Development of an improved oxygen electrode for use in alkaline H2-O2 fuel cells Quarterly report, 1 Oct. - 31 Dec. 1967
Interstitial compounds of transition metals for cathodic oxygen reduction in alkaline hydrogen oxygen fuel cells
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Interstitial compounds of transition metals for cathodic oxygen reduction in alkaline hydrogen oxygen fuel cells
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The NASA Space Station will employ alkaline regenerative fuel cells (RFCs) as its sole electrochemical energy storage system, in virtue of demonstrated technology readiness and a high degree of system-level design flexibility. NASA Johnson and NASA Lewis are currently engaged in the development of a 10-kW alkaline engineering model system, for 1987 delivery, which will encompass a fully autonomous 120-V system with 55 percent overall electrical efficiency and a 20,000-hr service life.
Polymer electrolyte membranes that conduct hydroxide ions have potential use in fuel cells. A variety of polystyrene-based quaternary ammonium hydroxides have been reported as anion exchange fuel cell membranes. However, the hydrolytic stability and conductivity of the commercially available membranes are not adequate to meet the requirements of fuel cell applications. When compared with commercially available membranes, polystyrene-imidazolium alkaline membrane electrolytes are more stable and more highly conducting. At the time of this reporting, this has been the first such usage for imidazolium-based polymeric materials for fuel cells. Imidazolium salts are known to be electrochemically stable over wide potential ranges. By controlling the relative ratio of imidazolium groups in polystyrene-imidazolium salts, their physiochemical properties could be modulated. Alkaline anion exchange membranes based on polystyrene-imidazolium hydroxide materials have been developed. The first step was to synthesize the poly(styrene-co-(1-((4-vinyl)methyl)-3- methylimidazolium) chloride through a free-radical polymerization. Casting of this material followed by in situ treatment of the membranes with sodium hydroxide solutions provided the corresponding hydroxide salts. Various ratios of the monomers 4-chloromoethylvinylbenzine (CMVB) and vinylbenzine (VB) provided various compositions of the polymer. The preferred material, due to the relative ease of casting the film, and its relatively low hygroscopic nature, was a 2:1 ratio of CMVB to VB. Testing confirmed that at room temperature, the new membranes outperformed commercially available membranes by a large margin. With fuel cells now in use at NASA and in transportation, and with defense potential, any improvement to fuel cell efficiency is a significant development.
Of all the fuel cell systems only alkaline and solid polymer electrolyte fuel cells are capable of achieving high power densities (greater than 1 W/sq cm) required for terrestrial and extraterrestrial applications. Electrode kinetic criteria for attaining such high power densities are discussed. Attainment of high power densities in solid polymer electrolyte fuel cells has been demonstrated earlier by different groups using high platinum loading electrodes (4 mg/sq cm). Recent works at Los Alamos National Laboratory and at Texas A and M University (TAMU) demonstrated similar performance for solid polymer electrolyte fuel cells with ten times lower platinum loading (0.45 mg/sq cm) in the electrodes. Some of the results obtained are discussed in terms of the effects of type and thickness of membrane and of the methods platinum localization in the electrodes on the performance of a single cell.
Summarized are the results of a 12-month study to identify high performance regenerative hydrogen-oxygen fuel cell concepts for geosynchronous satellite application. Emphasis was placed on concepts with the potential for high energy density (W-hr/lb) and passive means for water and heat management to maximize system reliability. Both polymer membrane and alkaline electrolyte fuel cells were considered, with emphasis on the alkaline cell because of its high performance, advanced state of development, and proven ability to operate in a launch and space environment. Three alkaline system concepts were studied. The first, the integrated design, utilized a configuration in which the fuel cell and electrolysis cells are alternately stacked inside a pressure vessel. Product water is transferred by diffusion during electrolysis and waste heat is conducted through the pressure wall, thus using completely passive means for transfer and control. The second alkaline system, the dedicated design, uses a separate fuel cell and electrolysis stack so that each unit can be optimized in size and weight based on its orbital operating period. The third design was a dual function stack configuration, in which each cell can operate in both fuel cell and electrolysis mode, thus eliminating the need for two separate stacks and associated equipment. Results indicate that using near term technology energy densities between 46 and 52 W-hr/lb can be achieved at efficiencies of 55 percent. System densities of 115 W-hr/lb are contemplated.
In the last 20 years, direct alcohol fuel cells (DAFCs) have been the subject of tremendous research efforts for the potential application as on-demand power sources. Two leading technologies respectively based on proton exchange membranes (PEMs) and anion exchange membranes (AEMs) have emerged: the first one operating in an acidic environment and conducting protons; the second one operating in alkaline electrolytes and conducting hydroxyl ions. In this review, we present an analysis of the state-of-the-art acidic and alkaline DAFCs fed with methanol and ethanol with the purpose to support a comparative analysis of acidic and alkaline systems, which is missing in the current literature. A special focus is placed on the effect of the reaction stoichiometry in acidic and alkaline systems. Particularly, we point out that, in alkaline systems, OH – participates stoichiometrically to reactions, and that alcohol oxidation products are anions. This aspect must be considered when designing the fuel and when making an energy evaluation from a whole system perspective.
