Development of cathodic electrocatalysts for use in low temperature H2/O2 fuel cells with an alkaline electrolyte, January 1-31, 1966
Cathodic electrocatalyst development for use in low temperature hydrox fuel cell in alkaline electrolyte
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Cathodic electrocatalyst development for use in low temperature hydrox fuel cell in alkaline electrolyte
Oxygen reduction reactions (ORRs) at the cathode are the rate-limiting step in fuel cell performance. The ORR is 100 times slower than the corresponding hydrogen oxidation at the anode. Speeding up the reaction at the cathode will improve fuel cell efficiency. The cathode material is generally Pt powder painted onto a substrate (e.g., graphite paper). Recent efforts in the fuel cell area have focused on replacing Pt with Pt-X alloys (where X = Co, Ni, Zr, etc.) in order to (a) reduce cost, and (b) increase ORR rates. One of these strategies is to increase ORR rates by reducing the powder size, which would result in an increase in the surface area, thereby facilitating faster reaction rates. In this work, a process has been developed that creates Pt-Ni or Pt-Co alloys that are finely divided (on the nano scale) and provide equivalent performance at lower Pt loadings. Lower Pt loadings will translate to lower cost. Precursor salts of the metals are dissolved in water and mixed. Next, the salt mixtures are dried on a hot plate. Finally, the dried salt mixture is heattreated in a furnace under flowing reducing gas. The catalyst powder is then used to fabricate a membrane electrode assembly (MEA) for electrochemical performance testing. The Pt- Co catalyst-based MEA showed comparable performance to an MEA fabri cated using a standard Pt black fuel cell catalyst. The main objective of this program has been to increase the overall efficiencies of fuel cell systems to support power for manned lunar bases. This work may also have an impact on terrestrial programs, possibly to support the effort to develop a carbon-free energy source. This catalyst can be used to fabricate high-efficiency fuel cell units that can be used in space as regenerative fuel cell systems, and terrestrially as primary fuel cells. Terrestrially, this technology will become increasingly important when transition to a hydrogen economy occurs.
Cathodic electrocatalysts development for use in low temperature hydrogen-oxygen fuel cells with alkaline electrolyte
Potentiostatic and corrosion resistance tests for metallic ingots prepared as rotating disk electrodes - cathodic electrocatalysts for use in low temperature hydrogen-oxygen fuel cells
Cathodic electrocatalysts for use in low temperature hydrogen-oxygen fuel cells with an alkaline electrolyte-corrosion resistance and activity testing of materials and elements
Cathodic electrocatalyst materials studied for use in low temperature hydrogen oxygen fuel cells with alkaline electrolyte
Development of cathodic electrocatalysts for use in low temperature hydrogen-oxygen fuel cells with alkaline electrolyte
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.
A perturbation testing method has been developed and tested for predictive testing of fuel cells. This method involves application of small changes to the operating conditions of the cell in a predetermined sequence. The resultant response of the cell is then measured and statistically correlated with the corresponding test conditions. This method has been applied to the phosphoric acid fuel cell, and the effect of operating and cell-component variables on cell-performance degradation has been studied. A strong effect of the cell temperature and cathode potential on fuel-cell-performance degradation has been observed. A cell-performance degradation model has been formulated, and the unknown parameters in the model have been estimated by a regression analysis of the experimental data. A reasonable agreement between the fuel cell performance predicted by this model (derived from the perturbation experiments) and the unperturbed test data supports fthe applicability of the perturbation method.
Hydrogen-oxygen electrolytic regenerative fuel cell development and cycling tests of cathode catalyst loading and asbestos mat type, and electrolyte/asbestos weight ratio variations
Cathodic electrocatalysts for use in low temperature hydrogen oxygen fuel cells with alkaline electrolyte
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.
Cathodic catalysts evaluated for hydrazine-air fuel cells employing alkaline electrolytes
Fuel cell designs and techniques for converting chemical energy into electrical energy uses a fuel cell are disclosed. The designs and techniques include an anode to receive fuel, a cathode to receive oxygen, and an electrolyte chamber in the fuel cell, including an electrolyte medium, where the electrolyte medium includes an inorganic salt mixture in the fuel cell. The salt mixture includes pre-determined quantities of at least two salts chosen from a group consisting of ammonium trifluoromethanesulfonate, ammonium trifluoroacetate, and ammonium nitrate, to conduct charge from the anode to the cathode. The fuel cell includes an electrical circuit operatively coupled to the fuel cell to transport electrons from the cathode.
Attention is given to topics of advanced concepts, hydrogen-oxygen fuel cells and electrolyzers, nickel electrodes, and advanced rechargeable batteries. Papers are presented on human exploration mission studies, advanced rechargeable sodium batteries with novel cathodes, advanced double-layer capacitors, recent advances in solid-polymer electrolyte fuel cell technology with low platinum loading electrodes, electrocatalysts for oxygen electrodes in fuel cells and water electrolyzers for space applications, and the corrosion testing of candidates for the alkaline fuel cell cathode. Other papers are on a structural comparison of nickel electodes and precursor phases, the application of electrochemical impedance spectroscopy for characterizing the degradation of Ni(OH)2/NiOOH electrodes, advances in lightweight nickel electrode technology, multimission nickel-hydrogen battery cell for the 1990s, a sodium-sulfur battery flight experiment definition study, and advances in ambient-temperature secondary lithium cells.
A difficulty encountered in designing a unitized regenerative proton exchange membrane (PEM) fuel cell lies in the incompatibility of electrode structures and electrocatalyst materials optimized for either of the two functions (fuel cell or electrolyzer) with the needs of the other function. This difficulty is compounded in previous regenerative fuel cell designs by the fact that water, which is needed for proton conduction in the PEM during both modes of operation, is the reactant supplied to the anode in the electrolyzer mode of operation and the product formed at the cathode in the fuel cell mode. Drawbacks associated with existing regenerative fuel cells have been addressed in work performed at Lynntech. In a first innovation, electrodes function either as oxidation electrodes (hydrogen ionization or oxygen evolution) or as reduction electrodes (oxygen reduction or hydrogen evolution) in the fuel cell and electrolyzer modes, respectively. Control of liquid water within the regenerative fuel cell has been brought about by a second innovation. A novel PEM has been developed with internal channels that permit the direct access of water along the length of the membrane. Lateral diffusion of water along the polymer chains of the PEM provides the water needed at electrode/PEM interfaces. Fabrication of the novel unitized regenerative fuel cell and results obtained on testing it will be presented.
A difficulty encountered in designing a unitized regenerative proton exchange membrane (PEM) fuel cell lies in the incompatibility of electrode structures and electrocatalyst materials optimized for either of the two functions (fuel cell or electrolyzer) with the needs of the other function. This difficulty is compounded in previous regenerative fuel cell designs by the fact that water, which is needed for proton conduction in the PEM during both modes of operation, is the reactant supplied to the anode in the electrolyzer mode of operation and the product formed at the cathode in the fuel cell mode. Drawbacks associated with existing regenerative fuel cells have been addressed. In a first innovation, electrodes function either as oxidation electrodes (hydrogen ionization or oxygen evolution) or as reduction electrodes (oxygen reduction or hydrogen evolution) in the fuel cell and electrolyzer modes, respectively. Control of liquid water within the regenerative fuel cell has been brought about by a second innovation. A novel PEM has been developed with internal channels that permit the direct access of water along the length of the membrane. Lateral diffusion of water along the polymer chains of the PEM provides the water needed at electrode/PEM interfaces. Fabrication of the novel single cell unitized regenerative fuel cell and results obtained on testing it are presented.
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.