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Ultrahigh Areal Capacity Holey Graphene Air Cathodes for Li-O2 and Li-CO2 Batteries

Advanced lithium (Li) batteries using gaseous cathode reactants such as oxygen (O2) and carbon dioxide (CO2)are attractive energy storage platforms because the gases are obtained externally and thus not accounted for in the total battery weight when fully charged.The discharge products at the cathode, typically Li2O2 for Li-O2 batteries and Li2CO3 for Li-CO2 batteries, are insoluble in the electrolyte.Therefore, in order for such batteries to function properly, an “air cathode”,which is a conductive scaffold within the battery cell,is required as a physical location for cathode electrochemical reactions to occur. Prior research has identified many carbon nanomaterials such as carbon nanotubes and graphene as viable choices for air cathode scaffold, while various metallic and metal-free catalytic systems integrated onto carbon-based air cathodes have been developed to improve the sluggish discharge and charge reactions. For future practical applications, the air cathode must exhibit a usable capacity per unit electrode area, or areal capacity, a critical parameter that has been largely overlooked so far in this field. In order to achieve high areal capacity, the air cathode must exhibit a sufficient amount of accessible void volume per unit electrode area while maintaining the conductive scaffold integrity during the entire electrochemical process. Here we present an ultrathick,holey graphene-based air cathode platform fabricated from a facile dry compression process that exhibits remarkable areal capacity values. Holey graphene is a carbon nanomaterial derived from graphene, but with nanometer sized holes through the nanosheet thickness.The presence of these holes enhances mass transport through electrode thickness and also enables the unique dry-press fabrication process that is not achievable using other carbon scaffold materials.The dry-pressed holey graphene air cathode platform is not only compatible with catalyst incorporation to improve battery reaction kinetics, but also allows for novel engineering of electrode architectures that is not achievable using conventional electrode fabrication approaches.The applications of such highly versatile, ultrahigh areal capacity air cathode platforms to both Li-O2 and Li-CO2 battery chemistries will be discussed.

Li-O2 batteries, Li-CO2 batteries, holey graphene,

Design, construction and long life endurance testing of cathode assemblies for use in microwave high-power transmitting tubes

The cathode life test program sponsored by NASA Lewis Research Center at Watkins-Johnson Company has been in continuous operation since 1972. Its primary objective has been to evaluate the long life capability of barium dispenser cathodes to produce emission current densities of 2 A sq. cm. or more in an operational environment simulating that of a highpower microwave tube. The life test vehicles were equipped with convergent flow electron guns, drift space tubes with solenoid magnets for electron beam confinement and water-cooled depressed collectors. A variety of cathode types has been tested, including GE Tungstate, Litton Impregnated, Philips Type B and M, Semicon types S and M, and Spectra-Mat Type M. Recent emphasis has been on monitoring the performance of Philips Type M cathodes at 2 A sq. cm. and Sprectra-Mat and Semicon Type M cathodes at 4 A sq. cm. These cathodes have been operated at a constant current of 616 mA and a cathode anode voltage on the order of 10 kV. Cathode temperatures were maintained at 1010 C true as measured from black body holes in the backs of the cathodes. This report presents results of the cathode life test program from July l982 through April l986. The results include hours of operation and performance data in the form of normalized emission current density versus temperature curves (Miram plots).

Batra, R.

