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62 records · Page 4

Proton exchange membrane fuel cells for space and electric vehicle applications: From basic research to technology development

The proton exchange membrane fuel cell (PEMFC) is one of the most promising electrochemical power sources for space and electric vehicle applications. The wide spectrum of R&D activities on PEMFC's, carried out in our Center from 1988 to date, is as follows (1) Electrode Kinetic and Electrocatalysis of Oxygen Reduction; (2) Optimization of Structures of Electrodes and of Membrane and Electrode Assemblies; (3) Selection and Evaluation of Advanced Proton Conducting Membranes and of Operating Conditions to Attain High Energy Efficiency; (4) Modeling Analysis of Fuel Cell Performance and of Thermal and Water Management; and (5) Engineering Design and Development of Multicell Stacks. The accomplishments on these tasks may be summarized as follows: (1) A microelectrode technique was developed to determine the electrode kinetic parameters for the fuel cell reactions and mass transport parameters for the H2 and O2 reactants in the proton conducting membrane. (2) High energy efficiencies and high power densities were demonstrated in PEMFCs with low platinum loading electrodes (0.4 mg/cm(exp 2) or less), advanced membranes and optimized structures of membrane and electrode assemblies, as well as operating conditions. (3) The modeling analyses revealed methods to minimize mass transport limitations, particularly with air as the cathodic reactant; and for efficient thermal and water management. (4) Work is in progress to develop multi-kilowatt stacks with the electrodes containing low platinum loadings.

Srinivasan, Supramaniam↗

Near-ambient solid polymer fuel cell

Fuel cells are extremely attractive for extraterrestrial and terrestrial applications because of their high energy conversion efficiency without noise or environmental pollution. Among the various fuel cell systems the advanced polymer electrolyte membrane fuel cells based on sulfonated fluoropolymers (e.g., Nafion) are particularly attractive because they are fairly rugged, solid state, quite conductive, of good chemical and thermal stability and show good oxygen reduction kinetics due to the low specific adsorption of the electrolyte on the platinum catalyst. The objective of this program is to develop a solid polymer fuel cell which can efficiently operate at near ambient temperatures without ancillary components for humidification and/or pressurization of the fuel or oxidant gases. During the Phase 1 effort we fabricated novel integral electrode-membrane structures where the dispersed platinum catalyst is precipitated within the Nafion ionomer. This resulted in electrode-membrane units without interfacial barriers permitting unhindered water diffusion from cathode to anode. The integral electrode-membrane structures were tested as fuel cells operating on H2 and O2 or air at 1 to 2 atm and 10 to 50 C without gas humidification. We demonstrated that cells with completely dry membranes could be self started at room temperature and subsequently operated on dry gas for extended time. Typical room temperature low pressure operation with unoptimized electrodes yielded 100 mA/cm(exp 2) at 0.5V and maximum currents over 300 mA/cm(exp 2) with low platinum loadings. Our results clearly demonstrate that operation of proton exchange membrane fuel cells at ambient conditions is feasible. Optimization of the electrode-membrane structure is necessary to assess the full performance potential but we expect significant gains in weight and volume power density for the system. The reduced complexity will make fuel cells also attractive for smaller and portable power supplies and as replacement for batteries.

Holleck, G. L.↗

The kinetics of the O2/CO2 reaction in molten carbonate - Reaction orders for O2 and CO2 on NiO

The kinetics of the O2/CO2 reaction in molten carbonate is investigated using paste electrolytes and nickel sinter electrodes. A two-step approach to the determination of reaction orders is employed. First, exchange currents at various P(CO2) and P(O2) were measured using the low polarization method. Second, alpha(+) and alpha(-) values were obtained from the slope of the Allen-Hickling plot for current densities low enough so that concentration polarization within the electrode can be neglected. The reaction orders are + 1/4 in CO2 and + 5/8 in O2 in the cathodic direction, and - 3/4 in CO2 and + 1/8 in O2 in the anodic direction.

