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A study was made of the effect of arc length, cathode thickness, current strength, gas pressure and the chemical nature of the cathode material and filling gases upon the material loss from Cu, Fe, and Ag cathodes in arcs. The results show that the analysis of the phenomenon is complex and the energy balance is difficult to formulate.
Commercialization of lithium-air batteries faces many challenges, such as electrolyte decomposition, short cycle life, low energy and power density, etc. However, commercialization of Li-O2 batteries for aeronautics is much more challenging due to additional safety constraints on cyclability and performance (high specific power and specific energy). For this presentation, we will discuss inter-related aspects of physics-based modeling of a pack: cell and battery model calibration. In addition, we will evaluate and present optimal battery designs for high discharge current density, high discharge time, and low battery mass using simulation-based optimization.The Finite Element Model (FEM) used to simulate a Li-O2 cell is based on the work of Bevara [1]. The different aspects of the model are based on: porous electrode theory and concentrated electrolyte theory; quantum tunneling model for the resistance of conformal layer of discharge product (Li2O2) [1]; Butler-Volmer kinetics for electrochemical reaction; Fick's diffusion for oxygen transport; and an oxygen dissolution model is applied at the air/electrolyte interface [2]. The electrolyte properties such as ion conductivity, ion diffusion, oxygen diffusion, and mass density of the electrolyte were taken from Molecular Dynamics (MD) simulations [3]; while the other model parameters, which includes mass of cell components, were calibrated to match experiments at high discharge current densities. The cell mass includes the anode, cathode, separator, electrolyte, and other components (such as current collector). This calibrated model is used to perform parametric studies on cathode thickness, porosity, tortuosity, carbon particle size, electrolyte transport and material properties, partial pressure of oxygen, discharge time, and discharge current density to study optimal designs for high specific power and energy. References:1. Bevara, V. & Andrei, P. (2014), J. Electrochem. Soc. 161 (14), A2068-A2079.2.Mehta, M. & Andrei, P. (2015), J. Power Sources. 286, 299-308.3.Liyana-Arachchi, T.; Haskins, J.; Burke, C.; Diederichsen, K.; McCloskey, B.; & Lawson, J. (2018), J. Phys. Chem. B. 122 (36), 8548 - 8559.4.Choi, W.; Kikumoto, H.; Choudhary, R. & Ooka, R. (2018), Applied Energy, 209, 306-321.
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Electronic cathodes for use in electron bombardment ion thrustors
Electrode materials that exhibit mixed conductivity (that is, both electronic and ionic conductivity) have been investigated in a continuing effort to improve the performance of the alkali metal thermal-to-electric converter (AMTEC). These electrode materials are intended primarily for use on the cathode side of the sodium-ion-conducting solid electrolyte of a sodium-based AMTEC cell. They may also prove useful in sodium-sulfur batteries, which are under study for use in electric vehicles. An understanding of the roles played by the two types of conduction in the cathode of a sodium-based AMTEC cell is prerequisite to understanding the advantages afforded by these materials. In a sodium-based AMTEC cell, the anode face of an anode/solid-electrolyte/cathode sandwich is exposed to Na vapor at a suitable pressure. Upon making contact with the solid electrolyte on the anode side, Na atoms oxidize to form Na+ ions and electrons. Na+ ions then travel through the electrolyte to the cathode. Na+ ions leave the electrolyte at the cathode/electrolyte interface and are reduced by electrons that have been conducted through an external electrical load from the anode to the cathode. Once the Na+ ions have been reduced to Na atoms, they travel through the cathode to vaporize into a volume where the Na vapor pressure is much lower than it is on the anode side. Thus, the cathode design is subject to competing requirements to be thin enough to allow transport of sodium to the low-pressure side, yet thick enough to afford adequate electronic conductivity. The concept underlying the development of the present mixed conducting electrode materials is the following: The constraint on the thickness of the cathode can be eased by incorporating Na+ -ionconducting material to facilitate transport of sodium through the cathode in ionic form. At the same time, by virtue of the electronically conducting material mixed with the ionically conducting material, reduction of Na+ ions to Na atoms can take place throughout the thickness of the cathode. The net effect is to reduce the diffusion and flow resistance to sodium through the electrode while reducing the electronic resistance by providing shorter conduction paths for electrons. Reduced resistance to both sodium transport and electronic conductivity results in an increase in electric power output.
