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At least 19 records

Impact of Sr-Containing Secondary Phases on Oxide Conductivity in Solid-Oxide Electrolyzer Cells

Solid-oxide electrolyzer cells (SOECs) based on a yttria-stabilized zirconia (YSZ) oxide electrolyte produce hydrogen from water with the assistance of excess thermal energy; however, Sr diffusion within the Gd-doped CeO 2 (GDC) barrier layer during processing or operation can lead to the formation of unwanted secondary phases such as SrO and SrZrO 3 . Here, to establish and compare the degree of impact of these phases on SOEC performance, we conduct first-principles calculations to study their bulk oxide conductivities and compare them to that of the YSZ electrolyte. We find that SrO has a low conductivity arising from the poor mobility and low concentration of mobile oxygen vacancies, and its presence in SOECs should therefore be avoided. SrZrO 3 also has a lower oxide conductivity than YSZ; however, this discrepancy is primarily due to lower vacancy concentrations rather than low mobility. We find that sufficient levels of Y-doping on the Zr site can increase oxygen vacancy concentrations in SrZrO 3 to achieve an oxide ionic conductivity on par with that of YSZ, thereby mitigating any potential deleterious effect on transport performance. Energy-dispersive X-ray spectroscopy confirms that Y is the most common minority element present in SrZrO 3 forming near the GDC–YSZ interface, alleviating concerns regarding the impact of SrZrO 3 on device performance. These results from our combined computational–experimental analysis can inform future engineering strategies designed to limit the detrimental effects of Sr-induced secondary phase formation on SOEC performance.

08 HYDROGEN

Kinetics and Thermodynamics of Sr Permeation in CeO 2 -Based Barrier Layers for Solid-Oxide Electrolyzer Cells

Solid-oxide electrolyzer cells (SOECs) convert steam to hydrogen efficiently at high temperatures. However, during operation, the diffusion of cations or impurities through the cells due to electrode degradation can cause unwanted secondary phases to form, which may degrade device performance. Here, in this study, we use atomistic and mesoscale simulations coupled with experimental analysis to study the diffusion of Sr through the Gd-doped CeO 2 (GDC) barrier layer used to protect the yttria-stabilized zirconia (YSZ) electrolyte in SOECs. From our atomistic calculations, we find Sr diffusion to be negligibly slow in bulk GDC; however, surface diffusion is much more favorable. Subsequent mesoscale simulations show that Sr diffusion is activated when the porosity of GDC exceeds ∼10% and significantly exceeds diffusion in bulk and grain boundary regions. We also find that SrO-based species can accumulate at GDC surfaces; however, SrO aggregation and coarsening will be limited by the large lattice mismatch between GDC and SrO. Energy-dispersive X-ray spectroscopy (EDS) and electron diffraction confirm that Sr can accumulate within GDC pores and form disperse Sr-containing secondary phases. Altogether, Sr diffusion in dense GDC is unlikely to give rise to thick SrO layers, which would severely limit device performance. The formation of Sr-containing secondary phases can largely be avoided by restricting the porosity of the GDC layer as much as possible.

36 MATERIALS SCIENCE

Effect of high scandium doping in barium zirconate on nickel diffusion and performance of proton-conducting solid oxide electrolyzer cells

Proton-conducting solid oxide electrolyzer cells (p-SOECs) are emerging but promising technologies for hydrogen production. However, due to the lack of a robust electrolyte, p-SOECs struggle simultaneously to display high performance, Faradaic efficiency, and durability. Motivated by its high proton concentrations and stability as a barium zirconate, we have investigated BaZr 0.6 Sc 0.4 O 3-δ (BZSc40) as a potential next-generation p-SOEC electrolyte. Here, we found elevated levels of NiO diffusion through BZSc40 electrolytes during high-temperature sintering, attributed to the large oxygen vacancy concentrations present in BZSc40, as revealed by first-principle computational results. Controlling NiO diffusion is critical, as it can facilitate densification and grain size growth, but it may also detrimentally impact performance by causing electronic leakage. By optimizing sintering temperature when fabricating BZSc40 cells, we successfully controlled NiO diffusion, achieving sufficient electrolyte densification along with high performance and Faradaic efficiency. BZSc40 cells reached −0.99 A/cm 2 at 1.3 V and 600 °C and exhibited enhanced durability with a 3.37 mV/kh degradation rate at −0.8 A/cm 2 over a 200-h testing period. BZSc40 electrolytes demonstrated superior performance over BaZr 0.8 Y 0.2 O 3-δ (BZY20). In addition to elevated current densities and grain sizes, BZSc40 cells achieved Faradaic efficiencies of 76 % compared to 54 % for BZY20 at −0.2 A/cm 2 and 600 °C. This work lays the foundation for BZSc40 as a potential electrolyte due to its advantages over BZY20 while demonstrating the significance of controlling NiO diffusion when fabricating p-SOECs.

