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At least 37 records · Page 2

Research on rechargeable oxygen electrodes.

A research program is described which consisted of studying the effects of electrode cycling in very pure KOH solutions, with and without controlled additions of impurities, on oxide formation, oxygen evolution kinetics, oxygen reduction kinetics (including hydrogen peroxide formation), and changes in electrode structure. Bright platinum, platinized platinum, and Teflon-bonded platinum black electrodes were studied. Three main problem areas are identified: the buildup of a refractory anodic layer on prolonged cycling, which leads to a degradation of performance; the dissolution and subsequent deposition of dendritic platinum in the separator, leading to short-circuit ing and loss of electrocatalyst; and the disruptive effect of bubbling during gas evolution on charge. Each of these problem areas is analyzed, and remedial solutions are proposed.

Giner, J.↗

Oxygen electrodes for rechargeable alkaline fuel cells

Electrocatalysts and supports for the positive electrode of moderate temperature single-unit rechargeable alkaline fuel cells are being investigated and developed. Candidate support materials were drawn from transition metal carbides, borides, nitrides and oxides which have high conductivity (greater than 1 ohm/cm). Candidate catalyst materials were selected largely from metal oxides of the form ABO sub x (where A = Pb, Cd, Mn, Ti, Zr, La, Sr, Na, and B = Pt, Pd, Ir, Ru, Ni (Co) which were investigated and/or developed for one function only, O2 reduction or O2 evolution. The electrical conductivity requirement for catalysts may be lower, especially if integrated with a higher conductivity support. All candidate materials of acceptable conductivity are subjected to corrosion testing. Materials that survive chemical testing are examined for electrochemical corrosion activity. For more stringent corrosion testing, and for further evaluation of electrocatalysts (which generally show significant O2 evolution at at 1.4 V), samples are held at 1.6 V or 0.6 V for about 100 hours. The surviving materials are then physically and chemically analyzed for signs of degradation. To evaluate the bifunctional oxygen activity of candidate catalysts, Teflon-bonded electrodes are fabricated and tested in a floating electrode configuration. Many of the experimental materials being studied have required development of a customized electrode fabrication procedure. In advanced development, the goal is to reduce the polarization to about 300 to 350 mV. Approximately six support materials and five catalyst materials were identified to date for further development. The test results will be described.

Swette, L.↗

Evaluation parameters for the alkaline fuel cell oxygen electrode

Studies were made of Pt- and Au-catalyzed porous electrodes, designed for the cathode of the alkaline H2/O2 fuel cell, employing cyclic voltammetry and the floating half-cell method. The purpose was to obtain parameters from the cyclic voltammograms which could predict performance in the fuel cell. It was found that a satisfactory relationship between these two types of measurement could not be established; however, useful observations were made of relative performance of several types of carbon used as supports for noble metal catalysts and of some Au catalysts. The best half-cell performance with H2/O2 in a 35 percent KOH electrolyte at 80 C was given by unsupported fine particle Au on Teflon; this electrode is used in the Orbiter fuel cell.

Singer, J.↗

Oxygen electrode bifunctional electrocatalyst NiCo2O4 spinel

A significant increase in energy density may be possible if a two-unit alkaline regenerative H2-O2 fuel cell is replaced with a single-unit system that uses passive means for H2O transfer and thermal control. For this single-unit system, new electrocatalysts for the O2 electrode will be required which are not only bifunctionally active but also chemically and electrochemically stable between the voltage range of about 0.7 and 1.5 V. NiCo2O4 spinel is reported to have certain characteristics that make it useful for a study of electrode fabrication techniques. High surface area NiCo2O4 powder was fabricated into unsupported, bifunctional, PTFE-bonded, porous gas fuel cell electrodes by commercial sources using varying PTFE contents and sintering temperatures. The object of this study is to measure the bifunctional activities of these electrodes and to observe what performance differences might result from different commercial electrode fabricators. O2 evolution and O2 reduction data were obtained at 80 C (31 percent KOH). An irreversible reaction (i.e., aging) occurred during O2 evolution at potentials greater than about 1.5 V. Anodic Tafel slopes of 0.06 and 0.12 V/decade were obtained for the aged electrodes. Within the range of 15 to 25 percent, the PTFE content was not a critical parameter for optimizing the electrode for O2 evolution activity. Sintering temperatures between 300 and 340 C may be adequate but heating at 275 C may not be sufficient to properly sinter the PTFE-NiCo2O4 mixture. Electrode disintegration was observed during O2 reduction. Transport of O2 to the NiCo2O4 surface became prohibitive at greater than about -0.02 A/sq cm. Cathodic Tafel slopes of -0.6 and -0.12 V/decade were assumed for the O2 reduction process. A PTFE content of 25 percent (or greater) appears to be preferable for sintering the PTFE-NiCo2O4 mixture.

