. Currently, Nafion made by Dupont is the most widely used polymer membrane in PEMFC. Nafion does not function well above 80 C due to a significant decrease in the conductivity of the membrane from a loss of hydration. In addition to the loss of conductivity at high temperatures, the long term stability and relatively high cost of Nafion have stimulated many researches to find a substitute for Nafion. Lithium ion batteries are popular for use in portable electronic devices, such as laptop computers and mobile phones. The high power density of lithium batteries makes them ideal for the high power demand of today s advanced electronics. NASA is developing a solid polymer electrolyte that can be used for lithium batteries. Solid polymer electrolytes have many advantages over the current gel or liquid based systems that are used currently. Among these advantages are the potential for increased power density and design flexibility. Automobiles, computers, and cell phones require highly efficient power density for lowering emissions and meeting increasing consumer demands. Many of the solutions can be provided by proton exchange membrane fuel cells and lithium batteries. NASA Glenn Research Center has recognized this need, and is presently engaged in a solution. The goals for the summer include mastering synthesis techniques, understanding the reactions occurring during the synthesis, and characterizing the resulting polymer membranes using NMR, DSC, and TGA for the PEMFC and lithium batteries.
The chromium (Cr(3+)/Cr(2+)) redox couple (electrolyte and electrode) was investigated to determine its suitability as negative electrode for the iron (Fe(3+)/Fe(2+))-chromium (Cr(3+)/Cr(2+)) redox flow battery. Literature search and laboratory investigation established that the solubility and stability of aqueous acidic solutions of chromium(3) chloride and chromium(2) chloride are sufficient for redox battery application. Four categories of electrode materials were tested; namely, metals and metalloid materials (elements and compounds), alloys, plated materials, and Teflon-bonded materials. In all, the relative performance of 26 candidate electrode materials was evaluated on the basis of slow scan rate linear sweep voltammetry in stirred solution. No single material tested gave both acceptable anodic an acceptable cathodic performance. However, the identification of lead as a good cathodic electrocatalyst and gold as a good anodic electrocatalyst led to the invention of the lead/gold combination electrocatalyst. This type of catalyst can be fabricated in several ways and appears to offer the advantages of each metal without the disadvantages associated with their use as single materials. This lead/gold electrocatalyst was tested by NASA-Lewis Research Center in complete, flowing, redox batteries comprising a stack of several cells. A large improvement in the battery's coulombic and energy efficiency was observed.