Optimization of design parameters for spacecraft nickel-cadmium cells containing recombination and control electrodes Quarterly report, Aug. - Oct. 1968
Oxygen sensing and recombination electrodes tested for fuel cell application
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Oxygen sensing and recombination electrodes tested for fuel cell application
Cycle capability of electrochemical cells built with oxygen recombination and oxygen sensing control electrodes
The objectives of this study were to use electrochemical impedance spectroscopy (EIS) to study the oxygen-reduction reaction under lower humidification conditions than previously studied. The EIS technique permits the discrimination of electrode kinetics of oxygen reduction, mass transport of O2 in the membrane, and the electrical characteristics of the membrane. Electrode-kinetic parameters for the oxygen-reduction reaction, corrosion current densities for Pt, and double-layer capacitances were calculated. The production of water due to electrochemical reduction of oxygen greatly influenced the EIS response and the electrode kinetics at the Pt/Nafion interface. From the finite-length Warburg behavior, a measure of the diffusion coefficient of oxygen in Nafion and diffusion-layer thickness was obtained. An analysis of the EIS data in the high-frequency domain yielded membrane and interfacial characteristics such as ionic conductivity of the membrane, membrane grain-boundary capacitance and resistance, and uncompensated resistance.
Oxygen signal and recombination electrodes developed for charge control of spacecraft nickel cadmium batteries
Plasma-polymerized tetrafluoroethylene (PPTFE) coated potassium bromide IR window are shown to possess better resistance to moisture than either ethylene or chlorotrifluoroethylene. The PPTFE-coated windows tolerated an upper limit relative humidity of about 80% at 297 K, without visible damage to either window or coating, over a period of 24 hours. Elemental analysis of the bulk, and photoelectron spectroscopy of the coating surface, showed that PPTFE coatings deposited downstream of the internal plasma reactor electrodes contained less atmospheric oxygen than coatings deposited between the electrodes; perhaps accounting for the improved moisture resistance.
Extraction of oxygen from Martian atmosphere and compression of lunar oxygen can utilize stabilized zirconia electrochemical pumps. Silver membranes can be used as electrodes to increase oxygen yield at relatively low temperatures. This study has investigated oxygen permeation through Ag 0.05Zr membranes with glow-discharge assisted disassociation. Data show that the overall process is controlled by bulk diffusion but the slow dissociative adsorption onto the surface limited the overall transport substantially. With glow-discharge assisted dissociation, an order of magnitude increase in oxygen throughput can be produced at relatively low temperatures (450-550C).
Electrochemical impedance spectra of rolled and bonded and sintered porous nickel battery electrodes were recorded periodically during charge/discharge cycling in concentrated KOH solution at various temperatures. A transmission line model (TLM) was adopted to represent the impedance of the porous electrodes, and various model parameters were adjusted in a curve fitting routine to reproduce the experimental impedances. Degradation processes for rolled and bonded electrodes were deduced from changes in model parameters with electrode cycling time. In developing the TLM, impedance spectra of planar (non-porous) electrodes were used to represent the pore wall and backing plate interfacial impedances. These data were measured over a range of potentials and temperatures, and an equivalent circuit model was adopted to represent the planar electrode data. Cyclic voltammetry was used to study the characteristics of the oxygen evolution reaction on planar nickel electrodes during charging, since oxygen evolution can affect battery electrode charging efficiency and ultimately electrode cycle life if the overpotential for oxygen evolution is sufficiently low. Transmission line modeling results suggest that porous rolled and bonded nickel electrodes undergo restructuring during charge/discharge cycling prior to failure.
AC impedance spectra of porous nickel battery electrodes were recorded periodically during charge/discharge cycling in concentrated KOH solution at various temperatures. A transmission line model (TLM) was adopted to represent the impedance of the porous electrodes, and various model parameters were adjusted in a curve fitting routine to reproduce the experimental impedances. Degradation processes were deduced from changes in model parameters with electrode cycling time. In developing the TLM, impedance spectra of planar (nonporous) electrodes were used to represent the pore wall and backing plate interfacial impedances. These data were measured over a range of potentials and temperatures, and an equivalent circuit model was adopted to represent the planar electrode data. Cyclic voltammetry was used to study the characteristics of the oxygen evolution reaction on planar nickel electrodes during charging, since oxygen evolution can affect battery electrode charging efficiency and ultimately electrode cycle life if the overpotential for oxygen evolution is sufficiently low.