Microanalysis of extended-test xenon hollow cathodes

Four hollow cathode electron sources were analyzed via boroscopy, scanning electron microscopy, energy dispersive x ray analysis, and x ray diffraction analysis. These techniques were used to develop a preliminary understanding of the chemistry of the devices that arise from contamination due to inadequate feed-system integrity and improper insert activation. Two hollow cathodes were operated in an ion thruster simulator at an emission current of 23.0 A for approximately 500 hrs. The two tests differed in propellant-feed systems, discharge power supplies, and activation procedures. Tungsten deposition and barium tungstate formation on the internal cathode surfaces occurred during the first test, which were believed to result from oxygen contamination of the propellant feed-system. Consequently, the test facility was upgraded to reduce contamination, and the test was repeated. The second hollow cathode was found to have experienced significantly less tungsten deposition. A second pair of cathodes examined were the discharge and the neutralizer hollow cathodes used in a life-test of a 30-cm ring-cusp ion thruster at a 5.5 kW power level. The cathodes' test history was documented and the post-test microanalyses are described. The most significant change resulting from the life-test was substantial tungsten deposition on the internal cathode surfaces, as well as removal of material from the insert surface. In addition, barium tungstate and molybdate were found on insert surfaces. As a result of the cathode examinations, procedures and approaches were proposed for improved discharge ignition and cathode longevity.

Verhey, Timothy R.

Characterization of Hollow Cathode Performance and Thermal Behavior

Hollow cathodes are one of the main life-limiting components in ion engines and Hall thrusters. Although state-of-the-art hollow cathodes have demonstrated up to 30,352 hours of operation in ground tests with careful handling, future missions are likely to require longer life, more margin and greater resistance to reactive contaminant gases. Three alternate hollow cathode technologies that exploit different emitter materials or geometries to address some of the limitations of state-of-the-art cathodes are being investigated. Performance measurements of impregnated tungsten-iridium dispenser cathodes at discharge currents of 4 to 15 A demonstrated that they have the same operating range and ion production efficiency as conventional tungsten dispenser cathodes. Temperature measurements indicated that tungsten-iridium cathodes also operate at the same emitter temperatures. They did not exhibit the expected reduction in work function at the current densities tested. Hollow cathodes with lanthanum hexaboride emitters operated over a wide current range, but suffered from lower ion production efficiency at currents below about 12.4 A because of higher insert heating requirements. Differences in operating voltages and ion production rates are explained with a simple model of the effect of cathode parameters on discharge behavior.

ion engines

High Current Cathode Thermal Behavior, Part II: Theory

Cathode erosion is one of the life limiting mechanisms for several classes of electric thrusters. Since cathode erosion is strongly dependent on the cathode temperature, a quantitative understanding of the effects of cathode operation on the cathode temperature is required. The development of a cathode/plasma interaction model for determining the heat loads to the cathode as function of the various free stream plasma parameters is presented. This model is combined with a cathode thermal model in order to provide a complete and integrated picture of high current cathode operation.

cathode erosion cathode temperature high current c

Tests of high current hollow cathodes for ion engines

The development of high power, high thrust ion engines requires the development of long life hollow cathodes capable of producing emission currents of hundreds of amperes. This paper describes results obtained through the extended testing of two 12.7 mm diameter hollow cathodes at high emission currents. The first cathode, operated on xenon for a total of 170 hours at an emission current of 100 A, sustained very little damage except for an increase in the cathode orifice diameter, from 0.953 to 1.71 mm. The second cathode was operated on xenon at 150 A emission current continuously for 24 hours, and for over 1000 hours at 100 A on argon with essentially no change in the cathode operating characteristics. Operation of this cathode was terminated due to severe erosion of several discharge chamber components located downstream of the cathode. The erosion of these components occurred despite operation at discharge voltages less than 24 volts, and poses a serious challenge to the sucessful implementation of multi-hundred ampere cathodes and high thrust ion engines.

Brophy, John R.

