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At least 91 records · Page 5

Advanced fuel cell concepts for future NASA missions

Studies of primary fuel cells for advanced all electric shuttle type vehicles show an all fuel cell power system with peak power capability of 100's of kW to be potentially lighter and have lower life cycle costs than a hybrid system using advanced H2O2 APU's for peak power and fuel cells for low power on orbit. Fuel cell specific weights of 1 to 3 lb/kW, a factor of 10 improvement over the orbiter power plant, are projected for the early 1990's. For satellite applications, a study to identify high performance regenerative hydrogen oxygen fuel cell concepts for geosynchronous orbit was completed. Emphasis was placed on concepts with the potential for high energy density (Wh/lb) and passive means for water and heat management to maximize system reliability. Both alkaline electrolyte and polymer membrane fuel cells were considered.

Stedman, J. K.↗

Perovskite oxides: Oxygen electrocatalysis and bulk structure

Perovskite type oxides were considered for use as oxygen reduction and generation electrocatalysts in alkaline electrolytes. Perovskite stability and electrocatalytic activity are studied along with possible relationships of the latter with the bulk solid state properties. A series of compounds of the type LaFe(x)Ni1(-x)O3 was used as a model system to gain information on the possible relationships between surface catalytic activity and bulk structure. Hydrogen peroxide decomposition rate constants were measured for these compounds. Ex situ Mossbauer effect spectroscopy (MES), and magnetic susceptibility measurements were used to study the solid state properties. X ray photoelectron spectroscopy (XPS) was used to examine the surface. MES has indicated the presence of a paramagnetic to magnetically ordered phase transition for values of x between 0.4 and 0.5. A correlation was found between the values of the MES isomer shift and the catalytic activity for peroxide decomposition. Thus, the catalytic activity can be correlated to the d-electron density for the transition metal cations.

Carbonio, R. E.↗

Alkaline water electrolysis technology for Space Station regenerative fuel cell energy storage

The regenerative fuel cell system (RFCS), designed for application to the Space Station energy storage system, is based on state-of-the-art alkaline electrolyte technology and incorporates a dedicated fuel cell system (FCS) and water electrolysis subsystem (WES). In the present study, emphasis is placed on the WES portion of the RFCS. To ensure RFCS availability for the Space Station, the RFCS Space Station Prototype design was undertaken which included a 46-cell 0.93 cu m static feed water electrolysis module and three integrated mechanical components.

Schubert, F. H.↗

Perovskite-type oxides - Oxygen electrocatalysis and bulk structure

Perovskite type oxides were considered for use as oxygen reduction and generation electrocatalysts in alkaline electrolytes. Perovskite stability and electrocatalytic activity are studied along with possible relationships of the latter with the bulk solid state properties. A series of compounds of the type LaFe(x)Ni1(-x)O3 was used as a model system to gain information on the possible relationships between surface catalytic activity and bulk structure. Hydrogen peroxide decomposition rate constants were measured for these compounds. Ex situ Mossbauer effect spectroscopy (MES), and magnetic susceptibility measurements were used to study the solid state properties. X ray photoelectron spectroscopy (XPS) was used to examine the surface. MES has indicated the presence of a paramagnetic to magnetically ordered phase transition for values of x between 0.4 and 0.5. A correlation was found between the values of the MES isomer shift and the catalytic activity for peroxide decomposition. Thus, the catalytic activity can be correlated to the d-electron density for the transition metal cations.

Carbonio, R. E.↗

Space water electrolysis: Space Station through advance missions

Static Feed Electrolyzer (SFE) technology can satisfy the need for oxygen (O2) and Hydrogen (H2) in the Space Station Freedom and future advanced missions. The efficiency with which the SFE technology can be used to generate O2 and H2 is one of its major advantages. In fact, the SFE is baselined for the Oxygen Generation Assembly within the Space Station Freedom's Environmental Control and Life Support System (ECLSS). In the conventional SFE process an alkaline electrolyte is contained within the matrix and is sandwiched between two porous electrodes. The electrodes and matrix make up a unitized cell core. The electrolyte provides the necessary path for the transport of water and ions between the electrodes, and forms a barrier to the diffusion of O2 and H2. A hydrophobic, microporous membrane permits water vapor to diffuse from the feed water to the cell core. This membrane separates the liquid feed water from the product H2, and, therefore, avoids direct contact of the electrodes by the feed water. The feed water is also circulated through an external heat exchanger to control the temperature of the cell.

