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Electrode kinetics of oxygen reduction - A theoretical and experimental analysis of the rotating ring-disc electrode method

In order to calculate most of the rate constants for the intermediate formation of H2O2 in the electroreduction of O2 to H2O, the theoretical treatments of the rotating ring-disc electrode method by Damjanovic et al. (1966, 1967), Bagotskii et al. (1968, 1969), and Wroblowa et al. (1976) are modified. Rotating ring-disc electrode experimental data obtained for O2 reduction in Pt in 0.55 M H2SO4 are used to illustrate the calculations of rate constants according to the above theoretical treatments. A simple reaction model as proposed by the first author is consistent with the experimental data. The results indicate that O2 (97 percent) reduces to H2O in a direct four-electron transfer reaction. The adsorption of O2 is probably the rate-determining step in the potential region more negative than 0.5 V vs. reversible hydrogen electrode.

Hsueh, K.-L.↗

Single cell performance studies on the Fe/Cr Redox Energy Storage System using mixed reactant solutions at elevated temperature

Experimental studies in a 14.5 sq cm single cell system using mixed reactant solutions at 65 C are described. Systems were tested under isothermal conditions i.e., reactants and the cell were at the same temperature. Charging and discharging performance were evaluted by measuring watt-hour and coulombic efficiencies, voltage-current relationships, hydrogen evolution and membrane resistivity. Watt-hour efficiencies ranged from 86% at 43 ma/sq cm to 75% at 129 ma/sq cm with corresponding coulombic efficiencies of 92% and 97%, respectively. Hydrogen evolution was less than 1% of the charge coulombic capacity during charge-discharge cycling. Bismuth and bismuth-lead catalyzed chromium electrodes maintained reversible performance and low hydrogen evolution under normal and adverse cycling conditions. Reblending of the anode and cathode solutions was successfully demonstrated to compensate for osmotic volume changes. Improved performance was obtained with mixed reactant systems in comparison to the unmixed reactant systems.

Gahn, R. F.↗

Single cell performance studies on the FE/CR Redox Energy Storage System using mixed reactant solutions at elevated temperature

Experimental studies in a 14.5 sq cm single cell system using mixed reactant solutions at 65 C are described. Systems were tested under isothermal conditions, i.e., reactants and the cell were at the same temperature. Charging and discharging performance were evaluated by measuring watt-hour and coulombic efficiencies, voltage-current relationships, hydrogen evolution and membrane resistivity. Watt-hour efficiencies ranged from 86 percent at 43 ma/sq cm to 75 percent at 129 ma/sq cm with corresponding coulombic efficiencies of 92 percent and 97 percent, respectively. Hydrogen evolution was less than 1 percent of the charge coulumbic capacity during charge-discharge cycling. Bismuth amd bismuth-lead catalyzed chromium electrodes maintained reversible performance and low hydrogen evolution under normal and adverse cycling conditions. Reblending of the anode and cathode solutions was successfully demonstrated to compensate for osmotic volume changes. Improved performance was obtained with mixed reactant systems in comparison to the unmixed reactant systems. Previously announced in STAR as N83-25042

Gahn, R. F.↗

Additional Reversal Characteristics of Sealed Nickel Cadmium Cells

The reversal characteristics of nickel cadmium cells are discussed. The evolution of hydrogen from the positive electrode is described when the nickel cadmium cell is completely discharged. Results indicate that one ampere hour of overdischarge in reversal can generate enough hydrogen to increase the cell pressure of an average size cell, 20- to 50-ampere hour cell, by 120 psi.