Electrolyzer

Improving durability and performance of solid oxide electrolyzers by controlling surface composition on oxygen electrodes

Solid oxide electrolysis cell (SOEC) is a promising technology for high-efficiency energy conversion, enabling the production of hydrogen, syngas, synthetic fuels, and various commodity chemicals. Unlike traditional thermochemical processes, SOECs operate at elevated temperatures (600-850°C), benefiting from favorable thermodynamics and reaction kinetics. This makes them highly energy efficient compared to alkaline or polymer electrolyte membrane (PEM) electrolysis technologies. However, despite these advantages, SOECs face significant challenges related to performance degradation over time. A primary issue is the degradation of the oxygen electrode due to strontium (Sr) segregation and impurity poisoning from chromium (Cr) and sulfur (S). This is because the pathway to deposition of Cr and S include the reaction of Cr and S with the segregated SrO at the surface. Sr segregation leads to the formation of insulating compounds such as SrCrO4 and SrSO4, which block active sites, reduce oxygen exchange rates, and compromise the electrode's electrochemical stability. The degradation mechanisms involve complex interactions between the electrode material's surface chemistry, microstructure, and the operating environment. Sr segregation is particularly problematic because it facilitates the deposition of Cr and S impurities, exacerbating performance losses. Addressing these issues is critical to enhancing the durability and economic viability of SOEC technology. The primary goal of this project is to improve the durability and performance of SOECs by controlling the surface composition of the oxygen electrode. This is achieved by suppressing Sr segregation, thereby mitigating impurity poisoning pathways. The project aims to enhance the oxygen exchange rate, improve cell stability, and extend the operational lifespan of SOECs without necessitating major changes to electrode chemistry or stack components.

30 DIRECT ENERGY CONVERSION

Oxygen scrubbing and sensing in plant growth chambers using solid oxide electrolyzers

The maintenance of optimal levels of oxygen in the gaseous environment of a plant growth chamber during light and dark periods is an essential criterion for the correct growth of plants. The use of solid oxide electrolyzers to control the oxygen levels by removing the excess gaseous oxygen during periods of illumination and full-scale photosynthesis is described. A part of the oxygen removed can be stored and supplied back to the plants during dark periods. The excess oxygen can be used by the crew. The electrolizer can be additionally used in its open circuit mode, to sense the oxygen concentrations in the plant chamber. The solid oxide electrolysis process is described.

Sridhar, K. R.

Advanced Manifolds for Improved Solid Oxide Electrolyzer Performance

An investigation was conducted to see if additive manufacturing could be used to fabricate more efficient manifold designs for improved flow, reduced stresses, and decreased number of joints to be sealed for a solid oxide electrolyzer used to convert carbon dioxide to oxygen. Computational flow and mechanical modeling were conducted on a NASA Glenn Research Center patented cell and stack design with the potential to achieve a 3-4 times mass reduction. Various manifold designs were modeled, and two were downselected to be fabricated and tested. Some benefit was seen in a baffled manifold design, which directed incoming flow more effectively into the flow channels, compared to the original design, where the flow spent more time within the manifold itself. Flow measurements indicated some non-uniformity of flow across the channels at higher flow rates, which were not predicted by the model. Some possible explanations for the differences are discussed.

Linne, Diane L.

Real-Time Simulation of Solid Oxide Electrolyzers (SOEC) for Dynamic Operability Improvement and Cyber-Physical System Development

As more intermittent-renewable generations are being added to the power grid, solid oxide electrolysis cells (SOEC) must enhance their rapid load transition capabilities to load follow and support grid resilience. At NETL, we developed real-time SOEC models to research SOEC transients during load step changes. The gained insights can be useful for dynamic operability improvement. These real-time SOEC models also established the basis for cyber-physical SOEC hybrid energy systems. (Virtual presentation to the 2025 MILLENNIUM CLEAN and SUSTAINABLE POWER workshop, University of Genoa, Italy)