Ronald J Davenport↗

Endurance Test and Evaluation of Alkaline Water Electrolysis Cells

The overall objective of this program is to assess the state of alkaline water electrolysis cell technology and its potential as part of a Regenerative Fuel Cell System (RFCS) of a multikilowatt orbiting powerplant. The program evaluates the endurance capabilities of alkaline electrolyte water electrolysis cells under various operating conditions, including constant condition testing, cyclic testing and high pressure testing. The RFCS demanded the scale-up of existing cell hardware from 0.1 sq ft active electrode area to 1.0 sq ft active electrode area. A single water electrolysis cell and two six-cell modules of 1.0 sq ft active electrode area were designed and fabricated. The two six-cell 1.0 sq ft modules incorporate 1.0 sq ft utilized cores, which allow for minimization of module assembly complexity and increased tolerance to pressure differential. A water electrolysis subsystem was designed and fabricated to allow testing of the six-cell modules. After completing checkout, shakedown, design verification and parametric testing, a module was incorporated into the Regenerative Fuel Cell System Breadboard (RFCSB) for testing at Life Systems, Inc., and at NASA JSC.

Kovach, Andrew J.↗

Alkaline Capacitors Based on Nitride Nanoparticles

High-energy-density alkaline electrochemical capacitors based on electrodes made of transition-metal nitride nanoparticles are undergoing development. Transition- metal nitrides (in particular, Fe3N and TiN) offer a desirable combination of high electrical conductivity and electrochemical stability in aqueous alkaline electrolytes like KOH. The high energy densities of these capacitors are attributable mainly to their high capacitance densities, which, in turn, are attributable mainly to the large specific surface areas of the electrode nanoparticles. Capacitors of this type could be useful as energy-storage components in such diverse equipment as digital communication systems, implanted medical devices, computers, portable consumer electronic devices, and electric vehicles.

Aldissi, Matt↗

Comprehensive 3D Multiphysics Model on Electrochemical Recovery of O 2 from Metabolic CO 2 at the International Space Station (ISS)

The International Space Station (ISS) is presently equipped with an elaborate, heavy, and high-power consuming system that recovers approximately 50% of O 2 from metabolic CO 2 as part of the atmospheric revitalization (AR) at the ISS habitat. Future long-duration missions will require a sustainable and efficient system capable of yielding a minimum of 75% O 2 recovery to reach the self-sufficiency required for long space missions beyond earth’s low orbit. A Macrofluidic Electrochemical Reactor (MFECR) technology development effort is currently underway at NASA Marshall Space Flight Center (MSFC) to not only increase significantly current O 2 recovery efficiency, improving self-sufficiency on AR at the ISS habitat and future long missions, but also reduce the complexity of the system. The authors have developed and deployed a comprehensive 3D multiphysics model that thoroughly replicates the actual configuration and fluid/material domains of the MFECR. The coupled physics in this multiphysics model include multicomponent-multiphase electrochemical-driven reactions, non-ideal mass transport mechanism, free and porous flow, heat transfer, CO 2 solubility on alkaline electrolyte, water condensation on porous medium, and DC electrical current generation along with Joule heating effect. This model is aimed to conduct quantitive benchmark on three different MFECR’s layouts, one without serpentine paths (plain) and two with serpentines leading to four and twelve paths respectively. Once experimental data is generated via a test matrix of 200 tests, the model will be validated to conduct MFECR’s process optimization and revalidate the quantitive benchmark on three different MFECR’s layouts.

Jesus A. Dominguez↗

Endurance test and evaluation of alkaline water electrolysis cells

Utilization in the development of multi-kW low orbit power systems is discussed. The following technological developments of alkaline water electrolysis cells for space power application were demonstrated: (1) four 92.9 cm2 single water electrolysis cells, two using LST's advanced anodes and two using LST's super anodes; (2) four single cell endurance test stands for life testing of alkaline water electrolyte cells; (3) the solid performance of the advanced electrode and 355 K; (4) the breakthrough performance of the super electrode; (5) the four single cells for over 5,000 hours each significant cell deterioration or cell failure. It is concluded that the static feed water electrolysis concept is reliable and due to the inherent simplicity of the passive water feed mechanism coupled with the use of alkaline electrolyte has greater potential for regenerative fuel cell system applications than alternative electrolyzers. A rise in cell voltage occur after 2,000-3,000 hours which was attributed to deflection of the polysulfone end plates due to creepage of the thermoplastic. More end plate support was added, and the performance of the cells was restored to the initial performance level.