Extended testing of xenon ion thruster hollow cathodes

A hollow cathode wear-test of 508 hours was successfully completed at an emission current of 23.0 A and a xenon flow rate of 10 Pa-L/s. This test was the continuation of a hollow cathode contamination investigation. Discharge voltage was stable at 16.7 V. The cathode temperature averaged 1050 C with a 7 percent drop during the wear-test. Discharge ignition voltage was found to be approximately 20 V and was repeatable over four starts. Post-test analyses of the hollow cathode found a much improved internal cathode condition with respect to earlier wear-test cathodes. Negligible tungsten movement occurred and no formation of mono-barium tungstate was observed. These results correlated with an order-of-magnitude reduction in propellant feed-system leakage rate. Ba2CaWO6 and extensive calcium crystal formation occurred on the upstream end of the insert. Ba-Ca compound depositions were found on the Mo insert collar, on the Re electrical leads, and in the gap between the insert and cathode wall. This wear-test cathode was found to be in the best internal condition and had the most stable operating performance of any hollow cathode tested during this contamination investigation.

Sarver-Verhey, Timothy R.

Physical model and experimental results of cathode erosion related to power supply ripple

This paper discusses the physical effects of power supply ripple on cathode erosion and cathode arc attachment in a water-cooled, 30 kW nitrogen arcjet. Experimental results are presented for 2 percent thoriated tungsten, which show that the long-term cathode erosion rate is a decreasing function of current ripple over the range 1-13 percent. Above this range, the cathode discharge becomes unstable, and the erosion rate rapidly increases. A qualitative model of this effect is given in terms of a magnetically induced radial motion of the arc column, and an overall increase in the cathode spot radius due to the higher peak current associated with higher ripple. The most important effect of power supply ripple is therefore shown to be its ability to collectively drive the cathode attachment away from the cathode center. This leads to an increase in the cathode attachment area, and a subsequent decrease in the cathode erosion rate.

Harris, W. J.

Extended-testing of xenon ion thruster hollow cathodes

A hollow cathode wear-test of 508 hours was successfully completed at an emission current of 23.0 A and a xenon flow rate of 10 Pa-L/s. This test was the continuation of a hollow cathode contamination investigation. Discharge voltage was stable at 16.7 V. The cathode temperature averaged 1050 C with a 7 percent drop during the wear-test. Discharge ignition voltage was found to be approximately 20 V and was repeatable over four starts. Post-test analyses of the hollow cathode found a much improved internal cathode condition with respect to earlier wear-test cathodes. Negligible tungsten movement occurred and no formation of mono-barium tungsten was observed. These results correlated with an order-of-magnitude reduction in propellant feed-system leakage rate. Ba2CaWO6 and extensive calcium crystal formation occurred on the upstream end of the insert. Ba-Ca compound depositions were found on the Mo insert collar, on the Re electrical leads, and in the gap between the insert and cathode wall. This wear-test cathode was found to be in the best internal condition and had the most stable operating performance of any hollow cathode tested during this contamination investigation.

Sarver-Verhey, Timothy R.

Multiple Hollow Cathode Wear Testing for the Space Station Plasma Contactor

A wear test of four hollow cathodes was conducted to resolve issues associated with the Space Station plasma contactor. The objectives of this test were to evaluate unit-to-unit dispersions, verify the transportability of contamination control protocols developed by the project, and to evaluate cathode contamination control and activation procedures to enable simplification of the gas feed system and heater power processor. These objectives were achieved by wear testing four cathodes concurrently to 2000 hours. Test results showed maximum unit-to-unit deviations for discharge voltages and cathode tip temperatures to be +/-3 percent and +/-2 percent, respectively, of the nominal values. Cathodes utilizing contamination control procedures known to increase cathode lifetime showed no trends in their monitored parameters that would indicate a possible failure, demonstrating that contamination control procedures had been successfully transferred. Comparisons of cathodes utilizing and not utilizing a purifier or simplified activation procedure showed similar behavior during wear testing and pre- and post-test performance characterizations. This behavior indicates that use of simplified cathode systems and procedures is consistent with long cathode lifetimes.

Soulas, George C.

