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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 145 records · Page 8

Hydrogen Research for Spaceport and Space-Based Applications: Fuel Cell Projects

The activities presented are a broad based approach to advancing key hydrogen related technologies in areas such as fuel cells, hydrogen production, and distributed sensors for hydrogen-leak detection, laser instrumentation for hydrogen-leak detection, and cryogenic transport and storage. Presented are the results from research projects, education and outreach activities, system and trade studies. The work will aid in advancing the state-of-the-art for several critical technologies related to the implementation of a hydrogen infrastructure. Activities conducted are relevant to a number of propulsion and power systems for terrestrial, aeronautics and aerospace applications. Fuel cell research focused on proton exchange membranes (PEM), solid oxide fuel cells (SOFC). Specific technologies included aircraft fuel cell reformers, new and improved electrodes, electrolytes, interconnect, and seals, modeling of fuel cells including CFD coupled with impedance spectroscopy. Research was conducted on new materials and designs for fuel cells, along with using embedded sensors with power management electronics to improve the power density delivered by fuel cells. Fuel cell applications considered were in-space operations, aviation, and ground-based fuel cells such as; powering auxiliary power units (APUs) in aircraft; high power density, long duration power supplies for interplanetary missions (space science probes and planetary rovers); regenerative capabilities for high altitude aircraft; and power supplies for reusable launch vehicles.

Anderson, Tim↗

Long term durability test and post mortem for metal-supported solid oxide electrolysis cells

Hydrogen is a renewable energy carrier, and electrolysis to split water is the most environmentally friendly method to produce hydrogen. This work reports long-term durability and degradation mode analysis for metal-supported solid oxide electrolysis cells (MS-SOECs). Catalyst screening showed that MS-SOECs with composite electrode catalysts (samarium-doped ceria-nickel [SDC-Ni] serving as a fuel electrode catalyst, and praseodymium oxide [PrO x ]-SDC or La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 [LSCF]-SDC serving as an air electrode catalyst) exhibit the highest electrochemical performance at 700 °C. The degradation rate of cells with LSCF-SDC as the air electrode catalyst was as low as 1.3%/100 h in long term durability tests at a current density of 0.33 A cm -2 , in contrast to rapid degradation observed for a cell with a PrO x -SDC air electrode. Furthermore, post-mortem analysis reveals the degradation is dependent on the primary modes of fuel electrode catalyst coarsening and Cr poisoning on the air electrode catalyst, as well as secondary modes of oxidation of the metal support and local elemental accumulation of Ni. Other degradation modes reported in conventional anode-supported SOECs, such as Ni migration, foreign element contamination, delamination of the cell, and nano-voids on the electrolyte, are not observed in the present MS-SOECs.

25 ENERGY STORAGE↗

Demonstration of Electroreduction Technology to Convert GNF Uranium Oxide Powder to Metal

Global Nuclear Fuel – Americas LLC (GNF) has partnered with Argonne National Laboratory to demonstrate electroreduction of uranium oxides produced by deconversion of UF 6 to uranium metal through the Gateway for Accelerated Innovation in Nuclear (GAIN) program under the U.S. Department of Energy to accelerate the domestic production of metallic advanced reactor fuels. Electroreduction of uranium oxide was first demonstrated and patented by Argonne in the early 2000s as a technology to convert used oxide nuclear fuel from light water reactors to metal for further fuel reprocessing. More recently, electroreduction has been proposed as a front-end technology for metallization of uranium oxides produced by deconversion of UF 6 and for scrap recovery of oxide materials. During the electroreduction process, UO 2 powder is contained in a stainless-steel mesh basket with a cathode lead located in the center of the UO 2 bed. The basket is immersed in lithium chloride molten salt electrolyte containing 1 wt% lithium oxide along with a platinum anode and a nickel/nickel oxide (Ni/NiO) reference electrode. Current is applied to the cell between the cathode and anode to reduce the UO 2 to metallic uranium via a solid-state reduction reaction. Oxide ions released from the UO 2 during reduction are transported through the salt to the anode where oxygen gas is evolved. Once reduction is complete, the basket containing the metallicized uranium is removed from the salt and can be processed to remove the salt and consolidate the uranium into an ingot for use in metallic fuel fabrication. This project was performed to provide evidence of the electroreduction technology readiness level for metallization of UO 2 powder, identify and retire technical risks for industrialization of electroreduction, and accelerate the path to commercialization for metallic fast reactor fuel production. To that end, five electroreduction tests were performed with UO 2 provided by GNF and the resulting product was analyzed for the extent of conversion to metal and for impurity contents of the metal product to verify that electroreduction does not introduce impurities that would prevent use of the product in metallic fuel fabrication.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Scalable Nano-Scaffold SOFC Anode Architecture Enabling Direct Hydrocarbon Utilization