This paper describes the development of a thick-film microcathode for use in Li-ion microbatteries in order to provide increased power and energy per area. These cathodes take advantage of a composite porous electrode structure, utilizing carbon nanotubes (CNT) as the conductive filler. The use of carbon nanotubes was found to significantly reduce the measured resistance of the electrodes, increase active material accessibility, and improve electrode performance. In particular, the cycling and power performance of the thick-film cathodes was significantly improved, and the need for compression was eliminated. Cathode thickness and CNT content were optimized to maximize capacity and power performance. Power capability of >50 mW/sq cm (17 mA/sq cm) with discharge capacity of >0.17 mAh/sq cm was demonstrated. The feasibility of fabricating thick-film microcathodes capable of providing the power and capacity needed for use in autonomous microsensor systems was also demonstrated.
The contributions of Cerenkov emission, luminescence, secondary electron emission, and bremsstrahlung to radiation-induced data current and noise of multiplier phototubes were analyzed quantitatively. Fluorescence and Cerenkov emission in the tube window are the major contributors and can quantitatively account for dark count levels observed in orbit. Radiation-induced noise can be minimized by shielding, tube selection, and mode of operation. Optical decoupling of windows and cathode (side-window tubes) leads to further reduction of radiation-induced dark counts, as does reducing the window thickness and effective cathode area, and selection of window/cathode combinations of low fluorescence efficiency. In trapped radiation-free regions of near-earth orbits and in free space, Cerenkov emission by relativistic particles contributes predominantly to the photoelectron yield per event. Operating multiplier phototubes in the photon (pulse) counting mode will discriminate against these large pulses and substantially reduce the dark count and noise to levels determined by fluorescence.
Porous structure effects in oxygen consuming cathode, discussing electrode thickness, effective pore diameter, pressure difference and electrode performance
Field-emission devices (cold cathodes) having low electron affinities can be fabricated through lattice-mismatched epitaxial growth of nitrides of elements from group III of the periodic table. Field emission of electrons from solid surfaces is typically utilized in vacuum microelectronic devices, including some display devices. The present field-emission devices and the method of fabricating them were developed to satisfy needs to reduce the cost of fabricating field emitters, make them compatible with established techniques for deposition of and on silicon, and enable monolithic integration of field emitters with silicon-based driving circuitry. In fabricating a device of this type, one deposits a nitride of one or more group-III elements on a substrate of (111) silicon or other suitable material. One example of a suitable deposition process is chemical vapor deposition in a reactor that contains plasma generated by use of electron cyclotron resonance. Under properly chosen growth conditions, the large mismatch between the crystal lattices of the substrate and the nitride causes strains to accumulate in the growing nitride film, such that the associated stresses cause the film to crack. The cracks lie in planes parallel to the direction of growth, so that the growing nitride film becomes divided into microscopic growing single-crystal columns. The outer ends of the fully-grown columns can serve as field-emission tips. By virtue of their chemical compositions and crystalline structures, the columns have low work functions and high electrical conductivities, both of which are desirable for field emission of electrons. From examination of transmission electron micrographs of a prototype device, the average column width was determined to be about 100 nm and the sharpness of the tips was determined to be characterized by a dimension somewhat less than 100 nm. The areal density of the columns was found to about 5 x 10(exp 9)/sq cm . about 4 to 5 orders of magnitude greater than the areal density of tips in prior field-emission devices. The electric field necessary to turn on the emission current and the current per tip in this device are both lower than in prior field-emission devices, such that it becomes possible to achieve longer operational lifetime. Moreover, notwithstanding the lower current per tip, because of the greater areal density of tips, it becomes possible to achieve greater current density averaged over the cathode area. The thickness of the grown nitride film (equivalently, the length of the columns) could lie between about 0.5 microns and a few microns; in any event, a thickness of about 1 micron is sufficient and costs less than do greater thicknesses. It may be possible to grow nitride emitter columns on glass or other substrate materials that cost less than silicon does. What is important in the choice of substrate material is the difference between the substrate and nitride crystalline structures. Inasmuch as the deposition process is nondestructive, an ability to grow emitter columns on a variety of materials would be advantageous in that it would facilitate the integration of field-emitter structures onto previously processed integrated circuits.
