Test and evaluation of fuel cell catalysts Final report, 3 May 1967 - 3 May 1968
Corrosion resistance and anode activity data on interstitial compounds for fuel cell catalysts
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Corrosion resistance and anode activity data on interstitial compounds for fuel cell catalysts
The lead ruthenate pyrochlore Pb2Ru2O6.5, in both high- and low-area forms, has been characterized using thermogravimetric analysis, X-ray photoelectron spectroscopy, X-ray diffraction, cyclic voltammetry, and O2 reduction and generation kinetic-mechanistic studies. Mechanisms are proposed. Compounds in which part of the Ru is substituted with Ir have also been prepared. They exhibit somewhat better performance for O2 reduction in porous, gas-fed electrodes than the unsubstituted compound. The anodic corrosion resistance of pyrochlore-based porous electrodes was improved by using two different anionically conducting polymer overlayers, which slow down the diffusion of ruthenate and plumbate out of the electrode. The O2 generation performance was improved with both types of electrodes. With a hydrogel overlayer, the O2 reduction performance was also improved.
An understanding of fabrication processes, metallurgy, electrochemistry, and microbiology is crucial to the resolution of microbiologically influenced corrosion (MIC) problems. The object of this effort was to use AC impedance spectroscopy to characterize the corrosion resistance of Type II anodized aluminum alloy 2219-T87 in sterile and biologically active media and to examine the corrosion resistance of 316L, alloy 2219-T87, and titanium alloy 6-4 in the welded and unwelded conditions. The latter materials were immersed in sterile and biologically active media and corrosion currents were measured using the polarization resistance (DC) technique.
In the present work, a number of additives have been investigated for their effect on the charge characteristics of cells containing low temperature, high ester content electrolytes (1.0 M LiPF6 in ethylene carbonate (EC) + ethyl methyl carbonate (EMC) + methyl propionate (MP) 20:20:60 vol % + X additive). These experimental three-electrode cells are composed of graphite anodes, LiNiCoAlO2 cathodes, and a lithium metal reference electrode. Cells were first subjected to electrochemical characterization at various temperatures, consisting of performing Electrochemical Impedance Spectroscopy (EIS), linear micropolarization and Tafel polarization measurement to determine the kinetic parameters for both the anodes and cathodes. Following electrochemical characterization, the cells were subjected to charging at decreasing temperatures using C/5 rates to 4.10V, with a constant potential C/50 current taper. Analysis of the C/20 discharge following the charge at low temperature revealed either the presence or absence of a high voltage plateau during the initial stages of the discharge. This plateau has been linked to the presence of lithium metal on the anode previously and was used as a measure for the extent of lithium plating in the cell. Differential analysis (dV/dQ) was applied as well to more clearly visualize the position of the high voltage plateau and use the peak position (x-axis) in the dV/dQ plot as a gauge for the amount of plating which took place in the cell on the prior charge. Most additives investigated increased the resistance of the anode and decreased the resistance of the cathode, thereby leading to an overall increase in plating observed at low temperature. One additive, LiFSI, was found to be beneficial during low temperature charging, however studies of electrode kinetics from the cell containing LiFSI did not reveal significant improvements compared to the baseline.
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A summary of last years anode, plasma, and cathode findings is presented. A summary of this years activities and findings is also presented. A brief discussion of previous and current understanding is given and covers the following topics: existence of microinstabilities; the scaling of Va with the Hall parameter; the scaling of anomalous resistivity with the Hall parameter; the relation between anomalous resistivity and the anode drop; the presence of turbulence in the anode region; numerical simulation with anomalous transport; the use of magnets to decrease dissipation; performance testing with the new anode; the mechanisms behind the ionization sink; and lithiated cathode research.
Anodized coatings have been used as optical and thermal surfaces in spacecraft. Particulate contamination from cracked coatings is a concern for many applications. The major cause for the cracking is the difference in the coefficient of thermal expansion between the oxide coatings and the aluminum substrate. The loss of water when the coating is exposed to a vacuum also could induce cracking of the coating. Hot-water sealing was identified as the major cause for the cracking of the coatings because of the large temperature change when the parts were immersed in boiling water and the water was absorbed in the coating. when the hot-water sealing process was eliminated, the cracking resistance of the anodized coatings was greatly improved. Also, it was found that dyed black coatings were more susceptible than clear coatings to cracking during thermo-vacuum cyclings.
Chromic acid has long been used to produce a thin, corrosion resistant (Type I) coating on aluminum. Following anodizing, the hardware was sealed using a sodium dichromate solution. Sealing closes up pores inherent in the anodized coating, thus improving corrosion resistance. The thinness of the brittle coating is desirable from a fatigue standpoint, and chromium was absorbed by the coating during the sealing process, further improving corrosion resistance. Unfortunately, both chromic acid and sodium dichromate contain carcinogenic hexavalent chromium. Sulfuric acid is being considered as a replacement for chromic acid. Sulfuric acid of 10-20 percent concentration has traditionally been used to produce relatively thick (Types II and III) or abrasion resistant (Type III) coatings. A more dilute, that is five weight percent, sulfuric acid anodizing process, which produces a thinner coating than Type II or III, with nickel acetate as the sealant has been developed. The process was evaluated in regard to corrosion resistance, throwing power, fatigue life, and processing variable sensitivity, and shows promise as a replacement for the chromic acid process.