20 FOSSIL-FUELED POWER PLANTS

Technology Assessment for Producing Propellant From Lunar Water

Introduction: The presence of water ice in permanently shadowed regions (PSRs) on the lunar surface may enable a sustained human presence on the Moon with minimal need for consumables. One of the most valuable uses of lunar water is to produce rocket propellant. A sustained human presence on the Moon will re-quire frequent launches from the lunar surface, and each launch will require tons of propellant. However, many other volatiles are likely to be present in the areas where lunar water is stable1. Producing propellant from lunar water in-situ will require the separation and purification of water before it can be electrolyzed into oxygen and hydrogen gas. The Resource Exploration and Science of OUR Cosmic Environment (RESOURCE) project, funded by the Solar System Exploration Research Virtual Institute (SSERVI) program, includes a task to demonstrate the end-to-end process of water extraction, capture, purification and electrolysis to produce pure/dry oxygen gas sourced from an icy regolith mixture. Water Purification: The requirements for water purity are driven by the type of water electrolyzer used. For example, the water electrolyzer currently used on the International Space Station is based on proton ex-change membrane (PEM) technology. PEM-based electrolyzers require water to be ultrapure and deionized (>10 MegaOhm-cm) so that electrical conductivity is limited to the membranes themselves, where electrical current is used to convert H2O into H2 and O2.. A practical first step toward purifying water that is sourced from a lunar PSR is to use freeze distillation to separate water from other volatiles2. A sub-micronic filter can also be used to ensure that a minimal amount of dust is present in any lunar water that is captured. The combination of freeze distillation and sub-micronic filtration will result in relatively pure water but would require a deionization step if being fed into a PEM electrolyzer. Water Electrolysis: An alternative to PEM electrolysis is to use a Solid Oxide Electrolyzer (SOE). This technology operates at a much higher operating temperature (~800oC) and has a limited pressure range but does not require water to be ultrapure and deionized. Another advantage of SOE technology is that it produces pure dry oxygen gas without the need of an additional drying step. PEM electrolyzers produce humid oxygen gas and the humidity must be removed prior to liquefaction. Assessment: In order to compare PEM and SOE technologies side-by-side, they must be compared at a system level that includes water purification and gas drying steps. Engineers at the Johnson Space Center up-dated and utilized a detailed In-Situ Resource Utilization (ISRU) system model to compare and select the best option for the RESOURCE project which will conclude with a laboratory demonstration of the process of producing pure/dry oxygen from an icy regolith mixture in 2025.

A.J. Paz

Technology Assessment for Producing Propellant From Lunar Water

Introduction: The presence of water ice in permanently shadowed regions (PSRs) on the lunar surface may enable a sustained human presence on the Moon with minimal need for consumables. One of the most valuable uses of lunar water is to produce rocket propellant. A sustained human presence on the Moon will re-quire frequent launches from the lunar surface, and each launch will require tons of propellant. However, many other volatiles are likely to be present in the areas where lunar water is stable1. Producing propellant from lunar water in-situ will require the separation and purification of water before it can be electrolyzed into oxygen and hydrogen gas. The Resource Exploration and Science of OUR Cosmic Environment (RESOURCE) project, funded by the Solar System Exploration Research Virtual Institute (SSERVI) program, includes a task to demonstrate the end-to-end process of water extraction, capture, purification and electrolysis to produce pure/dry oxygen gas sourced from an icy regolith mixture. Water Purification: The requirements for water purity are driven by the type of water electrolyzer used. For example, the water electrolyzer currently used on the International Space Station is based on proton ex-change membrane (PEM) technology. PEM-based electrolyzers require water to be ultrapure and deionized (>10 MegaOhm-cm) so that electrical conductivity is limited to the membranes themselves, where electrical current is used to convert H2O into H2 and O2.. A practical first step toward purifying water that is sourced from a lunar PSR is to use freeze distillation to separate water from other volatiles2. A sub-micronic filter can also be used to ensure that a minimal amount of dust is present in any lunar water that is captured. The combination of freeze distillation and sub-micronic filtration will result in relatively pure water but would require a deionization step if being fed into a PEM electrolyzer. Water Electrolysis: An alternative to PEM electrolysis is to use a Solid Oxide Electrolyzer (SOE). This technology operates at a much higher operating temperature (~800oC) and has a limited pressure range but does not require water to be ultrapure and deionized. Another advantage of SOE technology is that it produces pure dry oxygen gas without the need of an additional drying step. PEM electrolyzers produce humid oxygen gas and the humidity must be removed prior to liquefaction. Assessment: In order to compare PEM and SOE technologies side-by-side, they must be compared at a system level that includes water purification and gas drying steps. Engineers at the Johnson Space Center up-dated and utilized a detailed In-Situ Resource Utilization (ISRU) system model to compare and select the best option for the RESOURCE project which will conclude with a laboratory demonstration of the process of producing pure/dry oxygen from an icy regolith mixture in 2025.