MoO3 Cathodes for High-Temperature Lithium Thin-Film Cells

MoO3 has shown promise as a cathode material that can extend the upper limit of operating temperature of rechargeable lithium thin-film electrochemical cells. Cells of this type are undergoing development for use as energy sources in cellular telephones, wireless medical sensors, and other, similarly sized portable electronic products. The LiCoO2 and LiMn2O4 cathodes heretofore used in these cells exhibit outstanding cycle lives (of the order of hundreds of thousands of cycles) at room temperature, but operation at higher temperatures reduces their cycle lives substantially: for example, at a temperature of 150 C, cells containing LiCoO2 cathodes lose half their capacities in 100 charge/discharge cycles. The superiority of MoO3 as a cathode material was demonstrated in experiments on lithium thin-film cells fabricated on glass slides. Each cell included a layer of Ti (for adhesion to the glass slide), a patterned layer of Pt that served as a cathode current collector, a cathode layer of MoO3, a solid electrolyte layer of Li3.3 PO3.8 N0.22 ("LiPON"), and an anode layer of Li. All the layers were deposited by magnetron sputtering except for the Li layer, which was deposited by thermal evaporation. These cells, along with similar ones containing LiCoO2 cathodes, were subjected to several tests, including measurements of specific capacity in charge/discharge cycling at a temperature of 150 C. The results of these measurements, plotted in the figure, showed that whereas specific capacity of the cells containing LiCoO2 cathodes faded to about half its initial value after only 100 cycles, the specific capacity of the cells containing the MoO3 cathodes faded only slightly during the first few hundred cycles and thereafter not only recovered to its initial value but continued to increase up to at least 5,500 cycles.

West, William

Numerical Simulations of the Partially-Ionized Gas in a 100-A LaB6 Hollow Cathode

Numerical simulations of a hollow cathode with a LaB6 emitter operating at 100 A have been performed for the first time using the 2-D Orificed Cathode (OrCa2D) code. Results for a variety of plasma properties are presented and compared with laboratory measurements. The large size of the device permits peak electron number densities in the cathode interior that are lower than those established in the NSTAR hollow cathode, which operates with a 7.3x lower discharge current and 3.2x lower mass flow rate. Also, despite the higher discharge current in the LaB6 cathode, the maximum electron current density is lower, by 4.2x, than that in the NSTAR cathode due to the larger orifice size. Simulations and direct measurements show that at 12 sccm of xenon flow the peak emitter temperature is in the range of 1594-1630 C. It is also found that the conditions for the excitement of current-driven streaming instabilities and ion-acoustic turbulence (IAT) are satisfied in this cathode, similarly to what was found in the past in its smaller counterparts like the NSTAR cathode. Based on numerical simulations, it has long been argued that these instabilities may be responsible for the anomalously large ion energies that have been measured in these discharges as well as for the enhancement of the plasma resistivity. Confirmation of the presence of IAT in this cathode is presented for the first time in a companion paper.

robotic exploration

Hollow Cathode Assembly Development for the HERMeS Hall Thruster

To support the operation of the HERMeS 12.5 kW Hall Thruster for NASA's Asteroid Redirect Robotic Mission, hollow cathodes using emitters based on barium oxide impregnate and lanthanum hexaboride are being evaluated through wear-testing, performance characterization, plasma modeling, and review of integration requirements. This presentation will present the development approach used to assess the cathode emitter options. A 2,000-hour wear-test of development model Barium Oxide (BaO) hollow cathode is being performed as part of the development plan. Specifically this test is to identify potential impacts cathode emitter life during operation in the HERMeS thruster. The cathode was operated with a magnetic field-equipped anode that simulates the HERMeS hall thruster operating environment. Cathode discharge performance has been stable with the device accumulating 743 hours at the time of this report. Observed voltage changes are attributed to keeper surface condition changes during testing. Cathode behavior during characterization sweeps exhibited stable behavior, including cathode temperature. The details of the cathode assembly operation of the wear-test will be presented.

