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At least 163 records · Page 9

Modeling Electrokinetics of Oxygen Electrodes in Solid Oxide Electrolyzer Cells

A microscale model is presented in this study to simulate electrode kinetics of the oxygen electrode in a solid oxide electrolyzer cell (SOEC). Two mixed ionic/electronic conducting structures are examined for the oxygen producing electrode in this work: single layer porous lanthanum strontium cobalt ferrite (LSCF), and bilayer LSCF/SCT (strontium cobalt tantalum oxide) structures. A yttrium-stabilized zirconia (YSZ) electrolyte separates the hydrogen and oxygen electrodes, as well as a gadolinium doped-ceria (GDC) buffer layer on the oxygen electrode side. Electrochemical reactions occurring at the two-phase boundaries (2PBs) and three-phase boundaries (3PBs) of single-layer LSCF and bilayer LSCF/SCT oxygen electrodes are modeled under various SOEC voltages with lattice oxygen stoichiometry as the key output. The results reveal that there exists a competition in electrode kinetics between 2PBs and 3PBs, but 3PBs are the primary reactive sites for single-layer LSCF oxygen electrode under high voltages. These locations experience the greatest oxygen stoichiometry variations and are therefore the most likely locations for dimensional changes. By applying an active SCT layer over LSCF, the 2PBs become activated to compete with the 3PBs, thus alleviating oxygen stoichiometry variations and reducing the likelihood of dimensional change. This strategy could reduce lattice structural expansion, proving to be valuable for electrode-electrolyte delamination prevention and will be the focus of future work.

30 DIRECT ENERGY CONVERSION↗

Oxy-combustion process with modular boiler design

A modular boiler system for implementing fuel combustion is provided. The system includes a first boiler and a second boiler of a plurality of boilers, an oxygen input unit, a fuel input unit, a recycled flue gas input unit, and a flue gas separator. The first boiler receives oxygen from the oxygen input unit, fuel from the fuel input unit, and recycled flue gas from the recycled flue gas input unit. The first boiler outputs intra-system flue gas. The flue gas separator separates the intra-system flue gas into a first and second flue gas stream, transfers the first flue gas stream to the second boiler, and transfers the second flue gas stream to a gas cleaning system. The second boiler receives oxygen from the oxygen input unit, fuel from the fuel input unit, and the first flue gas stream from the flue gas separator.

Axelbaum, Richard L.↗

Increased Oxygen Recovery from Sabatier Systems Using Plasma Pyrolysis Technology and Metal Hydride Separation

State-of-the-art life support carbon dioxide (CO2) reduction technology is based on the Sabatier reaction where less than 50% of the oxygen required for the crew is recovered from metabolic CO2. The reaction produces water as the primary product and methane as a byproduct. Oxygen recovery is constrained by the limited availability of reactant hydrogen. This is further exacerbated when Sabatier methane (CH4) is vented as a waste product resulting in a continuous loss of reactant hydrogen. Post-processing methane with the Plasma Pyrolysis Assembly (PPA) to recover hydrogen has the potential to dramatically increase oxygen recovery and thus drastically reduce the logistical challenges associated with oxygen resupply. The PPA decomposes methane into predominantly hydrogen and acetylene. Due to the highly unstable nature of acetylene, a separation system is necessary to purify hydrogen before it is recycled back to the Sabatier reactor. Testing and evaluation of a full-scale Third Generation PPA is reported and investigations into metal hydride hydrogen separation technology is discussed.

Zachary W Greenwood↗

Monatomic Oxygen Makes Materials Biocompatible

Treatment with monatomic oxygen activates surfaces of biomedical and biotechnical materials without adversely affecting properties of bulk and without introducing toxic or otherwise dangerous solvent residues. Treatment used to create carpetlike texture increasing surface area and encouraging cells to adhere and grow. On silicone tubing for vascular implants, carpet surface improves acceptance by body. On polymer beads and vessels, surface increases effectiveness of growing, storing, and separating cell cultures. Monatomic oxygen relatively abundant in upper atmosphere of Earth, thus treatments carried out on Space Shuttle missions. Alternatively, one of several high-energy neutral-beam devices used in terrestrial laboratories.

