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Results for “Tafel slope”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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12 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1992

Temperature dependence of the electrode kinetics of oxygen reduction at the platinum/Nafion interface - A microelectrode investigation

Results of a study of the temperature dependence of the oxygen reduction kinetics at the Pt/Nafion interface are presented. This study was carried out in the temperature range of 30-80 C and at 5 atm of oxygen pressure. The results showed a linear increase of the Tafel slope with temperature in the low current density region, but the Tafel slope was found to be independent of temperature in the high current density region. The values of the activation energy for oxygen reduction at the platinum/Nafion interface are nearly the same as those obtained at the platinum/trifluoromethane sulfonic acid interface but less than values obtained at the Pt/H3PO4 and Pt/HClO4 interfaces. The diffusion coefficient of oxygen in Nafion increases with temperature while its solubility decreases with temperature. These temperatures also depend on the water content of the membrane.

Parthasarathy, Arvind↗
NASA NTRS1988

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.↗
NASA NTRS1974

Electrode kinetics of a water vapor electrolysis cell

The anodic electrochemical behavior of the water vapor electrolysis cell was investigated. A theoretical review of various aspects of cell overvoltage is presented with special emphasis on concentration overvoltage and activation overvoltage. Other sources of overvoltage are described. The experimental apparatus controlled and measured anode potential and cell current. Potentials between 1.10 and 2.60 V (vs NHE) and currents between 0.1 and 3000 mA were investigated. Different behavior was observed between the standard cell and the free electrolyte cell. The free electrolyte cell followed typical Tafel behavior (i.e. activation overvoltage) with Tafel slopes of about 0.15, and the exchange current densities of 10 to the minus 9th power A/sq cm, both in good agreement with literature values. The standard cell exhibitied this same Tafel behavior at lower current densities but deviated toward lower than expected current densities at higher potentials. This behavior and other results were examined to determine their origin.

Jacobs, G.↗
NASA NTRS1972

Electrochemical behavior of the boron anode in aqueous solutions

The electrochemical oxidation of p-type boron in 0.2 N NaNO3 solutions of pH 0.4 to 13.1 was studied by galvanostatic techniques. The capacitance of the electrode, Tafel slopes, and a limited analysis of reaction mechanisms are reported. The anodic dissolution in acid solution is a charge-transfer-limited one-electron reaction to form a monovalent species in the over-potential region of 0.25 to 0.70 V. The dissolution in basic solution is most probably a one-electron charge-transfer reaction from a monovalent to divalent species involving three hydroxyl ions. Open circuit potentials were mixed potentials, probably due to hydrogen formation at open circuit but not contributing to the electrochemical reaction at the applied overpotential. Exchange current, estimated by extrapolation of the Tafel line to the standard oxidation potential for the boron reaction, were of the order of 10 to the minus 6th power A/cm2 in acid solution and 10 to the minus 12th power A/cm2 in basic solution. The reaction order of the rate determining acidic and basic reactions was determined with regard to (H+) and (OH-). The level of illumination had no effect on the electrochemical behavior of the electrode.

Delduca, B. S.↗
NASA NTRS1975

Electrochemical generation of oxygen. 1: The effects of anions and cations on hydrogen chemisorption and anodic oxide film formation on platinum electrode. 2: The effects of anions and cations on oxygen generation on platinum electrode

The effects were studied of anions and cations on hydrogen chemisorption and anodic oxide film formation on Pt by linear sweep voltammetry, and on oxygen generation on Pt by potentiostatic overpotential measurement. The hydrogen chemisorption and anodic oxide film formation regions are greatly influenced by anion adsorption. In acids, the strongly bound hydrogen occurs at more cathodic potential when chloride and sulfate are present. Sulfate affects the initial phase of oxide film formation by produced fine structure while chloride retards the oxide-film formation. In alkaline solutions, both strongly and weakly bound hydrogen are influenced by iodide, cyanide, and barium and calcium cations. These ions also influence the oxide film formation. Factors considered to explain these effects are discussed. The Tafel slope for oxygen generation was found to be independent on the oxide thickness and the presence of cations or anions. The catalytic activity indicated by the exchange current density was observed decreasing with increasing oxide layer thickness, only a minor dependence on the addition of certain cations and anions was found.

Huang, C. J.↗
NASA NTRS1977

Electrochemical behavior of 0.2 to 3 molar ferrous chloride-ferric chloride mixtures on edge-on pyrolytic graphite rotated disk electrodes

Potentiostatic determinations in various mixtures of FeCl2-FeCl3 with excess HCl show rest potentials that are 0.1 V less electropositive than the theoretical values from the formulated ratios of FeII to FeIII (probably as a result of complexing). The standard rate constant sub s. ranges between 0.0001 and 0.000 cm/sec. Tafel slopes b of roughly 0.12V per decade indicate single-electron exchange kinetics. No significant trend in either b or sub s was attributed to mixture composition. The higher sub s. values occurred with and edge-on pyrolytic graphite that had undergone a permanent surface change.

Miller, R. O.↗
NASA NTRS1981

Cathode catalysts for primary phosphoric acid fuel cells

Alkylation or carbon Vulcan XC-72, the support carbon, was shown to provide the most stable bond type for linking cobalt dehydrodibenzo tetraazannulene (CoTAA) to the surface of the carbon; this result is based on data obtained by cyclic voltammetry, pulse voltammetry and by release of 14C from bonded CoTAA. Half-cell tests at 100 C in 85% phosphoric acid showed that CoTAA bonded to the surface of carbon (Vulcan XC-72) via an alkylation procedure is a more active catalyst than is platinum based on a factor of two improvement in Tafel slope; dimeric CoTAA had catalytic activity equal to platinum. Half-cell tests also showed that bonded CoTAA catalysts do not suffer a loss in potential when air is used as a fuel rather than oxygen. Commercially available polytetrafluroethylene (PTFE) was shown to be unstable in the fuel cell environment with degradation occurring in 2000 hours or less. The PTFE was stressed at 200 C in concentrated phosphoric acid as well as electrochemically stressed in 150 C concentrated phosphoric acid; the surface chemistry of PTFE was observed to change significantly. Radiolabeled PTFE was prepared and used to verify that such chemical changes also occur in the primary fuel cell environment.