Preparation of institial compounds of transition metals for hydrogen oxygen fuel cell cathodes
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Mats were made from ultrafine polybenzimidazole (PBI) fibers to provide an alternate to the use of asbestos as separators in fuel cells and alkaline batteries. To minimize distortion during mat drying, a process to provide a dry fibrid was developed. Two fibrid types were developed: one coarse, making mats for battery separators; the other fine, making low permeability matrices for fuel cells. Eventually, it was demonstrated that suitable mat fabrication techniques yielded fuel cell separators from the coarser alkaline battery fibrids. The stability of PBI mats to 45% KOH at 123 C can be increased by heat treatment at high temperatures. Weight loss data to 1000 hours exposure show the alkali resistance of the mats to be superior to that of asbestos.
Based on general mass continuity and diffusive transport equations, a mathematical model was developed that simulates the transport of water in Bacon and alkaline-matrix fuel cells. The derived model was validated by using it to analytically reproduce various Bacon and matrix-cell experimental water transport transients.
The results of a 12 month study to identify high performance regenerative hydrogen-oxygen fuel cell concepts for geosynchronous satellite application are summarized. Emphasis was placed on concepts with the potential for high energy density and passive means for water and heat management to maximize system reliability. Both polymer membrane and alkaline electrolyte fuel cells were considered, with emphasis on the alkaline cell because of its high performance, advanced state of development, and proven ability to operate in a launch and space environment. Three alkaline system concepts were studied. Results indicate that using near term technology energy densities between 46 and 52 watt-hour/lb can be achieved at efficiencies of 55 percent. Using advanced light weight cell construction which was achieved in experimental cells, composite tankage material for the reactant gases and the reversible stack concept, system energy densities of 115 watt-hours/lb can be projected.
The results of a 12 month study to identify high performance regenerative hydrogen-oxygen fuel cell concepts for geosynchronous satellite application are summarized. Emphasis was placed on concepts with the potential for high energy density and passive means for water and heat management to maximize system reliability. Both polymer membrane and alkaline electrolyte fuel cells were considered, with emphasis on the alkaline cell because of its high performance, advanced state of development, and proven ability to operate in a launch and space environment. Three alkaline system concepts were studied. Results indicate that using near term technology energy densities between 46 and 52 watt-hour/lb can be achieved at efficiencies of 55 percent. Using advanced light weight cell construction which was achieved in experimental cells, composite tankage material for the reactant gases and the reversible stack concept, system energy densities of 115 watt-hours/lb can be projected.
Design, temperature, carbon dioxide, and current density effects on alkaline hydrogen oxygen fuel cell performance
An experimental study was conducted to assess the feasibility of internal voltage regulation of fuel cell systems. Two methods were tested. In one, reactant partial pressure was used as the voltage control parameter and in the other reactant total pressure was used for control. Both techniques were breadboarded and tested on a single alkaline-electrolyte fuel cell. Both methods were found to be possible forms of regulation, however, of the two the total pressure technique would be more efficient, simpler to apply and would provide better transient characteristics.
Although pyridinic-nitrogen (pyri-N) doped graphene is highly active for the oxygen reduction reaction (ORR) of fuel cells in alkaline media, the activity critically decreases under acidic conditions. Herein we report on how to prevent the deactivation based on the mechanistic understanding that O 2 + pyri–NH ⁺ + e – → O 2,a + pyri–NH governs the ORR kinetics. First, we considered that the deactivation is due to the hydration of pyri-NH + , leading to a lower shift of the redox potential. Introducing the hydrophobic cavity prevented the hydration of pyri-NH + but inhibited the proton transport. We then increased proton conductivity in the hydrophobic cavity by introducing SiO 2 particles coated with ionic liquid polymer/Nafion® which kept the high onset potentials with an increased current density even in acidic media.
Here, we present a facile colloidal synthesis method for producing {101}-facet-tailored CoMn 2 O 4 spinel nano-octahedra with uniform size (9 nm). These nano-octahedra exhibit superior electrocatalytic activity for the oxygen reduction reaction (ORR) in alkaline media compared to their spherical counterparts and previously reported spinel electrocatalysts. At 0.85 V, they achieve a high mass activity (MA) of 60.0 A/g, surpassing the spherical counterparts (38.6 A/g). Furthermore, the CoMn 2 O 4 nano-octahedra demonstrate excellent stability, maintaining an MA of 47.2 A/g after 10,000 durability cycles. This work highlights a promising approach for synthesizing advanced spinel nano-oxides with controlled crystal facets, offering potential as non-precious metal ORR electrocatalysts. The exposed active catalyst surfaces and well-defined structures contribute to their enhanced ORR performance.