Spaulding, Glenn↗

Electrochemical measurements and thermodynamic calculations of redox equilibria in pallasite meteorites - Implications for the eucrite parent body

The intrinsic oxygen fugacity (IOF) of olivine separates from the Salta, Springwater, and Eagle Station pallasites was measured between 850 and 1150 C using oxygen-specific solid zirconia electrolytes at 100,000 Pa. Thermodynamic calculations of redox equilibria involving equalibrium pallasite assemblages are in good agreement with the experimental results and provide a lower limit to pallasite redox stability; others involving disequilibrium assemblages, suggest that pallasites experienced localized, late-stage oxidation and reduction effects. Consideration of the redox buffer metal-olivine-orthopyroxene utilizing calculated Eucrite Parent Body (EPB) mantle phase compositions indicates that small redox gradients may have existed in the EPB. Such gradients may have produced strong compositional variation within the EPB. In addition, there is apparently significant redox heterogeneity in the source area of Eagle Station Trio pallasites and Bocaiuva iron meteorites.

Righter, Kevin↗

Comparative Study on the Photoelectrochemical Hydrogen Production from the Layout Optimization in a Unit Cell

Solar-driven water splitting is achieved by connecting photovoltaics with electrolysis. Recently, integrated approaches of the two configurations for photoelectrochemical reactions have shown great potential in a combined unit, but strategies to address further material and cell development face significant scientific challenges. Here, in this work, we present an experimental demonstration of photoelectrochemical (PEC) unit-cells with efficient separate dual compartments for oxygen evolution and hydrogen evolution reactions. The design and fabrication of cell architectures with various degrees of integration are investigated efficient and sustainable PEC processes. The effect of the nanostructured silicon (Si) photoelectrodes, including the adoption of layer architectures, surface protection layer deposition, and membrane electrode assembly is further studied to optimize the design parameters of the PEC unit-cells. This developed PEC cell with the Si photocathode achieved a photocurrent density of -4.8 mA cm –2 at -2.0 V cell and -2.87 mA cm –2 at -1.6 V cell . It clearly provides a critical milestone for unbiased solar water splitting. Practical solar to hydrogen (STH) can be directly estimated in investigating PEC performance in this unit-cell as assembled with a solar cell. It is a significantly meaningful step forward in practical solar fuel production.

08 HYDROGEN↗

In Situ Tracking of Nonthermal Plasma Etching of ZIF-8 Films

Surface characterization is critical for understanding the processes used for preparing catalysts, sorbents, and membranes. Nonthermal plasma (NTP) is a process that achieves high reactivity at low temperatures and is used to tailor the surface properties of materials. In this work, we combine the capabilities of infrared reflection absorption spectroscopy (IRRAS) with NTP for the in situ interrogation of zeolitic imidazolate framework-8 (ZIF-8) thin films to probe modifications in the material induced by oxygen and nitrogen plasmas. The IRRAS measurements in oxygen plasma reveal etching of organic ligands with sequential removal of the methyl group and imidazole ring and with the formation of carbonyl moieties (C═O). In contrast, nitrogen plasma induces mild etching and grafting of nitrile groups (−C≡N). Scanning electron microscopy imaging shows that oxygen plasma, at prolonged times, significantly degrades the ZIF-8 film at the grain boundaries. Treatment of ZIF-8 membranes using mild plasma conditions yields a fivefold enhancement for H 2 /N 2 and CO 2 /CH 4 ideal selectivities and an eightfold enhancement for CO 2 /N 2 ideal selectivity. Additionally, the new tools described here can be used for spectroscopic in situ tracking of plasma-induced chemistry on thin films in general.

IRRAS↗

REDOTHERM: a thermodynamic modeling framework for redox-based thermochemical processes

Two-step thermochemical redox cycles are being developed as a potential pathway for the production of hydrogen and syngas. While there are many possible reactor and system configurations, moving oxide systems are considered promising in terms of the redox thermodynamics, due to the potential implementation of a countercurrent system that can achieve higher performance compared to other configurations. There is a lack of a robust thermodynamic modeling framework in the field, with multiple models incorporating incorrect thermodynamic assumptions that violate the second law of thermodynamics. We present in this work REDOTHERM, an open-source system model for moving oxides that incorporates the correct thermodynamic limits, as well as various options for the system auxiliary units including product separation, heat recovery, and oxygen removal. The model is agnostic to the energy source, and could be used for solar thermal or other configurations. We highlight the uses of this model, presenting some of the tradeoffs and challenges in redox-active material selection and how they affect the entire thermochemical hydrogen production process. This model could be easily adapted and used for material exploration, system/reactor design, and technoeconomic analysis.