Winnick, J.↗

Electrochemical impedance spectroscopy of lithium-titanium disulfide rechargeable cells

The two-terminal alternating current impedance of Li/TiS2 rechargeable cells was studied as a function of frequency, state-of-charge, and extended cycling. Analysis based on a plausible equivalent circuit model for the Li/TiS2 cell leads to evaluation of kinetic parameters for the various physicochemical processes occurring at the electrode/electrolyte interfaces. To investigate the causes of cell degradation during extended cycling, the parameters evaluated for cells cycled 5 times were compared with the parameters of cells cycled over 600 times. The findings are that the combined ohmic resistance of the electrolyte and electrodes suffers a tenfold increase after extended cycling, while the charge-transfer resistance and diffusional impedance at the TiS2/electrolyte interface are not significantIy affected. The results reflect the morphological change and increase in area of the anode due to cycling. The study also shows that overdischarge of a cathode-limited cell causes a decrease in the diffusion coefficient of the lithium ion in the cathode.

Narayanan, S. R.↗

High-Power, High-Efficiency Ka-Band Space Traveling-Wave Tube

The L-3 Communications Model 999H traveling-wave tube (TWT) has been demonstrated to generate an output power of 144 W at 60-percent overall efficiency in continuous-wave operation over the frequency band from 31.8 to 32.3 GHz. The best TWT heretofore commercially available for operation in the affected frequency band is characterized by an output power of only 35 W and an efficiency of 50 percent. Moreover, whereas prior TWTs are limited to single output power levels, it has been shown that the output power of the Model 999H can be varied from 54 to 144 W. A TWT is a vacuum electronic device used to amplify microwave signals. TWTs are typically used in free-space communication systems because they are capable of operating at power and efficiency levels significantly higher than those of solid-state devices. In a TWT, an electron beam is generated by an electron gun consisting of a cathode, focusing electrodes, and an anode. The electrons pass through a hole in the anode and are focused into a cylindrical beam by a stack of periodic permanent magnets and travel along the axis of an electrically conductive helix, along which propagates an electromagnetic wave that has been launched by an input signal that is to be amplified. The beam travels within the helix at a velocity close to the phase velocity of the electromagnetic wave. The electromagnetic field decelerates some of the electrons and accelerates others, causing the beam to become formed into electron bunches, which further interact with the electromagnetic wave in such a manner as to surrender kinetic energy to the wave, thereby amplifying the wave. The net result is to amplify the input signal by a factor of about 100,000. After the electrons have passed along the helix, they impinge on electrodes in a collector. The collector decelerates the electrons in such a manner as to recover most of the remaining kinetic energy and thereby significantly increase the power efficiency of the TWT.

Krawczyk, Richard↗

The impedance characteristic of a spherical probe in an isotropic plasma.

Experimental investigation of the impedance characteristic of a spherical plasma probe for a quantitative assessment of theoretical work, and of hydrodynamic or fluid theory in particular. A stable, low-temperature (about 500K) plasma was produced in nitrogen by a cold-cathode discharge, with a plasma frequency of the order of 15 MHz and with an electron collision frequency in the range from one to ten million per sec. Hydrodynamic probe theory was tested against the experimental results for the specific cases corresponding to the probe at floating potential and at space potential. Good agreement was obtained for both the real and imaginary parts. The real part of the impedance shows a peak near the plasma frequency, a small shift being explicable in terms of realistic sheath profiles. Electron density can thus be deduced rather accurately, and electron temperature approximately, on the basis of hydrodynamic theory. Accurate values of the electron-neutral collision frequency were also obtained for plasmas where the collision frequency was larger than 0.4 times the radian plasma frequency. At lower pressures the presence of collisionless or Landau damping was clearly established, and the more accurate kinetic theory is necessary to explain the experimental results.