This paper describes tests designed to predict the performance of fuel cell electrodes, as applied to an alkaline oxygen-fuel cell having specially fabricated porous-carbon electrodes with various amounts of dispersed platinum or gold as active catalysts. The tests are based on information obtained from the techniques of cyclic voltammetry and polarization. The parameters obtained from cyclic voltammetry were of limited use in predicting fuel cell performance of the cathode. On the other hand, half-cell polarization measurements offered close simulation of the oxygen electrode, although a predictor of the electrode life is still lacking. The very low polarization of the Au-10 percent Pt catalytic electrode suggests that single-phase catalysts should be considered.
Measurement of the influence of differential pressure on electrode activity in oxygen cathodes made up of beds of uniform silver spheres (156 micron diameter). The extent and nature of this dependence could be explained through use of the concept of pendular and funicular liquid configuration in the pore space of the electrode.
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.
An ambient temperature oxygen microsensor, based on a Nafion polymer electrolyte, has been developed and was microfabricated using thin-film technologies. A challenge in the operation of Nafion-based sensor systems is that the conductivity of Nafion film depends on the humidity in the film. Nafion film loses conductivity when the moisture content in the film is too low, which can affect sensor operation. The advancement here is the identification of a method to retain the operation of the Nafion films in lower humidity environments. Certain salts can hold water molecules in the Nafion film structure at room temperature. By mixing salts with the Nafion solution, water molecules can be homogeneously distributed in the Nafion film increasing the film s hydration to prevent Nafion film from being dried out in low-humidity environment. The presence of organics provides extra sites in the Nafion film to promote proton (H+) mobility and thus improving Nafion film conductivity and sensor performance. The fabrication of ambient temperature oxygen microsensors includes depositing basic electrodes using noble metals, and metal oxides layer on one of the electrode as a reference electrode. The use of noble metals for electrodes is due to their strong catalytic properties for oxygen reduction. A conducting polymer Nafion, doped with water-retaining components and extra sites facilitating proton movement, was used as the electrolyte material, making the design adequate for low humidity environment applications. The Nafion solution was coated on the electrodes and air-dried. The sensor operates at room temperature in potentiometric mode, which measures voltage differences between working and reference electrodes in different gases. Repeat able responses to 21-percent oxygen in nitrogen were achieved using nitrogen as a baseline gas. Detection of oxygen from 7 to 21 percent has also been demonstrated. The room-temperature oxygen micro sensor developed has extremely low power consumption (no heating for operation, no voltage applied to the sensor, only a voltmeter is needed to measure the output), is small in size, is simple to batch-fabricate, and is high in sensor yield. It is applicable in a wide humidity range, with improved operation in low humidity after the additives were added to the Nafion film. Through further improvement and development, the sensor can be used for aerospace applications such as fuel leak detection, fire detection, and environmental monitoring.
The parts of an electrical contact device are treated by sputter etching to remove the parent metal oxide. Prior to exposure of the electrodes to any oxygen, a sacrificial metal is sputter deposited on the parts. Preferably this sacrificial metal is one that oxidizes slowly and is readily dissolved by the liquid metal. The sacrificial metal may then be removed from unwanted areas. The remainder of the ring and the probe to be wet by the liquid metal are submerged in the liquid metal or the liquid metal is flushed over these areas, preferably while they are being slightly abraded, unitl all the sacrificial material on these portions is wet by the liquid metal. In doing so the liquid metal dissolves the sacrificial metal and permanently wets the parent metal. Preferred materials used in the process and for the electrodes of electrical contact devices are high purity (99.0%) nickel or AISI type 304 stainless steel for the electrical contact devices, gallium as the liquid metal, and gold as the sacrificial material.