Burke, K. A.↗

High-Efficiency Artificial Photosynthesis Using a Novel Alkaline Membrane Cell

A new cell designed to mimic the photosynthetic processes of plants to convert carbon dioxide into carbonaceous products and oxygen at high efficiency, has an improved configuration using a polymer membrane electrolyte and an alkaline medium. This increases efficiency of the artificial photosynthetic process, achieves high conversion rates, permits the use of inexpensive catalysts, and widens the range of products generated by this type of process. The alkaline membrane electrolyte allows for the continuous generation of sodium formate without the need for any additional separation system. The electrolyte type, pH, electrocatalyst type, and cell voltage were found to have a strong effect on the efficiency of conversion of carbon dioxide to formate. Indium electrodes were found to have higher conversion efficiency compared to lead. Bicarbonate electrolyte offers higher conversion efficiency and higher rates than water solutions saturated with carbon dioxide. pH values between 8 and 9 lead to the maximum values of efficiency. The operating cell voltage of 2.5 V, or higher, ensures conversion of the carbon dioxide to formate, although the hydrogen evolution reaction begins to compete strongly with the formate production reaction at higher cell voltages. Formate is produced at indium and lead electrodes at a conversion efficiency of 48 mg of CO2/kilojoule of energy input. This efficiency is about eight times that of natural photosynthesis in green plants. The electrochemical method of artificial photosynthesis is a promising approach for the conversion, separation and sequestration of carbon dioxide for confined environments as in space habitats, and also for carbon dioxide management in the terrestrial context. The heart of the reactor is a membrane cell fabricated from an alkaline polymer electrolyte membrane and catalyst- coated electrodes. This cell is assembled and held in compression in gold-plated hardware. The cathode side of the cell is supplied with carbon dioxide-saturated water or bicarbonate solution. The anode side of the cell is supplied with sodium hydroxide solution. The solutions are circulated past the electrodes in the electrochemical cell using pumps. A regulated power supply provides the electrical energy required for the reactions. Photovoltaic cells can be used to better mimic the photosynthetic reaction. The current flowing through the electrochemical cell, and the cell voltage, are monitored during experimentation. The products of the electrochemical reduction of carbon dioxide are allowed to accumulate in the cathode reservoir. Samples of the cathode solution are withdrawn for product analysis. Oxygen is generated on the anode side and is allowed to vent out of the reservoir.

Narayan, Sri↗

Sulfide electrolyte additive enables multi-ionic transfer pathways in alkaline iron redox

Traditional alkaline iron (Fe) batteries rely on the conversion reaction between Fe and Fe(OH) 2 but suffer from hydrogen generation upon Fe formation on charging. Fe 2+ /Fe 3+ redox is a promising anode reaction for alkaline Fe batteries, as it alleviates the formation of hydrogen gas during charging. However, achieving complete Fe 2+ /Fe 3+ redox with a one-electron transfer reaction is challenging due to the formation of electrochemically inert Fe 3 O 4 materials. Here, we demonstrate that an alkaline sulfide-containing electrolyte facilitates the reversible multi-ion transfer and transport pathways within (and beyond) the Fe 2+ /Fe 3+ redox system, including Fe(OH) 2 /Fe 3 O 4 conversion, intercalation of hydrosulfide into layered Fe(OH) 2 , and hydrogen deposition, mediated by hydroxyl ions, hydrosulfide anions, and protons, respectively. This multi-ionic charge storage mechanism delivers a compelling discharge capacity of up to 330 mA h g −1 , as determined by chronopotentiometry measurements at a current density of 0.1 A g −1 , exceeding the theoretical iron redox capacity solely relying on Fe 2+ /Fe 3+ redox (∼299 mA h g −1 ). Our study will highlight the potential of alkaline iron redox as a green anode reaction for various aqueous energy storage systems by utilizing a scalable and low-concentration hydrosulfide electrolyte additive.