Ritterman, P. F.↗

The characteristics of sealed nickel-cadmium cells during voltage reversal

A mechanism which allows a cell voltage reversal in a nickel cadmium battery are discussed. The effects of reconditioning and the characteristics of Ni-Cd cells during voltage reversal at low overdischarge rates are outlined. Graphs are presented for: (1) hydrogen pressure decay-effect of state of charge (open circuit stand); (2) hydrogen pressure increase during overdischarge; (3) hydrogen pressure decay-effect of temperature (cells terminals connected through resistors); (4) cell, positive and negative electrode voltage during reversal when reconditioning a 13 cell-24-Ah battery pack through a 40 Omega resistor; (5) pressure discharge current and recombination current during voltage reversal when reconditioning a 13 cell-24-Ah battery pack through a 40 Omega resistor; (6) theoretical hydrogen gas pressure if there were no recombination; and (7) effect of hydrogen pressure on recombination rate during overcharge.

Ritterman, P. F.↗

Apparatus for Pumping a Fluid

An electrochemically actuated pump and an electrochemical actuator for use with a pump. The pump includes one of various stroke volume multiplier configurations with the pressure of a pumping fluid assisting actuation of a driving fluid bellows. The electrochemical actuator has at least one electrode fluidically coupled to the driving fluid chamber of the first pump housing and at least one electrode fluidically coupled to the driving fluid chamber of the second pump housing. Accordingly, the electrochemical actuator selectively pressurizes hydrogen gas within a driving fluid chamber. The actuator may include a membrane electrode assembly including an ion exchange membrane with first and second catalyzed electrodes in contact with opposing sides of the membrane, and first and second hydrogen gas chambers in fluid communication with the first and second electrodes, respectively. A controller may reverse the polarity of a voltage source electrically coupled to the current collectors.

van Boeyen, Roger W.↗

Hydrogen /Hydride/-air secondary battery

The use of metal hydrides as negative electrodes in a hydrogen-air secondary battery seems promising. However, in an unpressurized cell, more stable hydrides that LaNi5H6 must be selected. Partial substitutions of nickel by aluminium or manganese increase the stability of hydrides. Combined with an air reversible electrode, a specific energy close to 100 Wh/kg can be expected.

Sarradin, J.↗

Gas-operated actuator: A concept

Recyclable actuator does depend on valves for its operation. Palladium cathode tube in electrochemical cell is used to generate hydrogen by electrolysis. Hydrogen pressure generated inside tube causes expansion of bellows, which raises load. Bellows can be retracted by reversing electrical connections to cell electrodes.

Simmonds, P. G.↗

Novel metal-filled polyimide electrodes

Palladium-coated polyimide films are evaluated as electrochemical electrodes. The film electrodes exhibit essentially identical behavior compared to bulk palladium electrodes. In aqueous 0.5M H2SO4, current peaks due to oxide formation, oxide stripping, hydrogen adsorption, and H2 oxidation are observed. The ferri/ferrocyanide redox couple is grossly irreversible in the same electrolyte. Reversible electrochemical behavior is obtained for Fe(EDTA)(1-/2-) in 1M KCl/H2O, and for ferrocene/ferricenium in 0.1M TEAP/dimethylacetamide.

Furtsch, T. A.↗

The TMI Regenerative Solid Oxide Fuel Cell

Energy storage and production in space requires rugged, reliable hardware which minimizes weight, volume, and maintenance while maximizing power output and usable energy storage. Systems generally consist of photovoltaic solar arrays which operate (during sunlight cycles) to provide system power and regenerate fuel (hydrogen) via water electrolysis and (during dark cycles) fuel cells convert hydrogen into electricity. Common configurations use two separate systems (fuel cell and electrolyzer) in conjunction with photovoltaic cells. Reliability, power to weight and power to volume ratios could be greatly improved if both power production (fuel cells) and power storage (electrolysis) functions can be integrated into a single unit. The solid oxide fuel cell (SOFC) based design integrates fuel cell and electrolyzer functions and potentially simplifies system requirements. The integrated fuel cell/electrolyzer design also utilizes innovative gas storage concepts and operates like a rechargeable 'hydrogen-oxygen battery'. Preliminary research has been completed on improved H2/H20 electrode (SOFC anode/electrolyzer cathode) materials for regenerative fuel cells. Tests have shown improved cell performance in both fuel and electrolysis modes in reversible fuel cell tests. Regenerative fuel cell efficiencies, ratio of power out (fuel cell mode) to power in (electrolyzer mode), improved from 50 percent using conventional electrode materials to over 80 percent. The new materials will allow a single SOFC system to operate as both the electolyzer and fuel cell. Preliminary system designs have also been developed to show the technical feasibility of using the design for space applications requiring high energy storage efficiencies and high specific energy. Small space systems also have potential for dual-use, terrestrial applications.