ISRU

High temperature electrolyzer/fuel cell power cycle: Preliminary design considerations

A model of a high temperature electrolyzer/fuel cell, hydrogen/oxygen, thermally regenerative power cycle is developed and used to simulate system performance for varying system parameters. Initial estimates of system efficiency, weight, and volume are provided for a one KWe module assuming specific electrolyzer and fuel cell characteristics, both current and future. Specific interest is placed on examining the system responses to changes in device voltage versus current density operating curves, and the associated optimum operating ranges. The performance of a solar-powered, space based system in low earth orbit is examined in terms of the light-dark periods requiring storage. The storage design tradeoffs between thermal energy, electrical energy, and hydrogen/oxygen mass storage are examined. The current technology module is based on the 1000 C solid oxide electrolyzer cell and the alkaline fuel cell. The Future Technology system examines benefits involved with developing a 1800K electrolyzer operating with an advanced fuel cell.

Morehouse, Jeffrey H.

Separation of Carbon Monoxide and Carbon Dioxide for Mars ISRU-Concepts

Solid oxide electrolyzers, such as electrolysis cells utilizing yttria-stabilized zirconia, can produce oxygen from Mars atmospheric carbon dioxide and reject carbon monoxide and unreacted carbon dioxide in a separate stream. The oxygen-production process has been shown to be far more efficient if the high-pressure, unreacted carbon dioxide can be separated and recycled back into the feed stream. Additionally, the mass of the adsorption compressor can be reduced. Also, the carbon monoxide by-product is a valuable fuel for space exploration and habitation, with applications from fuel cells to production of hydrocarbons and plastics. In our research, we will design, construct, and test an innovative, robust, low mass, low power separation device that can recover carbon dioxide and carbon monoxide for Mars ISRU. Such fundamental process technology, involving gas-solid phase separation in a reduced gravitational environment, will help to enable Human Exploration and Development of Space. The separation device will be scaled to operate with a CO2 sorption compressor and a zirconia electrolysis device built at the NASA Ames Research Center and the University of Arizona, respectively. In our research, we will design, construct, and test an innovative, robust, low mass, low power separation device that can recover carbon dioxide and carbon monoxide for Mars ISRU, Such fundamental process technology, involving gas-solid phase separation in a reduced gravitational environment, will help to enable Human Exploration and Development of Space. The separation device will be scaled to operate with a CO2 sorption compressor and a zirconia electrolysis device built at the NASA Ames Research Center and the University of Arizona, The separation device will be scaled to operate with a CO2 sorption compressor and a zirconia electrolysis device built at the NASA Ames Research Center and the University of Arizona, Research needs for the design shown are as follows: (1) The best adsorbent for the process must be determined. (2) Adsorption isotherms must be measured, both for pure components and mixtures. (3) Mathematical modeling must be performed to provide a solid framework for design. (4) The separation system must be constructed and tested. (5) System integration must be studied.

LeVan, M. Douglas

Solid oxide electrolysis cell and stack testing best practices

Solid oxide electrolyzer (SOE) technology is an emerging method for hydrogen production, noted for its superior electrical efficiency. Despite the significant progress made in recent years, the broad development of SOE technology is often constrained by the necessary and extensive "skill of the craft" required to successfully test simple single cell test articles. This may be linked to the dearth of practical and pragmatic guidance within the literature for safe, reliable, and performant test equipment and test procedures. Researchers at the Idaho National Laboratory (INL) have been actively testing SOEs ranging from button cells to stacks up to 500 kW, in collaboration with industry and other national laboratories. Based on operational experience, INL has developed system design procedures that ensure safe and reliable operation of SOE systems with the level of support required for each test. This paper presents key aspects of SOE stack and system testing, including safe design procedures, balance of plant components design, and specific implementations at INL. Practical design details of reactants, heat, and power management are presented along with lessons learned from the SOE test facility operations at INL.