This study presents a novel polymer-in-salt (PIS) zwitterionic polyurethane-based solid polymer electrolyte (zPU-SPE) that offers high ionic conductivity, strong interaction with electrodes, and excellent mechanical and electrochemical stabilities, making it promising for high-performance all solid-state lithium batteries (ASSLBs). The zPU-SPE exhibits remarkable lithium-ion (Li+) conductivity (3.7 × 10⁻⁴ S cm−1 at 25 °C), enabled by exceptionally high salt loading of up to 90 wt.% (12.6 molar ratio of Li salt to polymer unit) without phase separation. It addresses the limitations of conventional SPEs by combining high ionic conductivity with a Li+ transference number of 0.44, achieved through the incorporation of zwitterionic groups that enhance ion dissociation and transport. The high surface energy (338.4 J m−2) and elasticity ensure excellent adhesion to Li anodes, reducing interfacial resistance and ensuring uniform Li+ flux. When tested in Li||zPU||LiFePO₄ and Li||zPU||S/C cells, the zPU-SPE demonstrated remarkable cycling stability, retaining 76% capacity after 2000 cycles with the LiFePO4 cathode, and achieving 84% capacity retention after 300 cycles with the S/C cathode. Molecular simulations and a range of experimental characterizations confirm the superior structural organization of the zPU matrix, contributing to its outstanding electrochemical performance. The findings strongly suggest that zPU-SPE is a promising candidate for next-generation ASSLBs.
To date, very little is understood about electrotransport in thin films. One reason for this is the lack of methods in which electromigration can be adequately monitored dynamically. In this thesis, a new nondestructive method for the study of the electrotransport phenomenon in thin aluminum films is presented. This method makes use of electrical resistance measurements of various regions along the test sample to monitor changes in resistance resulting from electromigration. The advantage of this method is that resistance changes can be observed long before void formation can be seen using standard microscopy methods. In order to achieve the best efficiency using this method, special consideration must be given to the design of the sample. Design problems and their respective solutions are given. The results of the electrical resistance measurements are interpreted by means of photographs taken with an scanning electron microscope. The increase in resistance of the aluminum samples is interpreted to be due to void formation. The expected decrease in resistance near the anode was never observed. It is shown that mass accumulation takes on the form of hillocks and whiskers on the surface of the aluminum film, which does not contribute appreciably to conductivity.
An apparatus for producing a vacuum arc plasma source device using a low mass, compact inductive energy storage circuit powered by a low voltage DC supply acts as a vacuum arc plasma thruster. An inductor is charged through a switch, subsequently the switch is opened and a voltage spike of Ldi/dt is produced initiating plasma across a resistive path separating anode and cathode. The plasma is subsequently maintained by energy stored in the inductor. Plasma is produced from cathode material, which allows for any electrically conductive material to be used. A planar structure, a tubular structure, and a coaxial structure allow for consumption of cathode material feed and thereby long lifetime of the thruster for long durations of time.
Anodized aluminum components can be treated to make them sufficiently electrically conductive to suppress discharges of static electricity. The treatment was conceived as a means of preventing static electric discharges on exterior satin-anodized aluminum (SAA) surfaces of spacecraft without adversely affecting the thermal-control/optical properties of the SAA and without need to apply electrically conductive paints, which eventually peel off in the harsh environment of outer space. The treatment can also be used to impart electrical conductivity to anodized housings of computers, medical electronic instruments, telephoneexchange equipment, and other terrestrial electronic equipment vulnerable to electrostatic discharge. The electrical resistivity of a typical anodized aluminum surface layer lies between 10(exp 11) and 10(exp 13) Omega-cm. To suppress electrostatic discharge, it is necessary to reduce the electrical resistivity significantly - preferably to < or = 10(exp 9) Omega-cm. The present treatment does this. The treatment is a direct electrodeposition process in which the outer anodized surface becomes covered and the pores in the surface filled with a transparent, electrically conductive metal oxide nanocomposite. Filling the pores with the nanocomposite reduces the transverse electrical resistivity and, in the original intended outer-space application, the exterior covering portion of the nanocomposite would afford the requisite electrical contact with the outer-space plasma. The electrical resistivity of the nanocomposite can be tailored to a value between 10(exp 7) and 10(exp 12) Omega-cm. Unlike electrically conductive paint, the nanocomposite becomes an integral part of the anodized aluminum substrate, without need for adhesive bonding material and without risk of subsequent peeling. The electrodeposition process is compatible with commercial anodizing production lines. At present, the electronics industry uses expensive, exotic, electrostaticdischarge- suppressing finishes: examples include silver impregnated anodized, black electroless nickel, black chrome, and black copper. In comparison with these competing finishes, the present nanocomposite finishes are expected to cost 50 to 20 percent less and to last longer.