Cable, Thomas L.↗

The TMI regenerable solid oxide fuel cell

Energy storage and production in space requires rugged, reliable hardware which minimizes weight, volume, and maintenance while maximizing power output and usable energy storage. These systems generally consist of photovoltaic solar arrays which operate during sunlight cycles to provide system power and regenerate fuel (hydrogen) via water electrolysis; during dark cycles, hydrogen is converted by the fuel cell into system. The currently preferred configuration uses two separate systems (fuel cell and electrolyzer) in conjunction with photovoltaic cells. Fuel cell/electrolyzer system simplicity, reliability, and power-to-weight and power-to-volume ratios could be greatly improved if both power production (fuel cell) and power storage (electrolysis) functions can be integrated into a single unit. The Technology Management, Inc. (TMI), solid oxide fuel cell-based system offers the opportunity to both integrate fuel cell and electrolyzer functions into one unit and potentially simplify system requirements. Based an the TMI solid oxide fuel cell (SOPC) technology, the TMI integrated fuel cell/electrolyzer utilizes innovative gas storage and operational concepts and operates like a rechargeable 'hydrogen-oxygen battery'. Preliminary research has been completed on improved H2/H2O electrode (SOFC anode/electrolyzer cathode) materials for solid oxide, regenerative fuel cells. Improved H2/H2O electrode materials showed improved cell performance in both fuel cell and electrolysis modes in reversible cell tests. ln reversible fuel cell/electrolyzer mode, regenerative fuel cell efficiencies (ratio of power out (fuel cell mode) to power in (electrolyzer model)) improved from 50 percent (using conventional electrode materials) to over 80 percent. The new materials will allow the TMI SOFC system to operate as both the electrolyzer and fuel cell in a single unit. Preliminary system designs have also been developed which indicate the technical feasibility of using the TMI SOFC technology for space applications with high energy storage efficiencies and high specific energy. Development of small space systems would also have potential dual-use, terrestrial applications.

Cable, Thomas L.↗

Fuel cells and the theory of metals.

Metal theory is used to study the role of metal catalysts in electrocatalysis, with particular reference to alkaline hydrogen-oxygen fuel cells. Use is made of a simple model, analogous to that used to interpret field emission in vacuum. Theoretical values for all the quantities in the Tafel equation are obtained in terms of bulk properties of the metal catalysts (such as free electron densities and Fermi level). The reasons why some processes are reversible (H-electrodes) and some irreversible (O-electrodes) are identified. Selection rules for desirable properties of catalytic materials are established.

Bocciarelli, C. V.↗

Light Weight Design Nickel-Alkaline Cells Using Fiber Electrodes

Using fiber electrode technology, currently produced by Bekaert Corporation (Bekaert), Electro Energy, Inc., (EEI) Mobile Energy Products Group (formerly, Eagle-Picher Technologies, LLC., Power Systems Department) in Colorado Springs, CO has demonstrated that it is feasible to manufacture flight weight nickel-hydrogen cells having about twice the specific energy (80 vs. 40 watt-hr/kg) as state-of-the-art nickel-hydrogen cells that are flown on geosynchronous communications satellites. Although lithium-ion battery technology has made large in-roads to replace the nickel-alkaline technology (nickel-cadmium, nickel-metal hydride), the technology offered here competes with lithium-ion weight and offers alternatives not present in the lithium-ion chemistry such as ability to undergo continuous overcharge, reversal on discharge and sustain rate capability sufficient to start automotive and aircraft engines at subzero temperatures. In development to date seven 50 ampere-hour nickel-hydrogen have been constructed, acceptance tested and briefly tested in a low earth orbit (LEO) cycle regime. The effort was jointly funded by Electro Energy, Inc. and NASA Glenn Research Center, Cleveland, OH. Five of the seven cells have been shipped to NASA GRC for further cycle testing. Two of the cells experienced failure due to internal short circuits during initial cycle testing at EEL Destructive Physical Analysis (DPA) of one of the cells has shown the failure mode to be due to inadequate hydrogen catalyst electrodes that were not capacity balanced with the higher energy density nickel oxide electrodes. In the investigators opinion, rebuild of the cells using proper electrode balance would result in cells that could sustain over 30,000 cycles at moderate depths-of-discharge in a LEO regime or endure over 20 years of geosynchronous orbit (GEO) cycling while realizing a two-fold increase in specific energy for the battery or a 1.1 kg weight savings per 50 ampere-hour cell. Additional information is included in the original extended abstract.