08 HYDROGEN

Oxygen Generator System Mars In-Situ Propellant Production Precursor Flight

The 2001 Lander to Mars will carry the first ever ISRU payload to Mars. This payload, the Mars In-situ Propellant production Precursor (MIP), will demonstrate a variety of technologies that will be required for future ISRU Mars indigenous material processing plant designs. One of those technologies is that of extracting oxygen from the predominantly carbon dioxide atmosphere of Mars, a prerequisite for future sample return and human missions to Mars. The Oxygen Generator Subsystem (OGS) portion of the MIP will demonstrate this and is the focus of this paper. The primary objective of the OGS is to demonstrate the production of oxygen from Mars atmospheric gases. Secondary objectives are to measure the performance and reliability of oxygen generation hardware in actual mission environments over an extended time. Major constraints on the OGS design came from several sources. The Lander provides power to the system from solar power that is harnessed by photovoltaic arrays. This limited OGS to daytime only operations (six to eight hours) and a maximum power of 15W. The reliance on solar power necessitated thermal cycling of the OGS between Mars ambient and OGS operating temperatures. The Lander also limited the total mass of the MIP payload to 7.5 kg with a correspondingly small volume, and the OGS was one of six experiments in the MIP. Mass and volume were to be minimized. Another constraint was cost. Mission funding, as always, was tight. Cost was to be minimized. In short the OGS design had to be low power (<15 Watts), low mass (1 kg), low volume, low cost, and be capable of cyclical operations for an extended stay on Mars. After extensive research, a zirconia based solid oxide electrolyzer design was selected.

Sridhar, K. R.

Oxygen Generator System Mars In-Situ Propellant Production Precursor Flight

The 2001 Lander to Mars will carry the first ever In situ Resource Utilization (ISRU) payload to Mars. This payload, the Mars In-situ Propellant production Precursor (MIP), will demonstrate a variety of technologies that will be required for future ISRU Mars indigenous material processing plant designs. One of those technologies is that of extracting oxygen from the predominantly carbon dioxide atmosphere of Mars, a prerequisite for future sample return and human missions to Mars. The Oxygen Generator Subsystem (OGS) portion of the MIP will demonstrate this and is the focus of this paper. The primary objective of the OGS is to demonstrate the production of oxygen from Mars atmospheric gases. Secondary objectives are to measure the performance and reliability of oxygen generation hardware in actual mission environments over an extended time. Major constraints on the OGS design came from several sources. The Lander provides power to the system from solar power that is harnessed by photovoltaic arrays. This limited OGS to daytime only operations (six to eight hours) and a maximum power of 15W. The reliance on solar power necessitated thermal cycling of the OGS between Mars ambient and OGS operating temperatures. The Lander also limited the total mass of the MIP payload to 7.5 kg with a correspondingly small volume, and the OGS was one of six experiments in the MIP Mass and volume were to be minimized. Another constraint was cost. Mission funding, as always, was tight. Cost was to be minimized. In short the OGS design had to be low power (<15 Watts), low mass (1 kg), low volume, low cost, and be capable of cyclical operations for an extended stay on Mars. After extensive research, a zirconia based solid oxide electrolyzer design was selected.

Sridhar, K. R.

Modeling of Gaseous Oxygen Liquefaction Inside Mars Ascent Vehicle Propellant Tank

The In-Situ production of propellants for Mars missions has been considered to utilize the Carbon dioxide (CO2) in Mars atmosphere to produce Oxygen using a high temperature solid oxide electrolyzer. The oxygen then needs to be cooled, liquefied, and stored to be available for propulsion and other end users. The storage period could be up to two years either in the actual Mars ascent propulsion tanks or in a separate tank. Recent investigations have demonstrated the feasibility of both achieving zero-boil-off and controlling the pressure of oxygen within a tank using high efficiency cryocoolers. A representative configuration of tube on tank liquefaction using cryocooler is shown in Fig. 1.

Cryogenic fluids

Development Status for a Combined Solid Oxide Co-Electrolyzer and Carbon Formation Reactor System for Oxygen Regeneration

A critical component in spacecraft life support loop closure is the removal of carbon dioxide (CO2, produced by the crew) from the cabin atmosphere and chemical reduction of this CO2 to recover the oxygen. In 2015, we initiated development of an oxygen recovery system for life support applications consisting of a solid oxide co-electrolyzer (SOCE) and a carbon formation reactor (CFR). The SOCE electrolyzes a combined stream of carbon dioxide (CO2) and water (H2O) gas mixtures to produce synthesis gas (e.g., CO and H2 gas) and pure dry oxygen as separate products. This SOCE is being developed from a NASA GRC solid oxide fuel cell and stack design originally developed for aeronautics long-duration power applications. The CFR, being developed by pHMatter LLC, takes the CO and H2 output from the SOCE, and converts it primarily to solid carbon (C(s)) and H2O and CO2. Although the solid carbon accumulates in the CFR, the innovative design allows easy removal of the carbon product, requiring minimal crew member (CM) time and low resupply mass (1.0 kg/year/CM) for replacement of the solid carbon catalyst, a significant improvement over previous Bosch reactor approaches. In this work, we will provide a status of our Phase I efforts in the development and testing of both the SOCE and CFR prototype units, along with an initial assessment of the combined SOCE-CFR system, including a mass and power projections, along with an estimate of the oxygen recovery rate.

air revitalization