Propulsion Technology

Preparation for Hollow Cathode Testing for the Advanced Electric Propulsion System at NASA Glenn Research Center

NASA Glenn Research Center is performing activities to support the unique needs of hollow cathode development and testing for the Advanced Electric Propulsion System (AEPS). Three existing vacuum facilities have been outfitted as cathode test facilities, and each will serve a different role in upcoming testing. Vacuum Facility 67 is being developed to serve as a long-duration test facility for the Engineering Development Unit cathode, which is to be delivered by the AEPS contractor. It will feature a thruster-like magnetic field simulator and cold-cycle capability via a liquid nitrogen-cooled cold plate. Vacuum Facility 17 is being developed as a test facility for short- to medium-duration experiments in order to provide auxiliary support for the long-duration testing. It will feature a magnetic field simulator but not cold-cycling. Finally, Vacuum Facility 1 will be a high-pumping speed cathode development environment, and will feature an array of plasma and temperature diagnostics. In addition to the facility preparation work, a new cathode, referred to as the Mark II, has been designed. The Mark II is an evolution of the Technology Demonstration Unit cathodes that better evokes the geometry, fabrication, and construction of the forthcoming Engineering Development Unit. This cathode serves as a transition between the Technology Demonstration Unit cathodes used during early thruster development and the forthcoming Engineering Development Unit cathodes. It will be used as a means of verifying the new test facilities prior to arrival of Engineering Development Unit hardware. Details of the Mark II design and key features are presented, as well as details of future work to be performed.

Hall, Scott J.

Preparation for Hollow Cathode Testing for the Advanced Electric Propulsion System at NASA Glenn Research Center

NASA Glenn Research Center is performing activities to support the unique needs of hollow cathode development and testing for the Advanced Electric Propulsion System (AEPS). Three existing vacuum facilities have been outfitted as cathode test facilities, and each will serve a different role in upcoming testing. Vacuum Facility 67 is being developed to serve as a long-duration test facility for the Engineering Development Unit cathode, which is to be delivered by the AEPS contractor. It will feature a thruster-like magnetic field simulator and cold-cycle capability via a liquid nitrogen-cooled cold plate. Vacuum Facility 17 is being developed as a test facility for short- to medium-duration experiments in order to provide auxiliary support for the long-duration testing. It will feature a magnetic field simulator but not cold-cycling. Finally, Vacuum Facility 1 will be a high-pumping speed cathode development environment, and will feature an array of plasma and temperature diagnostics. In addition to the facility preparation work, a new cathode, referred to as the Mark II, has been designed. The Mark II is an evolution of the Technology Demonstration Unit cathodes that better evokes the geometry, fabrication, and construction of the forthcoming Engineering Development Unit. This cathode serves as a transition between the Technology Demonstration Unit cathodes used during early thruster development and the forthcoming Engineering Development Unit cathodes. It will be used as a means of verifying the new test facilities prior to arrival of Engineering Development Unit hardware. Details of the Mark II design and key features are presented, as well as details of future work to be performed.

Advanced Electric Propulsion System (AEPS)

Preparation for Hollow Cathode Testing for the Advanced Electric Propulsion System at NASA Glenn Research Center

NASA Glenn Research Center is performing activities to support the unique needs of hollow cathode development and testing for the Advanced Electric Propulsion System (AEPS). Three existing vacuum facilities have been outfitted as cathode test facilities, and each will serve a different role in upcoming testing. Vacuum Facility 67 is being developed to serve as a long-duration test facility for the Engineering Development Unit cathode, which is to be delivered by the AEPS contractor. It will feature a thruster-like magnetic field simulator and cold-cycle capability via a liquid nitrogen-cooled cold plate. Vacuum Facility 17 is being developed as a test facility for short- to medium-duration experiments in order to provide auxiliary support for the long-duration testing. It will feature a magnetic field simulator but not cold-cycling. Finally, Vacuum Facility 1 will be a high-pumping speed cathode development environment, and will feature an array of plasma and temperature diagnostics. In addition to the facility preparation work, a new cathode, referred to as the Mark II, has been designed. The Mark II is an evolution of the Technology Demonstration Unit cathodes that better evokes the geometry, fabrication, and construction of the forthcoming Engineering Development Unit. This cathode serves as a transition between the Technology Demonstration Unit cathodes used during early thruster development and the forthcoming Engineering Development Unit cathodes. It will be used as a means of verifying the new test facilities prior to arrival of Engineering Development Unit hardware. Details of the Mark II design and key features are presented, as well as details of future work to be performed.