Fielder, William L.↗

Electrocatalysts for oxygen electrodes in fuel cells and water electrolyzers for space applications

In most instances separate electrocatalysts are needed to promote the reduction of O2 in the fuel cell mode and to generate O2 in the energy storage-water electrolysis mode in aqueous electrochemical systems operating at low and moderate temperatures (T greater than or equal to 200 C). Interesting exceptions are the lead and bismuth ruthenate pyrochlores in alkaline electrolytes. These catalysts on high area carbon supports have high catalytic activity for both O2 reduction and generation (1,2). Rotating ring-disk electrode measurements provide evidence that the O2 reduction proceeds by a parallel four-electron pathway. The ruthenates can also be used as self-supported catalysts to avoid the problems associated with carbon oxidation, but the electrode performance so far achieved in the research at Case Western Reserve University (CWRU) is considerably less. At the potentials involved in the anodic mode the ruthenate pyrochlores have substantial equilibrium solubility in concentrated alkaline electrolyte. This results in the loss of catalyst into the bulk solution and a decline in catalytic activity. Furthermore, the hydrogen generation counter electrode may become contaminated with reduction products from the pyrochlores (lead, ruthenium). A possible approach to this problem is to immobilize the pyrochlore catalyst within an ionic-conducting solid polymer, which would replace the fluid electrolyte within the porous gas diffusion O2 electrode. For bulk alkaline electrolyte, an anion-exchange polymer is needed with a transference number close to unity for the Oh(-) ion. Preliminary short-term measurements with lead ruthenates using a commercially available partially-fluorinated anion-exchange membrane as an overlayer on the porous gas-fed electrode indicate lower anodic polarization and virtually unchanged cathodic polarization.

Prakash, Jai↗

Electrocatalysis for oxygen electrodes in fuel cells and water electrolyzers for space applications

In most instances separate electrocatalysts are needed to promote the reduction of O2 in the fuel cell mode and to generate O2 in the energy storage-water electrolysis mode in aqueous electrochemical systems operating at low and moderate temperatures (T greater than or equal to 200 C). Interesting exceptions are the lead and bismuth ruthenate pyrochlores in alkaline electrolytes. These catalysts on high area carbon supports have high catalytic activity for both O2 reduction and generation. Rotating ring-disk electrode measurements provide evidence that the O2 reduction proceeds by a parallel four-electron pathway. The ruthenates can also be used as self-supported catalysts to avoid the problems associated with carbon oxidation, but the electrode performance so far achieved in the research at Case Western Reserve University (CWRU) is considerably less. At the potentials involved in the anodic mode the ruthenate pyrochlores have substantial equilibrium solubility in concentrated alkaline electrolyte. This results in the loss of catalyst into the bulk solution and a decline in catalytic activity. Furthermore, the hydrogen generation counter electrode may become contaminated with reduction products from the pyrochlores (lead, ruthenium).

Prakash, Jai↗

Oxygen electrodes for rechargeable alkaline fuel cells-II

The primary objective of this program is the investigation and development of electrocatalysts and supports for the positive electrode of moderate temperature single-unit rechargeable alkaline fuel cells. Approximately six support materials and five catalyst materials have been identified to date for further development.

Swette, L.↗

Electrocatalysis for oxygen electrodes in fuel cells and water electrolyzers for space applications

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.

Prakash, Jai↗

Oxygen electrodes for rechargeable alkaline fuel cells. II

The primary objective of this program is the investigation and development of electrocatalysts and supports for the positive electrode of moderate temperature, single-unit, rechargeable alkaline fuel cells. Approximately six support materials and five catalyst materials have been identified to date for further development.

Swette, L.↗

Oxygen electrodes for rechargeable alkaline fuel cells, 3

The investigation and development of electrocatalysts and supports for the positive electrode of moderate-temperature single unit rechargeable alkaline fuel cells is described with focus on chemical and electrochemical stability and O2 reduction/evolution activity.

L Swette↗

Bifunctional catalytic electrode

The present invention relates to an oxygen electrode for a unitized regenerative hydrogen-oxygen fuel cell and the unitized regenerative fuel cell having the oxygen electrode. The oxygen electrode contains components electrocatalytically active for the evolution of oxygen from water and the reduction of oxygen to water, and has a structure that supports the flow of both water and gases between the catalytically active surface and a flow field or electrode chamber for bulk flow of the fluids. The electrode has an electrocatalyst layer and a diffusion backing layer interspersed with hydrophilic and hydrophobic regions. The diffusion backing layer consists of a metal core having gas diffusion structures bonded to the metal core.

Cisar, Alan↗

A Multifunctional Isostructural Bilayer Oxygen Evolution Electrode for Durable Intermediate-Temperature Electrochemical Water Splitting

The overarching goal of the proposed research is to address SOEC’s degradation problem by advancing a new isostructural highly electrocatalytically active bilayer oxygen evolution reaction (OER) electrode, consisting of a LSCF (La 1-x Sr x Co 1-y Fe y O 3-δ ) core and a SCT (SrCo 0.9 Ta 0.1 O 3-δ ) shell, to achieve high and sustainable rate of oxygen evolution matching operating current densities without encountering delamination. To realize this goal, the project has adopted a combined experimental and theoretical approach to conduct research in the following six areas closely associated with SOPO tasks: 1) Development of electrocatalytically active bilayer oxygen electrodes (SOPO task-1) 2) Development of new symmetric three electrode cell (STEC) methodology to extract electrokinetic data of oxygen electrodes (SOPO task-2) 3) Quantification of electrokinetics of bilayer oxygen electrodes and correlation with degradation and delamination (SOPO task-2) 4) Performances of bilayer oxygen electrodes under fuel cells and electrolyzers modes (SOPO task-3) 5) Microscale modeling of oxygen electrode/electrolyte interface in solid oxide electrolysis cells (SOPO task-4) 6) Prediction of crack growth rate at oxygen electrode/electrolyte interface in solid oxide electrolysis cells (SOPO task-4)

08 HYDROGEN↗