On the lunar surface, production of commodi-ties to support human presence, such as water, food and oxygen, and sustain the growth of a per-manent outpostwill likely require the use oflocal resources. The moon is covered almost entirely withfragmented oxide minerals known as regolithhundreds of meter thick.As a resource, it is rich in oxygen (> 42 wt.%) bound in a solid state with a variety of metals. The molten regolith electrolysis (MRE)reactor is a promising technology for the production of gaseous oxygen from the lunar reg-olithin a simple, single-stepreaction that requires minimalconsumable materials, produces oxygen and metals with high electrical efficiency and high yields from any regolithcomposition.This process involvesmelting regolith to~1600°C then electro-lyzing the molten pool to separate metal and oxy-gen ions that are then collected as liquid metal and gaseous oxygen at the respective electrodes. Lab-scale demonstrations of the MRE technology have previously reliedon external heating sources to bring the entirety of the reactor up to the operating temperaturewhich creates corrosive interfaces be-tween the molten regolith and the containment ma-terial in the reactor, limiting the overall lifespan of a reactor[1]. The Gaseous Lunar Oxygen from Regolith Electrolysis (GaLORE) project is focused on the development of a “cold-walled” or “Joule-heated” reactor design in which an internal heating source is used to selectively melt a pool of regolith between the electrodes of the reactor, leaving a shell of solidified regolith between the molten pool and the containment vessel of the reactor. This next generation reactor concept has been under development as molten oxide electrolysis (MOE) by MIT and Boston Metal for the production of iron from pure ores for terrestrial application [2]. The GaLORE project in engaged in early development of the technology for use with varying lunar regolith compositionsin the lunar environment. Thermal modelling of a proposed cold-walledreac-tor design were used as a scaffold to develop pa-rameters for a feasible reactor shape and size as well as target energy consumption[3]. The current development effort for the cold-walled reactor de-sign will be presented as a trade study of the most promising techniques for melting regolithwithin the constraints imposed by the lunar environment.Heater devices are designed to accommodate lim-ited electrical power availabilityon the moon, a wide range of regolith compositions that may be seen on the moon, limited metals available for re-placing consumed parts,and the low thermal con-ductivity of granular regolith in vacuum.Heater de-vices will be down-selectedbased on performance measurements within the above operationalcon-straints,and selected devices will be integrated into a reactor with electrodes to begin producing oxygen. [1]Sibille,L.,Sadoway, D.R.,Sirk, A., Tripathy,P.,Melendez, O., Standish, E., Dominguez, J. A., Stefanescu, D.M.,Curreri, P.A., Poizeau,S.,2009. “Recent Advancesin Scale-up Development of Molten Regolith Electrolysis for Oxygen Production in support of a Lunar Base.”AIAA 2009-659, 47th AIAA Aerospace Sciences Meeting, 5 -8 January 2009, Orlando, FL. [2] Boston Metal, https://www.boston-metal.com/moe-technology/#moe-process[3]Schreiner, S.S.,Sibille, L., Dominguez, J.A., Hoffman, J.A., 2016. "A parametric sizing model for Molten Regolith Electrolysis reactors to pro-duce oxygen on the Moon." Advances in Space Research 57.,7,1585-1603.
Volt-ampere characteristics improvement and life testing of electrodes for hydrogen oxygen fuel cells
A low maintenance battery comprises a sealed casing (102) having a cavity (204) receiving a stack (108) of monopolar and bipolar plates (110, 112) interspersed with mats (122) of fiberglass felt immobilizing electrolyte and forming a gas path for diffusion of oxygen to the negative electrode (112). The casing contains a single, resealable vent (202). During charging, oxygen generated at the positive plate (110) diffuses through the mat (122) and decomposes at the negative plate (112). The negative plate (112) has a larger capacity than the positive plate (110) to prevent evolution of hydrogen. Voltage potential is increased or decreased by placing one or more bipolar plates (120) in series relation between alternating positive and negative monopolar plates that are connected in parallel to respective positive and negative battery terminals (104, 106). The monoplates (110, 112) are connected in parallel to respective positive and negative battery terminals (104, 106) by way of bus plates (114, 116, 130, 132). The resealable vent permits operation by way of the oxygen cycle which prevents loss of electrolyte. The vent prevents invasion of oxygen from the ambient to discharge negative plates.
Previous reports have shown how a battery model was developed using porous electrode theory. Since then the model has been upgraded and expanded. These upgrades include oxygen reation and positive electrode intercalation and proton diffusion. The effects of additional details of the solid state physics of the nickel electrode will be reported here.
We study the carbon nanotube Schottky barrier at the metallic electrode interface in polarized gases using an equivalent circuit model. The gas-nanotube interaction is often weak and very little charge transfer is expected [l]. This is the case with'oxygen, but the gas-electrode interaction is appreciable and makes the oxygen molecules negatively charged. In the closed circuit condition, screening positive charges appear in the nanotube as well as in the electrode, and the Schottky barrier is modulated due to the resultant electrostatic effects [2]. In the case of ammonia, both the gas-nanotube and gas-electrode interactions are weak, but the Schottky barrier can still be modulated since the molecules are polarized and align in the preferred orientation within the gap between the electrode and nanotube in the open circuit condition (dipole layer formation). In the closed circuit condition, an electric field appears in the gap and strengthens or weakens the preferred dipole alignment reflecting the nanotube Fermi level. The modulation is visible when the nanotube depletion mode is involved, and the required dipole density is as low as 2 x 10(exp 13) dipoles/sq cm, which is quite feasible experimentally,