Lap joints in thin-wall piping, tanks, and complex shapes are resistance-welded with both anode and cathode on same side of wall.
This paper presents a characterization of a commercially available position-sensitive detector of energetic ions and neutrals. The detector consists of two microchannel plates followed by a resistive position-encoding anode. The work includes measurement of absolute efficiencies of H(+), He(+), and O(+) ions in the energy range between 250 and 5000 eV, measurement of relative detection efficiencies as a function of particle impact angle, and a simple method for accurate measurement of the time at which a particle strikes the detector.
The partial electrochemical reduction of CO2 using ceramic oxygen generators (COGs) is well known and has been studied. Conventional COGs use yttria-stabilized zirconia (YSZ) electrolytes and operate at temperatures greater than 700 C (1, 2). Operating at a lower temperature has the advantage of reducing the mass of the ancillary components such as insulation. Moreover, complete reduction of metabolically produced CO2 (into carbon and oxygen) has the potential of reducing oxygen storage weight if the oxygen can be recovered. Recently, the University of Florida developed ceramic oxygen generators employing a bilayer electrolyte of gadolinia-doped ceria and erbia-stabilized bismuth oxide (ESB) for NASA s future exploration of Mars (3). The results showed that oxygen could be reliably produced from CO2 at temperatures as low as 400 C. These results indicate that this technology could be adapted to CO2 removal from a spacesuit and other applications in which CO2 removal is an issue. This strategy for CO2 removal in advanced life support systems employs a catalytic layer combined with a COG so that the CO2 is reduced completely to solid carbon and oxygen. First, to reduce the COG operating temperature, a thin, bilayer electrolyte was employed. Second, to promote full CO2 reduction while avoiding the problem of carbon deposition on the COG cathode, a catalytic carbon deposition layer was designed and the cathode utilized materials shown to be coke resistant. Third, a composite anode was used consisting of bismuth ruthenate (BRO) and ESB that has been shown to have high performance (4). The inset of figure 1 shows the conceptual design of the tubular COG and the rest of the figure shows schematically the test apparatus. Figure 2 shows the microstructure of a COG tube prior to testing. During testing, current is applied across the cell and initially CuO is reduced to copper metal by electrochemical pumping. Then the oxygen source becomes the CO/CO2. This presentation details the results of testing the COG.
There is disclosed an anode for an arcjet thruster which resists erosion during start-up on constriction during steady-state operation. The anode includes a converging upstream portion, a diverging downstream portion and a constricted portion disposed therebetween. In one embodiment of the invention, rails formed in the constricted portion accelerate the passage of an arc during start-up reducing erosion. In a second embodiment, a higher strength material resists bulging as a result of the thermal gradient within the nozzle.
Quarternary lithium-ion battery electrolyte solutions containing ester co-solvents in mixtures of carbonates have been demonstrated to have high conductivity at low temperatures (< -20C). However, in some cases the presence of such co-solvents does not directly translate into improved low temperature cell performance, presumably due to the formation of ionically resistive surface films on carbonaceous anodes. In order to understand this behavior, a number of lithium-graphite cells have been studied containing electrolytes with various ester co-solvents, including methyl acetate (MA), ethyl acetate (EA), ethyl propionate (EP), and ethyl butyrate (EB). The charge/discharge characterization of these cells indicates that the higher molecular weight esters result in electrolytes which possess superior low temperature performance in contrast to the lower molecular weight ester-containing solutions, even though these solutions display lower conductivity values.
Ethyl acetate (EA) was identified as a promising electrolyte solvent for sodium-ion batteries (SIBs), exhibiting low viscosity, cost-effectiveness, and low toxicity. Despite a significant portion of aggregation being linked to the weak solvation of Na + /EA as revealed by molecular dynamics (MD) simulations, pulsed-field gradient nuclear magnetic resonance (pfg-NMR) analysis identified a noteworthy Na+ diffusion coefficient of 3.95×10 -10 m 2 s -1 at 25°C in the presence of 1 m NaPF 6 salt. Employing fluoroethylene carbonate (FEC) as a film-forming additive to create electrode-electrolyte interphase, this electrolyte surprisingly made ~210 mAh Na 0.97 Ca 0.03 [Mn 0.39 Fe 0.31 Ni 0.22 Zn 0.08 ]O 2 (NCMFNZO)/hard carbon (HC) pouch cells achieve a lengthy cycling lifetime of 250 cycles with ~80 % capacity retention, cycled up to 4.0 V at 40°C. X-ray photoelectron spectroscopy (XPS) revealed increasing interphasial organic species over cycling, augmenting charge transfer resistance on both cathode and anode, particularly during fast charging or low temperatures (<10°C), promoting Na plating. Finally, gas chromatography-mass spectrometry combined with density functional theory identified CO 2 as the major gas generated from charged cathode/electrolyte interactions, exhibiting temperature/voltage dependence.