This project is based on WVU’s pending patents, technology and aims to design and modify the internal surfaces of the Ni/YSZ anode from currently commercially viable Solid Oxide Fuel Cells (SOFCs) using the additive manufacturing process of Atomic Layer Deposition (ALD). The surface architecture/scaffold added onto the internal surface of the anode possesses an engineered nanostructure but it features only commonly-used oxide conductors and electro-catalyst materials. The surface layer possesses a minimum thickness of ~2-40 nm and is solely designed to control the surface reforming reactions and to increase catalytic activity. Three-dimensional (3D) nano scaffold architectures with the noble metal nano-catalyst, low-cost bimetallic catalytic alloys, and nano-scale ionic conducting oxide fully compatible with the state-of-the-art Ni/YSZ anode, were applied to the internal surface of the entire porous SOFC anode using ALD. In the present work, the surface scaffold architecture is essentially multi-functional at the nano-scale, facilitated by the multiple heterostructured interfaces. It will significantly enhance the power density and cell durability for direct hydrocarbon utilization by (1) increasing the number of electrochemical reaction sites to enhance the hydrogen/hydrocarbon oxidation reactions; (2) reducing carbon formation; (3) mitigating the coarsening of backbone Ni phase and the oxidation attack of Ni from oxidants (e.g., H2O, CO2); and (4) promoting the internal reforming capabilities, especially for natural gas applications. ALD is employed to generate stable anode surface architectures that are uniform, precisely controllable at the atomic scale, and accurately repeatable for processing. The engineered anode surface nano-scaffold architecture was cataloged and analyzed using High-resolution Transmission Electron Microscopy (TEM), and cell power/durability performance assessed via comprehensive electrochemical performance testing with commercial specimens and relevant environments using hydrocarbon fuels. To the best of our knowledge, this project is the First Report on ALD of Ni/YSZ. The actual achievement of this Project includes (1). Successful demonstration of 7 types of ALD layers on Ni/YSZ anode, including Co, Ni, Mn, Pt, Ru, ZrOx and multi-functional nano-composite. (1). Conformal coating and subsequently spontaneously pinning the discrete nano-catalyst, including the precious metal nano-catalyst and the Ni and Co catalysts, on the YSZ surface upon the electrochemical operation in the reduced atmosphere. Those nano-catalysts on the ionic-conducting YSZ provided excellent sites for promoting internal reforming; (2). Demonstrated ALD coating increased both catalytic activity and conductivity of Ni/YSZ. Conformal coating provided dopants and introduced additional electrical conducting pathways on the YSZ ionic conductor. The doped surface layer of YSZ with mixed conductivity thus further introduces the active triple phase boundaries adjacent to the ALD-coated nano-catalysts such as Pt, Co, and Ni that are pinned on the YSZ surface. The nano-composite ALD coating on Ni/YSZ anode has significantly increased cell durability; and (3). ALD coating of Ni/YSZ anode increased the power density of the entire cell by 300%. For a long time, the SOFC performance, such as the power density, was deemed hindered by the cathode. The sluggish oxygen reduction reaction (ORR) in the cathode was deemed as hindering the power density of the SOFCs. For the anode-supported commercial SOFCs, the cell performance is considered to be limited by the cathode's performance. For the first time in the field of SOFC, this project has demonstrated that (1). the performance of commercial SOFCs can be further increased by the ALD coating on Ni/YSZ anode backbone. (2). ALD coating on Ni/YSZ fuel electrodes results in the enhancement of power density, and increased reliability, robustness, and endurance of SOFCs, for their application using both hydrogen and hydrocarbon fuels over the entire operating temperature range of 650-800ºC for the inherently functional commercial cells. (3). ALD coating provides alternative approaches of exsolutions for introducing the stable catalyst onto the internal surface of the Ni/YSZ electrode. ALD coating could be much more versatile than exsolution in employing the catalysts with various chemistries onto the various backbones. (4). Due to the negligible amount of ALD materials coated onto the internal surface of the porous cathode of the as-fabricated cells, a peak power density increase up to 300 % induced by ALD coating was simultaneously achieved in terms of both power density and specific power. (5). The ALD coating developed through this project was applied to both the SOFC and Solid Oxide Electrolysis Cells (SOEC). SOEC’s face a similar but more demanding need to improve the fuel electrode's performance. It opens further research directions for electrocatalytic surface nanoionics with a wide range of chemistry. It will revolutionize our ability to render the formation of a nanostructured electrode that has been constantly pursued yet barely achieved for practical SOFC/SOEC applications. The research is also immediately transformative since both the preliminary data and the proposed work are on the direct implantation of nanoionics into the state-of-the-art inherently functional SOCs. It represents an immediate impact on the commercial sectors in SOC technology since the applied ALD processing is computer-controlled ALD coating using the commercial ALD systems, and it is scalable to both the single cells and SOC stacks.