08 HYDROGEN↗

Photocatalytic water splitting for large-scale solar-to-chemical energy conversion and storage

Sunlight-driven water splitting allows renewable hydrogen to be produced from abundant and environmentally benign water. Large-scale societal implementation of this green fuel production technology within energy generation systems is essential for the establishment of sustainable future societies. Among various technologies, photocatalytic water splitting using particulate semiconductors has attracted increasing attention as a method to produce large amounts of green fuels at low cost. The key to making this technology practical is the development of photocatalysts capable of splitting water with high solar-to-fuel energy conversion efficiency. Furthermore, advances that enable the deployment of water-splitting photocatalysts over large areas are necessary, as is the ability to recover hydrogen safely and efficiently from the produced oxyhydrogen gas. This lead article describes the key discoveries and recent research trends in photosynthesis using particulate semiconductors and photocatalyst sheets for overall water splitting, via one-step excitation and two-step excitation (Z-scheme reactions), as well as for direct conversion of carbon dioxide into renewable fuels using water as an electron donor. We describe the latest advances in solar water-splitting and carbon dioxide reduction systems and pathways to improve their future performance, together with challenges and solutions in their practical application and scalability, including the fixation of particulate photocatalysts, hydrogen recovery, safety design of reactor systems, and approaches to separately generate hydrogen and oxygen from water.

30 DIRECT ENERGY CONVERSION↗

Effect of LEO cycling on 125 Ah advanced design IPV nickel-hydrogen battery cells

An advanced 125 Ah individual pressure vessel (IPV) nickel-hydrogen cell was designed. The primary function of the advanced cell, is to store and deliver energy for long term, low earth-orbit (LEO) spacecraft missions. The new features of this design are: (1) use of 26 percent rather than 31 percent potassium hydroxide (KOH) electrolyte, (2) use of a patented catalyzed wall wick, (3) use of serrated edge separators to facilitate gaseous oxygen and hydrogen flow within the cell, while still maintaining physical contact with the wall wick for electrolyte management, and (4) use of a floating rather than a fixed stack (state-of-the-art) to accommodate nickel electrode expansion. Six 125 Ah flight cells based on this design were fabricated by Eagle-Picher. Three of the cells contain all of the advanced features (test cells) and three are the same as the test cells except they don't have catalyst on the wall wick (control cells). All six cells are in the process of being evaluated in a LEO cycle life test. The cells have accumulated about 4700 LEO cycles (60 percent DOD 10 C). There have been no cell failures, the catalyzed wall wick cells however, are performing better.

Smithrick, John J.↗

Ion optics system incorporating radio frequency mass separation

Results of an experimental study are presented. They show that an RF mass discriminator, based on a Bennett mass spectrometer concept, can be used to discriminate between two species of ions with about a 2-to-1 charge-to-mass ratio. Such a device would be useful for separating monatomic and diatomic oxygen ions in a system designed to simulate the environment that spacecraft encounter in low earth orbit. The influence of changing mass discriminator parameters - such as the spacing of its grids, the amplitude and frequency of RF voltage signals applied to it and the current density of ions incident upon it - on its species discrimination capabilities is discussed. Experimental results are also compared to the results of a simple theoretical model to gain insight into the processes occurring in the discriminator. These results are shown to be in good agreement.

Anderson, John R.↗

Effect of LEO cycling on 125 Ah advanced design IPV nickel-hydrogen battery cells

An advanced 125 Ah individual pressure vessel (IPV) nickel-hydrogen cell was designed. The primary function of the advanced cell is to store and deliver energy for long-term, low earth-orbit (LEO) spacecraft missions. The new features of this design are: (1) use of 26 percent rather than 31 percent potassium hydroxide (KOH) electrolyte, (2) use of a patented catalyzed wall wick, (3) use of serrated-edge separators to facilitate gaseous oxygen and hydrogen flow within the cell, while still maintaining physical contact with the wall wick for electrolyte management, and (4) use of a floating rather than a fixed stack (state-of-the-art) to accommodate nickel electrode expansion. Six 125-Ah flight cells based on this design were fabricated by Eagle-Picher. Three of the cells contain all of the advanced features (test cells) and three are the same as the test cells except they don't have catalyst on the wall wick (control cells). All six cells are in the process of being evaluated in a LEO cycle life test. The cells have accumulated about 4700 LEO cycles (60 percent DOD 10 C). There have been no cell failures; the catalyzed wall wick cells, however, are performing better.