Refractory-metal heater base wound with a thin refractory metal wire increases the longevity of oxide-coated cathodes. The wire-wound unit is impregnated with the required thickness of metal oxide. This cathode is useful in magnetohydrodynamic systems and in electron tubes.
Eddy-current flaw detector with cathode-ray tube (CRT) used to compare layer thickness of conductive paint on metallic substrates.
By the use of fractional factorials, paths of steepest ascent and direct comparison experimentation, performance characteristics of the CuF2/LiAsF6-MF/Li electrochemical system were optimized under conditions of temperature environment, discharge rate, active stand, and use of anhydrous cathodes. Two hundred ampere-hours/lb of CuF2 and 600 watt-hours/lb of CuF2 were achieved in anhydrous cells at plus 40 C and at a discharge rate of 10 ma sq cm. Electrical performance is primarily altered by temperature and discharge rate; however, other factors such as cathode water content, cathode conductor content, separator thickness, and the use of SO2 gas also have significant effects.
Solid oxide fuel cell (SOFC) systems for aircraft applications require order of magnitude increase in specific power density and long life under aircraft operating conditions. Advanced SOFC materials and fabrication processes are being developed at NASA GRC to increase specific power density and durability of SOFC cell and stack. Initial research efforts for increasing specific power density are directed toward increasing the operating temperature for the SOFC system and reducing the weight of the stack. While significant research is underway to develop anode supported SOFC system operating at temperatures in the range of 650 - 850 C for ground power generation applications, such temperatures may not yield the power densities required for aircraft applications. For electrode-supported cells, SOFC stacks with power densities greater than 1.0 W/sq cm are favorable at temperatures in excess of 900 C. The performance of various commercial and developmental anode supported cells is currently being evaluated in the temperature range of 900 to 1000 C to assess the performance gains and materials reliability. The results from these studies will be presented. Since metal interconnects developed for lower temperature operation are not practical at these high temperatures, advanced perovskite based ceramic interconnects with high electronic conductivity and lower sintering temperatures are being developed. Another option for increasing specific power density of SOFC stacks is to decrease the stack weight. Since the interconnect contributes to a significant portion of the stack weight, considerable weight benefits can be derived by decreasing its thickness. Eliminating the gas channels in the interconnect by engineering the pore structure in both anode and cathode can offer significant reduction in thickness of the ceramic interconnect material. New solid oxide fuel cells are being developed with porous engineered electrode supported structures with a 10 - 20 micron thin electrolyte. The performance data for advanced SOFC cells with engineered porosity in both electrodes will be presented.
The transport of the zincate ion to the alkaline zinc cathode was studied by observing the decay of the zincate concentration gradient at a horizontal zinc cathode after charging. This decay was found to approximate first order kinetics as expected from a proposed boundary layer model. The concentrations were calculated from polarization voltages. The decay half life was shown to be a linear function of the thickness of porous zinc deposit on the cathode indicating a very rapid transport of zincate through porous zinc metal. The rapid transport is attributed to an electrochemical mechanism. From the linear dependence of the half life on the thickness the boundary layer thickness was found to be about 0.010 cm when the cathode was at the bottom of the cell. No significant dependence of the boundary layer thickness on the viscosity of electrolyte was observed. The data also indicated a relatively sharp transition between the diffusion and convection transport regions. When the cathode was at the top of the cell, the boundary layer thickness was found to be roughly 0.080 cm. The diffusion of zincate ion through asbestos submerged in alkaline electrolyte was shown to be comparable with that predicted from the bulk diffusion coefficient of the zincate ion in alkali.