36 MATERIALS SCIENCE↗

Trioxane: A Fuel For Direct-Oxidation Fuel Cells

Trioxane identified as high-energy, nontoxic, solid substitute for formaldehyde as water-soluble fuel for use in direct-oxidation fuel cells. Found to undergo facile electrochemical oxidation to water and carbon dioxide at platinum and platinum-alloy electrodes in liquid-feed-type fuel cells that contain acid electrolytes or solid proton-exchange membrane electrolytes. Exhibits less crossover than do such conventional fuels as methanol and formaldehyde. Being solid at ambient temperature, trioxane offers significant advantages in handling and transportation. Synthesized from natural gas with relative ease.

Olah, George A.↗

Defect Thermodynamics and Transport Properties of Perovskite and Fluorite Materials for Solid-Oxide and Proton Conducting Oxide Cells Evaluated Based on Density Functional Theory Modeling

Density functional theory based defect thermodynamic modeling was performed to determine the effect of humidity and H2/O2 gas pressure on various defect chemistry and transport properties of perovskite and fluorite oxides for solid-oxide and proton-conducting-oxide cell applications, with inclusion of the electronic-conducting oxides (as electrodes) and insulating oxides (as electrolytes). Automatic defect generation workflow and first-principles charged defect analysis were implemented on NETL Joule supercomputer for modeling defect equilibria and transport properties of insulating oxides as electrolytes in SOCs and proton-conducting ceramic cells. A GNU Octave defect model subroutines were developed to facilitate defect modeling of electronic conducting oxides in a wide range of operating conditions guided by modeling and experiments. The model includes the hydride defect formation reaction under reducing conditions and allows to incorporate nonstoichiometry effects on the defect thermodynamic parameters. The developed model serves as a platform to facilitate fundamental understanding of the defect thermodynamics in SOC oxide materials and can be used as a novel tool in computational materials screening for SOC and other energy applications.

Lee, Yueh-Lin↗

Some recent studies with the solid-ionomer electrochemical capacitor

Giner, Inc. has developed a high-energy-density, all-solid-ionomer electrochemical capacitor, completely free of liquid electrolyte. The novel features of this device include 1) a three-dimensional metal oxide-particulate-ionomer composite electrode structure, and 2) a unitized repeating cell element. The composite electrode structures are bonded to opposite sides of a thin sheet of a solid proton-conducting ionomer membrane and form an integrally bonded membrane and electrode assembly (MEA). Individual MEAs can be stacked in series as bipolar elements to form a multiple cell device. The discharge characteristics and energy storage properties of these devices are described. Typical capacitance measured for a unit cell is 1 F/cm(exp 2). Life testing of a multicell capacitor on an intermittent basis has shown, that over a 10,000 hour period, the capacitance and resistance of the cell has remained invariant. There has been no maintenance required on the device since it was fabricated. Other multicell units of shorter life duration have exhibited similar reliable performance characteristics. Recent work has focused on increasing the capacitance of the unitized structure and improving the low-temperature characteristics. The approaches and experimental results will be presented. Some possible advanced NASA applications for these unique all-solid-ionomer devices will be discussed.