Hall, Scott J.

The Effect of Anode Position on Operation of a 25-A Class Hollow Cathode

The effect of the distance between a hollow cathode and a cylindrical anode on cathode operation is investigated for two anode geometries. Neutral flow simulations demonstrate that the anode diameter and distance from the cathode exit can elevate the downstream pressure as much as two orders of magnitude above what the cathode experiences while operating within a Hall thruster. Based on the results of this modeling, two axially-segmented cylindrical molybdenum anodes were constructed: a 64-mm diameter one that replicated the anode geometry used in recent NASA hollow cathode development testing and a larger 254-mm diameter one designed to reduce the neutral pressure in front of the cathode to thruster-like values. For each anode design, cathode performance was characterized for varying anode/cathode distance using metrics such as discharge voltage and oscillation magnitudes, and the ion voltage spectra were characterized using a radially-positioned retarding potential analyzer. It was found that as local neutral pressure decreased, discharge voltage and high-voltage ion content in the plume increased. For the 254-mm diameter anode, an ion voltage tail in excess of 200 V was found for nominal cathode flow rates. The implications of these results for standalone hollow cathode development tests are discussed.

Hall, Scott J.

Investigations of Spot-to-plume Mode Transition in a Hollow Cathode Discharge Using 2-D Axisymmetric Plasma Simulations

After decades of laboratory investigations that provided invaluable measurements and insight, the physics behind the transition from spot to plume modes in hollow cathodes remains one of the longest standing theoretical problems in electric propulsion. This has prohibited the development of ab initio models that allow for the prediction of the transition across different cathodes and operating conditions. Since the beginning of its development over a decade ago, simulations with the 2-D axisymmetric Orificed Cathode (OrCa2D) code have helped elucidate a wide range of processes in hollow cathode discharges. However, the code has never been used to investigate the onset of plume mode. We present results from the first OrCa2D simulations of a 25-A LaB6 cathode for a range of flow rates (5-20 sccm) in which transition from spot to plume modes is known to occur. The cathode in this study was one of the two technologies considered for the 12.5 kW Hall Effect Rocket with Magnetic Shielding (HERMeS) and operates nominally at 21 A and 14.8 sccm. The simulations capture the characteristic rise of the peak-to-peak amplitude in the keeper voltage oscillations and underscore the significance of the plume neutral gas in the transition. The plasma inside the cathode is found to be relatively quiescent throughout the transition, in agreement with previous experimental observations. The computed keeper voltage fluctuations at low flow rates (<8 sccm) are found to be driven by oscillations of the same frequency in the plasma plume with the following main characteristics: (1) they are of low frequency (<10 kHz), and associated with small longitudinal motion in the direction of the applied magnetic field, (2) they occur in a region of the plume where the neutral gas provided by the cathode has been fully depleted, and (3) they have a (small) wave velocity of about 100 m/s, which is at least ~10 smaller than the drift, thermal and acoustic speeds of the ions. At 8 sccm, when the transition to the large-amplitude oscillations begins, the ionization frequency in the neutral-depleted plume region ranges ~2-100 kHz. The frequency of the oscillations in the plasma (and keeper voltage) is found to be equal to the ionization frequency (~5 kHz) at the center of this region. The findings suggest that the transition to plume mode is driven by ionization processes in the near-plume of the cathode, in line with previous conjectures that were based solely on laboratory observations.

Polk, James E.