Pickett, David F.↗

Capacity retention in hydrogen storage alloys

Results of our examination of the properties of several candidate materials for hydrogen storage electrodes and their relation to the decrease in H-storage capacity upon open-circuit storage over time are reported. In some of the alloy samples examined to date, only about 10 percent of the hydrogen capacity was lost upon storage for 20 days, while in others, this number was as high as 30 percent for the same period of time. This loss in capacity is attributed to two separate mechanisms: (1) hydrogen desorbed from the electrode due to pressure differences between the cell and the electrode sample; and (2) chemical and/or electrochemical degradation of the alloy electrode upon exposure to the cell environment. The former process is a direct consequence of the equilibrium dissociation pressure of the hydride alloy phase and the partial pressure of hydrogen in the hydride phase in equilibrium with that in the electrolyte environment, while the latter is related to the stability of the alloy phase in the cell environment. Comparison of the equilibrium gas-phase dissociation pressures of these alloys indicate that reversible loss of hydrogen capacity is higher in alloys with P(eqm) greater than 1 atm than in those with P(eqm) less than 1 atm.

Anani, A.↗

Integrated regenerative fuel cell experimental evaluation

An experimental test program was conducted to investigate the performance characteristics of an integrated regenerative fuel cell (IRFC) concept. The IRFC consists of a separate fuel cell unit and electrolysis cell unit in the same structure, with internal storage of fuel cell product water and external storage of electrolysis cell produced hydrogen and oxygen. The fuel cell unit incorporates an enhanced Orbiter-type cell capable of improved performance at reduced weight. The electrolysis cell features a NiCo2O4 catalyst oxygen evolution eletrode with a porous Teflon cover to retard electrolyte loss. Six complete IRFC assemblies were assembled and performance tested at an operating temperature of 200 F (93.3 C) and reactant pressures up to 170 psia (117.2 n/cu cm) on IRFC No. 4. Anomalous pressure charge/discharge characteristics were encountered during performance evaluation. A reversible fuel cell incorporating a proprietary bi-functional oxygen electrode operated satisfactory at 200 F (93.3 C) at reactant pressures up to 50 psia (41.4 n/cu cm) as a regenerative fuel cell for one cycle, before developing an electrical short in the fuel cell mode. Electrolysis cell 300-hour endurance tests demonstrated the electrolyte retention capability of the electrode Teflon cover and the performance stability of the bi-functional oxygen electrode at high potential.