S Sarangapani↗

Some Recent Studies With the Solid-Ionomer Electrochemical Capacitor

Giner, Inc., has developed a high-energy-density, all-solid-ionomer electro-chemical capacitor, completely free of liquid electrolyte. The novel features of this device include: (1) a three-dimensional metal oxide-particulate-ionomer composite electrode structure and (2) a unitized repeating cell element. The composite electrode structures are bonded to opposite sides of a thin sheet of a solid proton-conducting ionomer membrane and form an integrally bonded membrane and electrode assembly (MEA). Individual MEAs can be stacked in series as bipolar elements to form a multiple cell device. The discharge characteristics and energy storage properties of these devices are described. Typical capacitance measured for a unit cell is 1 F/cm. Life testing of a multicell capacitor on an intermittent basis has shown that, over a 10,000-hour period, the capacitance and resistance of the cell has remained invariant. There has been no maintenance required on the device since it was fabricated. Other multicell units of shorter life duration have exhibited similar reliable performance characteristics. Recent work has focused on increasing the capacitance of the unitized structure and improving the low-temperature characteristics. The approaches and experimental results will be presented. Some possible advanced NASA applications for these unique all-solid-ionomer devices will be discussed.

Sarangapani, S.↗

Rationally designed negative electrode for selective CO 2 -to-CO conversion in protonic ceramic electrochemical cells

Protonic ceramic electrochemical cells (PCECs) are solid-state electrochemical devices that employ proton-conducting oxides as electrolytes, which offer a promising approach for electrification of chemical manufacturing, including CO 2 reduction to produce value-added chemicals (e.g., CO). The primary advantage of PCECs is their intermediate operating temperatures (300–600 °C), which thermodynamically and kinetically favor the CO 2 reduction chemistry at the negative electrode. However, the conventional negative electrodes of PCECs, such as BaZr 0.8–x Ce x Y 0.2 O 3-δ -Ni or BaZr 0.8–x Ce x Y 0.1 Yb 0.1 O 3-δ -Ni, cannot reduce CO 2 to either CH 4 or CO with a selectivity of >99 %, leading to the production of a CO and CH 4 mixture. Herein, an oxide-supported in-situ exsolved Ni-Fe alloyed nanoparticle electrocatalyst, Sr 2 Fe 1.4 Mo 0.5 O 6-δ -Ni0.175 (SFM-Ni0.175), is first employed as the negative electrode of PCECs. The PCECs equipped with this new negative electrode selectively favor the CO 2 -to-CO conversion. A selectivity of ~100 % toward CO has been demonstrated over a wide range of operating temperatures (400–600 °C) and applied potentials/current densities. The negative electrode demonstrated in this work fully suppresses the CH 4 production. In situ diffuse reflectance infrared spectroscopy (DRIFTS) was performed to probe the CO 2 reduction mechanisms over both SFM-Ni0.175 and the traditional negative electrode (BCZYYb7111 +Ni), which indicates SFM-Ni0.175 inhibits the formation of formate species, leading to selective production of CO. Finally, this work validates that PCECs equipped with the rationally designed negative electrode can selectively manufacture chemicals.

25 ENERGY STORAGE↗

On the role of the zirconia/ceria interface in the degradation of solid oxide electrolysis cells

Gd-doped Ceria (GDC) barrier layers are widely used in solid oxide electrolysis cells to prevent reactions between the Y-stabilized Zirconia (YSZ) electrolyte and oxygen electrode. In some cases, electrolysis operation causes fracture near the GDC/YSZ interface. Here, we explain this effect using a numerical calculation, showing that a peak oxygen pressure is observed near the GDC/YSZ interface during electrolysis operation. Moreover, GDC/YSZ interdiffusion and possible zirconate phase formation occurring during electrode firing yield a low oxygen ion conductivity region that introduces a much higher peak oxygen partial pressure at the interdiffusion layer/YSZ interface, thereby exacerbating degradation. The results indicate that the peak pressure can be reduced and, thereby, damage can be mitigated by altering processing in order to minimize interdiffusion, decreasing the GDC layer thickness, and reducing oxygen electrode polarization resistance or altering electrolyte transport properties, e.g., changing the Gd doping level of GDC to increase the oxygen vacancy diffusivity.

Physics↗

Combined Cr and S poisoning behaviors of La 1-x Sr x MnO 3±δ and La 1-x Sr x Co 1-y FeyO 3-δ cathodes in solid oxide fuel cells

Although the individual effects of airborne Cr and S contaminants on SOFC cathode performance degradation have been extensively studied, the combined effects of Cr and S contaminants remain largely unexplored. Under the real SOFC operating condition where the Cr and S species coexist, their effects may compete, affecting the poisoning behavior. Here, our investigation reveals that the combined Cr and S poisoning behavior of LSCF remains different from those of individual Cr and S poisonings, while the combined poisoning mechanism of LSM is equivalent to the sum of those of individual Cr and S effects. For LSCF electrode, gaseous Cr species are deposited mainly at the LSCF/GDC interface by electrochemical reduction, rather than forming SrCrO 4 on LSCF surfaces (as in the case of Cr-only poisoning), indicating no reaction between Cr vapors and SrO on the LSCF surface. Thermodynamic analysis demonstrates that the SrO on LSCF surface absorbs SO 2 (g) and thereby loses the Cr-gettering effect, allowing Cr vapors to flow through LSCF and to reach the LSCF/GDC interface where the Cr deposition occurs. Unlike LSCF, LSM electrode shows cumulative effects of Cr and S, as Cr accumulation occurs at the triple-phase boundary and S absorption takes place at localized Sr-rich regions.