Tarstrup, J.↗

Products of Dissociative Recombination in the Ionosphere

SRI International undertook a novel experimental measurement of the product states formed by dissociative recombination (DR) of O2(+), NO(+), and N2(+) as a function of both electron energy and reactant ion vibrational level. For these measurements we used a recently developed experimental technique for measuring dissociation product distributions that allows both the branching ratios to be accurately determined and the electronic and rovibrational state composition of the reactant ions to be specified. DR is the dominant electron loss mechanism in all regions of the ionosphere. In this process, electron attachment to the molecular ion produces an unstable neutral molecule that rapidly dissociates. For a molecular ion such as O2(+), the dissociation recombination reaction is (1) O2(+) + e yields O + O + W. The atomic products of this reaction, in this case two oxygen atoms, can be produced in a variety of excited states and with a variety of kinetic energies, as represented by W in Eq. (1). These atoms are not only active in the neutral chemistry of the ionosphere, but are also especially important because their optical emissions are often used to infer in situ concentrations of the parent molecular ion and ambient electron densities. Many laboratory measurements have been made of DR reaction rates under a wide range of electron temperatures, but very little is known about the actual distributions among the final states of the atomic products. This lack of knowledge seriously limits the validity and effectiveness of efforts to model both natural and man-made ionospheric disturbances. Bates recently identified major deficiencies in the currently accepted branching ratios for O2(+) as they relate to blue and green line emission measurements in the nocturnal F-region. During our two-year effort, we partially satisfied our ambitious goals. We constructed and operated a variable pressure, electron-impact ion source and a high pressure, hollow-cathode discharge ion source for O2(+), NO(+), and N2(+) beams. Translational spectroscopy of the products of dissociative charge transfer in Cs vapor was used to accurately assay the composition of the O2(+) and NO(+) beams and to develop a methodology for the vibrationally controlled preparation of the ground state ion beams. Attempts to assay the N2(+) beam revealed a novel two-electron process in the charge transfer reactions. A coaxial electron gun for the DR measurements was constructed following an extensive numerical design of the fields. Tests of the gun, however, found substantial perturbations of the magnetic fields by the soft iron (CMI-C) assembly containing the Langmuir probe that locates the electron beam. Hydrogen annealing of the iron failed to eliminate the field perturbations, necessitating the removal of the probe assembly. During this work on the coaxial electron gun, we discovered that predissociated high Rydberg states of O2 could be produced by subjecting the molecules to a sudden perturbation by an electromagnetic field. This technique allowed a measurement of the product branching to the atomic limits for the lowest seven vibrational levels of O2(+).

Cosby, Philip↗

High Power Flex-Propellant Arcjet Performance

A MW-class electrothermal arcjet based on a water-cooled, wall-stabilized, constricted arc discharge configuration was subjected to extensive performance testing using hydrogen and simulated ammonia propellants with the deliberate aim of advancing technology readiness level for potential space propulsion applications. The breadboard design incorporates alternating conductor/insulator wafers to form a discharge barrel enclosure with a 2.5-cm internal bore diameter and an overall length of approximately 1 meter. Swirling propellant flow is introduced into the barrel, and a DC arc discharge mode is established between a backplate tungsten cathode button and a downstream ringanode/ spin-coil assembly. The arc-heated propellant then enters a short mixing plenum and is accelerated through a converging-diverging graphite nozzle. This innovative design configuration differs substantially from conventional arcjet thrusters, in which the throat functions as constrictor and the expansion nozzle serves as the anode, and permits the attainment of an equilibrium sonic throat (EST) condition. During the test program, applied electrical input power was varied between 0.5-1 MW with hydrogen and simulated ammonia flow rates in the range of 4-12 g/s and 15-35 g/s, respectively. The ranges of investigated specific input energy therefore fell between 50-250 MJ/kg for hydrogen and 10-60 MJ/kg for ammonia. In both cases, observed arc efficiencies were between 40-60 percent as determined via a simple heat balance method based on electrical input power and coolant water calorimeter measurements. These experimental results were found to be in excellent agreement with theoretical chemical equilibrium predictions, thereby validating the EST assumption and enabling the utilization of standard TDK nozzle expansion analyses to reliably infer baseline thruster performance characteristics. Inferred specific impulse performance accounting for recombination kinetics during the expansion process implied nearly frozen flow in the nozzle and yielded performance ranges of 800-1100 sec for hydrogen and 400-600 sec for ammonia. Inferred thrust-to-power ratios were in the range of 30-10 lbf/MWe for hydrogen and 60-20 lbf/MWe for ammonia. Successful completion of this test series represents a fundamental milestone in the progression of high power arcjet technology, and it is hoped that the results may serve as a reliable touchstone for the future development of MW-class regeneratively-cooled flex-propellant plasma rockets.

Litchford, Ron J.↗