Smithrick, John J.↗

Validation test of advanced technology for IPV nickel-hydrogen flight cells: Update

Individual pressure vessel (IPV) nickel-hydrogen technology was advanced at NASA Lewis and under Lewis contracts with the intention of improving cycle life and performance. One advancement was to use 26 percent potassium hydroxide (KOH) electrolyte to improve cycle life. Another advancement was to modify the state-of-the-art cell design to eliminate identified failure modes. The modified design is referred to as the advanced design. A breakthrough in the low-earth-orbit (LEO) cycle life of IPV nickel-hydrogen cells has been previously reported. The cycle life of boiler plate cells containing 26 percent KOH electrolyte was about 40,000 LEO cycles compared to 3,500 cycles for cells containing 31 percent KOH. The boiler plate test results are in the process of being validated using flight hardware and real time LEO testing at the Naval Weapons Support Center (NWSC), Crane, Indiana under a NASA Lewis Contract. An advanced 125 Ah IPV nickel-hydrogen cell was designed. The primary function of the advanced cell is to store and deliver energy for long-term, LEO spacecraft missions. The new features of this design are: (1) use of 26 percent rather than 31 percent KOH electrolyte; (2) use of a patented catalyzed wall wick; (3) use of serrated-edge separators to facilitate gaseous oxygen and hydrogen flow within the cell, while still maintaining physical contact with the wall wick for electrolyte management; and (4) use of a floating rather than a fixed stack (state-of-the-art) to accommodate nickel electrode expansion due to charge/discharge cycling. The significant improvements resulting from these innovations are: extended cycle life; enhanced thermal, electrolyte, and oxygen management; and accommodation of nickel electrode expansion. The advanced cell design is in the process of being validated using real time LEO cycle life testing of NWSC, Crane, Indiana. An update of validation test results confirming this technology is presented.

Smithrick, John J.↗

Validation test of 125 Ah advanced design IPV nickel-hydrogen flight cells

An update of validation test results confirming the advanced design nickel-hydrogen cell is presented. An advanced 125 Ah individual pressure vessel (IPV) nickel-hydrogen cell was designed. The primary function of the advanced cell is to store and deliver energy for long-term, Low-Earth-Orbit (LEO) spacecraft missions. The new features of this design, which are not incorporated in state-of-the-art design cells, are: (1) use of 26 percent rather than 31 percent potassium hydroxide (KOH) electrolyte; (2) use of a patented catalyzed wall wick; (3) use of serrated-edge separators to facilitate gaseous oxygen and hydrogen flow within the cell, while still maintaining physical contact with the wall wick for electrolyte management; and (4) use of a floating rather than a fixed stack (state-of-the-art) to accommodate nickel electrode expansion due to charge/discharge cycling. The significant improvements resulting from these innovations are extended cycle life; enhanced thermal, electrolyte, and oxygen management; and accommodation of nickel electrode expansion. Six 125 Ah flight cells based on this design were fabricated by Eagle-Picher. Three of the cells contain all of the advanced features (test cells) and three are the same as the test cells except they do not have catalyst on the wall wick (control cells). All six cells are in the process of being evaluated in a LEO cycle life test at the Naval Weapons Support Center, Crane, IN, under a NASA Lewis Research Center contract. The catalyzed wall wick cells have been cycled for over 19000 cycles with no cell failures in the continuing test. Two of the noncatalyzed wall wick cells failed (cycles 9588 and 13,900).

Smithrick, John J.↗

Plasma separation

This process employs a thermal plasma for the separation and production of oxygen and metals. It is a continuous process that requires no consumables and relies entirely on space resources. The almost complete absence of waste renders it relatively clean. It can be turned on or off without any undesirable side effects or residues. The prime disadvantage is its high power consumption.

Steurer, Wolfgang↗