36 MATERIALS SCIENCE↗

Effects of surface chemical potentials on cation segregation

Surface cation segregation on perovskite-type electrodes is one of the major issues limiting the durability of high-temperature solid-oxide electrochemical cells, and this process is strongly dependent on temperature, the external gas-environment, and impurities in air, such as CO 2 . Here cation segregation on La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF) is systematically evaluated under a set of chemical potentials to determine the origin of surface segregation and the dominant factors that govern the segregation process. Temperature is the main driving force for surface strontium segregation as the thermodynamic stability of each phase varies, and the SrO particles appear primarily in a specific operating window. In addition to the required thermal energy, the presence of gaseous oxygen-containing molecules as reactants help drive the precipitation of SrO. Oxygen partial pressure (pO 2 ) controls the defect chemistry of LSCF, leading to promotion or suppression of surface segregation. The presence of CO 2 promotes the nucleation process and suppresses the surface migration step, significantly altering the surface morphology. We also show that A-site deficiency can limit the SrO segregation in certain conditions but shows no effect in others. This study reveals the impact of gas–solid interactions on surface segregation and highlights the subtle relationship between multiple segregation driving forces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Creating and Preserving Nanoparticles during Co-Sintering of Solid Oxide Electrodes and Its Impact on Electrocatalytic Activity

A novel processing method that creates and preserves ceramic nanoparticles in solid oxide electrodes during co-sintering at traditional sintering temperatures is introduced. Specifically, carbon templated samarium-doped ceria nanoparticles (nSDC) were successfully integrated with commercial lanthanum strontium cobalt ferrite (LSCF) and commercial SDC powders, producing LSCF-SDC-nSDC cathodes upon processing. The effect of nSDC concentration on cathode electrocatalytic activity was investigated at low operational temperatures, 600 °C–700 °C, with symmetrical cells. Low nSDC loadings, ≤5 wt% nSDC, significantly decreased cell polarization resistance whereas higher loadings increased it. The best electrochemical performance was achieved with 5 wt% nSDC, lowering the polarization resistance by 41% at 600 °C. Fuel cell tests demonstrate that adding 5 wt% nSDC increased the maximum fuel cell power density by 38%. Electrochemical impedance spectra showed substantial improvements in both fuel cell polarization resistance and ohmic resistance, indicating that nSDC increased the electrocatalytically active area of the cathode. This work demonstrates a simple, novel method for effectively increasing electrocatalytic activity of solid oxide electrodes at low operational temperatures.

Muhoza, Sixbert P. (ORCID:0000000299864241)↗

Cascade CO 2 electroreduction enables efficient carbonate-free production of ethylene

CO 2 electroreduction provides a route to convert waste emissions into chemicals such as ethylene (C 2 H 4 ). However, the direct transformation of CO 2 -to-C 2 H 4 suffers from CO 2 loss to carbonate, consuming up to 72% of energy input. A cascade approach—coupling a solid-oxide CO 2 -to-CO electrochemical cell (SOEC) with a CO-to-C 2 H 4 membrane electrode assembly (MEA)—would eliminate CO 2 loss to carbonate. However, this approach requires a CO-to-C 2 H 4 MEA with energy efficiency well beyond demonstrations to date. Focusing on the MEA, in this study we find that an N-tolyl substituted tetrahydro-bipyridine film improves the stabilization of key reaction intermediates, while an SSC ionomer enhances CO transport to the Cu surface, enabling a C 2 H 4 faradaic efficiency of 65% at 150 mA cm –2 for 110 h. Demonstrating a cascade SOEC-MEA approach, we achieve CO 2 -to-C 2 H 4 with a ~48% reduction in energy intensity compared with the direct route. We further reduce the energy intensity by coupling CO electroreduction (CORR) with glucose electrooxidation.

10 SYNTHETIC FUELS↗