Nano-multiplication-region avalanche photodiodes (NAPDs), and imaging arrays of NAPDs integrated with complementary metal oxide/semiconductor (CMOS) active-pixel-sensor integrated circuitry, are being developed for applications in which there are requirements for high-sensitivity (including photoncounting) detection and imaging at wavelengths from about 250 to 950 nm. With respect to sensitivity and to such other characteristics as speed, geometric array format, radiation hardness, power demand of associated circuitry, size, weight, and robustness, NAPDs and arrays thereof are expected to be superior to prior photodetectors and arrays including CMOS active-pixel sensors (APSs), charge-coupled devices (CCDs), traditional APDs, and microchannelplate/ CCD combinations. Figure 1 depicts a conceptual NAPD array, integrated with APS circuitry, fabricated on a thick silicon-on-insulator wafer (SOI). Figure 2 presents selected aspects of the structure of a typical single pixel, which would include a metal oxide/semiconductor field-effect transistor (MOSFET) integrated with the NAPD. The NAPDs would reside in silicon islands formed on the buried oxide (BOX) layer of the SOI wafer. The silicon islands would be surrounded by oxide-filled insulation trenches, which, together with the BOX layer, would constitute an oxide embedding structure. There would be two kinds of silicon islands: NAPD islands for the NAPDs and MOSFET islands for in-pixel and global CMOS circuits. Typically, the silicon islands would be made between 5 and 10 m thick, but, if necessary, the thickness could be chosen outside this range. The side walls of the silicon islands would be heavily doped with electron-acceptor impurities (p+-doped) to form anodes for the photodiodes and guard layers for the MOSFETs. A nanoscale reach-through structure at the front (top in the figures) central position of each NAPD island would contain the APD multiplication region. Typically, the reach-through structure would be about 0.1 microns in diameter and between 0.3 and 0.4 nm high. The top layer in the reach-through structure would be heavily doped with electron-donor impurities (n+-doped) to make it act as a cathode. A layer beneath the cathode, between 0.1 and 0.2 nm thick, would be p-doped to a concentration .10(exp 17)cu cm. A thin n+-doped polysilicon pad would be formed on the top of the cathode to protect the cathode against erosion during a metal-silicon alloying step that would be part of the process of fabricating the array.
The study was carried out by observing the decay of the zincate concentration gradient at a horizontal zinc cathode after charging. This decay was found to approximate first order kinetics as expected from a proposed boundary layer model. The decay half life was shown to be a linear function of the thickness of porous zinc deposit on the cathode indicating a very rapid transport of zincate through porous zinc metal. The rapid transport is attributed to an electrochemical mechanism. The data also indicated a relatively sharp transition between the diffusion and convection transport regions. The diffusion of zincate ion through asbestos submerged in alkaline electrolyte was shown to be comparable with that predicted from the bulk diffusion coefficient of the zincate ion in alkali.
The performance of quasisteady multimegawatt MPD thrusters is significantly affected by anode thickness, location, and orifice radius, and by cathode length. Terminal voltage oscillations and electrode erosion are deferred until higher currents by anodes at more downstream locations and of smaller orifice radius and by cathodes of greater length. Without an optimized geometry, specific impulses of 3300 s and thrust efficiencies up to 31% are implied by the best data.
The goal of producing spiral wound D cell was met. The cell design and electrodes, particularly the carbon cathodes were produced in-house. Also all parts were assembled, the welding performed, the electrolyte aided and the cells sealed in-house. The lithium capacity (theoretical) was 19.3 Ah and that of the SOCl2 in the 1.8 m LiAlCl4 electrolyte, 16.4 Ah (a greater excess of SOCl2 is necessary for safe high rate operation). The electrode surface area was 452 sq cm. The carbon electrode comprised Shawinigen Black/Teflon -30 (90/10 by weight) mixture 0.020 inches thick on an expanded metal screen prepared in the JPL laboratory. There were two tab connections to the cathode. The 0.0078 inch thick lithium foil was rolled into an expanded nickel screen. The separator was Mead 934-5 fiberglass material.