Source record↗
NASA NTRS1980

Cathode catalyst for primary phosphoric fuel cells

Alkylation of Vulcan XC-72 provided the most stable bond type for linking CoTAA to the surface of the carbon; this result is based on data obtained by cyclic voltammetry, pulse voltammetry and by release of 14C from bonded CoTAA. Half-cell tests at 100 C in 85% phosphoric acid showed that CoTAA bonded to the surface of carbon (Vulcan XC-72) via an alkylation procedure is a more active catalyst than is platinum based on a factor of two improvement in Tafel slope; dimeric CoTAA has catalytic activity equal to platinum. Half-cell tests also showed that bonded CoTAA catalysts do not suffer a loss in potential when air is used as a fuel rather than oxygen. Commercially available PTFE was shown to be stable for four months in 200 C 85% phosphoric acid based on lack of change in surface wetting properties, IR and physical characteristics. When stressed electrochemically in 150 C 85% phosphoric acid, PTFE also showed no changes after one month.

Walsh, F.↗
NASA NTRS1991

A study of Na(x)Pt3O4 as an O2 electrode bifunctional electrocatalyst

The present study suggests that polytetrafluoroethylene (PTFE) bonded Na(X)Pt3O4 gas porous diffusion electrodes may be a viable candidate for bifunctional O2 reduction and evolution activity. The electrodes exhibited Tafel slopes of about 0.06 V/decade for both O2 reduction an evolution. For O2 reduction, the 0.06 slope doubled to 0.12 V/decade at larger current densities. Preliminary stability testing at 24 C suggest that the Na(x)Pt3O4 electrodes were relatively stable at reducing and oxidizing potentials typically encountered at the O2 electrodes in a regenerative fuel cell.

Fielder, William L.↗
NASA NTRS2021

Effect of Reactant Pressure on Proton Exchange Membrane Fuel Cell Performance

It is an objective of the National Aeronautics and Space Administration (NASA) to return to the moon and to create sustained lunar operations. Since many applicable lander and upper stage vehicles utilize cryogenic hydrogen and oxygen propellants, it is appealing to incorporate fuel cells into potential mission concepts. A fuel cell could generate electricity, heat, and water from the residual hydrogen and oxygen propellants. Such a concept depends on the capability of the fuel cell to utilize dry, propellant-grade reactants at reduced pressures compared to typical fuel cell operating conditions. This report describes a NASA evaluation of two passive water removal, non-flow-through proton exchange membrane (PEM) fuel cells: a twelve-cell 50 sq. cm active area stack and a seven-cell 150 sq. cm active area stack. Both stacks operated on research grade hydrogen and oxygen reactants supplied at pressures ranging from 20 psia up to the 45-48 psia design operating point, reliably supporting current densities of at least 450 mA/sq. cm at reduced pressures. Polarization curves, fitted with a semi-empirical equation for overpotential, show an increase in effective ohmic resistance and decrease in reversible cell potential, hydrogen crossover current, and Tafel slope when operating at lower pressures, resulting in a reduction in cell voltage at all current densities. Fitted parameters are compared to published values and rationalized with first principles explanations.

fuel cells↗
NASA NTRS1992

The O2 reduction at the IFC modified O2 fuel cell electrode

The International Fuel Corporation (IFC) state of the art (SOA) O2 electrode (Au-10 percent Pt electrocatalyst by weight) is currently being used in the alkaline H2-O2 fuel cell in the NASA Space Shuttle. Recently, IFC modified O2 electrode, as a possible replacement for the SOA electrode. In the present study, O2 reduction data were obtained for the modified electrode at temperatures between 23.3 and 91.7 C. BET measurements gave an electrode BET surface area of about 2070 sq. cm/sq. cm of geometric surface area. The Tafel data could be fitted to two straight line regions. The slope for the lower region, designated as the 0.04 V/decade region, was temperature dependent, and the transfer coefficient was about 1.5. The 'apparent' energy of activation for this region was about 19 kcal/mol. An O2 reduction mechanism for this 0.04 region is presented. In the upper region, designated as the 0.08 V/decade region, diffusion may be the controlling process. Tafel data are presented to illustrate the increase in performance with increasing temperature.

Fielder, William L.↗
NASA NTRS1990

O2 reduction at the IFC orbiter fuel cell O2 electrode

O2 reduction Tafel data were obtained for the IFC Orbiter fuel cell O2 electrode (Au-10 percent Pt catalyst) at temperatures between 24 and 81 C. BET measurements gave an electrode surface area of about 2040 sq cm per sq cm of geometric area. The Tafel data could be fitted to three straight line regions. For current densities less than 0.001 A/sq cm, the slope was essentially independent of temperature with a value of about 0.032 V/decade. Above 0.001 A/sq cm, the two regions, designated in the present study as the 0.04 and 0.12 V/decate regions, were temperature dependent. The apparent energies of activation for these two regions were about 9.3 and 6.5 kcal/mol, respectively. Tafel data (1 atmosphere O2) were extrapolated to 120 C for predicting changes in overpotential with increasing temperature. A mechanism is presented for O2 reduction.

Fielder, William L.↗