36 MATERIALS SCIENCE↗

Morphological Degradation of Oxygen Evolution Reaction-Electrocatalyzing Nickel Selenides at Industrially Relevant Current Densities

We investigated electrodeposited nanoparticulate nickel selenide (pre)catalysts that transform into nickel oxides/ oxyhydroxides under oxygen evolution reaction conditions in alkaline solutions. Previous studies of this transformation were conducted at lower current densities than those of industrial relevance (≥1 A cm −2 ). We used ultramicroelectrodes (UMEs) to achieve such current densities, benefiting from their small size, ensuring low absolute currents and low ohmic drop but high current densities. Morphological degradation of the catalyst material was only observed at current densities exceeding 1 A cm −2 but not for smaller ones. Using X-ray absorption, Xray photoemission spectroscopy, and X-ray diffraction, we confirmed that the degradation was accompanied by the literature-known transformation of nanoparticulate Ni 3 Se 2 (bulk)/NiSe (surface) into nickel oxyhydroxide. The transformation of the precatalyst goes along with a significant improvement in the charge transfer kinetics observed by decreasing Tafel slopes with ongoing experimental time extracted from cyclic voltammetry (CV) experiments and electrochemical impedance spectroscopy (EIS) in the high-frequency range. However, these kinetic improvements are accompanied by limitations in mass transport concluded from decreasing current responses at high overpotentials in CVs and increasing impedance in the low-frequency range of the EIS spectra after extended CV cycling. These mass transport limitations originated from morphological degradations at the UME exceeding 1 A cm −2 which we proved by applying identical location scanning electron microscopy. This has not been reported in studies that have been limited to lower current densities before. Our findings showcase how UMEs can be used to study (pre)catalysts (herein nickel selenides) under current densities of industrial relevance in the absence of ohmic drop-related ambiguities, combined with in-depth materials characterization studies, e.g., identical location microscopy and advanced spectroscopic methods. This approach enables direct evaluation and comparison of catalyst materials and thus demonstrates how to overcome long-standing limitations of electrocatalyst design and testing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

ZeroCAL: Eliminating Carbon Dioxide Emissions from Limestone’s Decomposition to Decarbonize Cement Production

Limestone (calcite, CaCO 3 ) is an abundant and cost-effective source of calcium oxide (CaO) for cement and lime production. However, the thermochemical decomposition of limestone (~800 °C, 1 bar) to produce lime (CaO) results in substantial carbon dioxide (CO 2(g) ) emissions and energy use, i.e., ~1 tonne [t] of CO 2 and ~1.4 MWh per t of CaO produced. Here, we describe a new pathway to use CaCO 3 as a Ca source to make hydrated lime (portlandite, Ca(OH) 2 ) at ambient conditions (p, T) while nearly eliminating process CO 2(g) emissions (as low as 1.5 mol. % of the CO 2 in the precursor CaCO 3 , equivalent to 9 kg of CO 2(g) per t of Ca(OH) 2 ) within an aqueous flowelectrolysis/ pH-swing process that coproduces hydrogen (H 2(g) ) and oxygen (O 2(g) ). Because Ca(OH) 2 is a zero-carbon precursor for cement and lime production, this approach represents a significant advancement in the production of zero-carbon cement. The Zero CArbon Lime (ZeroCAL) process includes dissolution, separation/recovery, and electrolysis stages according to the following steps: (Step 1) chelator (e.g., ethylenediaminetetraacetic acid, EDTA)-promoted dissolution of CaCO 3 and complexation of Ca 2+ under basic (>pH 9) conditions, (Step 2a) Ca enrichment and separation using nanofiltration (NF), which allows separation of the Ca-EDTA complex from the accompanying bicarbonate (HCO 3 – ) species, (Step 2b) acidity-promoted decomplexation of Ca from EDTA, which allows near-complete chelator recovery and the formation of a Ca-enriched stream, and (Step 3) rapid precipitation of Ca(OH) 2 from the Ca-enriched stream using electrolytically produced alkalinity. These reactions can be conducted in a seawater matrix yielding coproducts including hydrochloric acid (HCl) and sodium bicarbonate (NaHCO 3 ), resulting from electrolysis and limestone dissolution, respectively. Careful analysis of the reaction stoichiometries and energy balances indicates that approximately 1.35 t of CaCO 3 , 1.09 t of water, 0.79 t of sodium chloride (NaCl), and ~2 MWh of electrical energy are required to produce 1 t of Ca(OH) 2 , with significant opportunity for process intensification. This approach has major implications for decarbonizing cement production within a paradigm that emphasizes the use of existing cement plants and electrification of industrial operations, while also creating approaches for alkalinity production that enable cost-effective and scalable CO 2 mineralization via Ca(OH) 2 carbonation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