Martin, Ronald E.↗

NASA Tech Briefs, October 2010

Topics covered include: Hybrid Architecture Active Wavefront Sensing and Control; Carbon-Nanotube-Based Chemical Gas Sensor; Aerogel-Positronium Technology for the Detection of Small Quantities of Organic and/or Toxic Materials; Graphene-Based Reversible Nano-Switch/Sensor Schottky Diode; Inductive Non-Contact Position Sensor; High-Temperature Surface-Acoustic-Wave Transducer; Grid-Sphere Electrodes for Contact with Ionospheric Plasma; Enabling IP Header Compression in COTS Routers via Frame Relay on a Simplex Link; Ka-Band SiGe Receiver Front-End MMIC for Transponder Applications; Robust Optimization Design Algorithm for High-Frequency TWTs; Optimal and Local Connectivity Between Neuron and Synapse Array in the Quantum Dot/Silicon Brain; Method and Circuit for In-Situ Health Monitoring of Solar Cells in Space; BGen: A UML Behavior Network Generator Tool; Platform for Post-Processing Waveform-Based NDE; Electrochemical Hydrogen Peroxide Generator; Fabrication of Single, Vertically Aligned Carbon Nanotubes in 3D Nanoscale Architectures; Process to Create High-Fidelity Lunar Dust Simulants; Lithium-Ion Electrolytes Containing Phosphorous-Based, Flame-Retardant Additives; InGaP Heterojunction Barrier Solar Cells; Straight-Pore Microfilter with Efficient Regeneration; Determining Shear Stress Distribution in a Laminate; Self-Adjusting Liquid Injectors for Combustors; Handling Qualities Prediction of an F-16XL-Based Reduced Sonic Boom Aircraft; Tele-Robotic ATHLETE Controller for Kinematics - TRACK; Three-Wheel Brush-Wheel Sampler; Heterodyne Interferometer Angle Metrology; Aligning Astronomical Telescopes via Identification of Stars; Generation of Optical Combs in a WGM Resonator from a Bichromatic Pump; Large-Format AlGaN PIN Photodiode Arrays for UV Images; Fiber-Coupled Planar Light-Wave Circuit for Seed Laser Control in High Spectral Resolution Lidar Systems; On Calculating the Zero-Gravity Surface Figure of a Mirror; Optical Modification of Casimir Forces for Improved Function of Micro- and Nano-Scale Devices; Analysis, Simulation, and Verification of Knowledge-Based, Rule-Based, and Expert Systems; Core and Off-Core Processes in Systems Engineering; Digital Reconstruction Supporting Investigation of Mishaps; and Template Matching Approach to Signal Prediction.

Source record↗

Progress on the Plasmoid Thruster Experiment (PTX)

A plasmoid is a compact plasma structure with an integral magnetic field, that may be categorized according to the relative strength of the poloidal and toroidal magnetic field (B(sub p) and B(sub t), respectively). An object with B(sub p)/B(sub t), much much more than 1 is called a Field Reverse Configuration (FRC); if B(sub p) approximately equal to B(sub t), it is called a Spheromak. The thruster operates by repetitively producing plasmoids that are accelerated and ejected at high velocity. As this process is inductive, there are no electrodes. Also, the magnetic structure of the plasmoid should suppress thermal and mass losses to the wall, and improve detachment of the plasma exhaust from the thruster. This concept should be capable of producing an Isp in the range of 5,000 - 10,000 s with thrust densities of order 10(exp 5) N per square meters. The current experiment is designed to produce jet powers in the range of 5-10 kW, although the concept should be scalable into the MW range. In PTX, the plasmoid is formed inside of a single turn conical theta-pinch coil (17.58 cone angle). The coil is driven by a 640 nF, 35 kV capacitor bank, which rings at a frequency of 500 kHz. Previous experiments on PTX were conducted with a static-fill of propellant gas (6% H2 in He), and demonstrated reliable ionization over a pressure range of 40 - 200 mTorr. We are now adding a fast gas-puff valve to load the propellant, and a ringing pre-ionization circuit (f = 5 Mhz) to better control the plasmoid formation. An alternate coil (8.58 cone angle) will also be used, so as to investigate the effect of coil shape on performance. In addition, a variety of propellants will be used, including hydrogen, nitrogen, and argon. The plasmoid mass and velocity will be measured with a variety of diagnostics, including external B-dot probes and flux loops, a high-speed framing camera, and a HeNe laser interferometer. Internal B-dot probes and a quadruple Langmuir probe will provide additional measurements of the plasmoid shape and structure, as well as density, and will be described in a companion paper. The experimental results will be compared to calculations made using a 0-D coil-gun model and also a 2-D time dependent MHD code.

Martin, Adam↗