Search NASA⌕ Search

SEARCH · Search NASA

Results for “ionic current”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

718 records · Page 40
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Investigation into Reductive Separation of Tc-99 from Low Activity Waste Off-Gas Condensate by Zero Valent Iron Materials - 20311

This study is investigating the potential for reductive separation of technetium-99 (Tc) from off-gas condensate generated from vitrification of legacy tank waste at the Hanford Tank Waste Treatment and Immobilization Plant. Management of Tc is a high-priority activity for the U.S. Department of Energy (DOE) Office of Environmental Management (EM) complex, which must be addressed based on knowledge gaps and technology development needs outlined in the DOE-EM Technetium Management Program Plan [1]. Technetium is one of the main risk drivers in the permanent disposal of low activity waste (LAW) by vitrification at the Hanford Site due to its high volatility and only fractional incorporation into borosilicate glass. Volatilized Tc will be captured by an off-gas treatment system, and the current plan is to continuously recycle generated condensate back to the LAW glass melter feed. Off-gas recycling is effective at increasing Tc loading in the LAW glass, but it also disproportionately increases concentrations of sulfate, halides, and other volatile compounds impeding overall LAW processing leading to significantly greater waste glass volume requirements. Removal of Tc from secondary liquid waste offers an alternative disposal route to continuous off-gas recycling which may result in significant reduction of the volumes of LAW waste glass and substantial cost savings. The objective of this research funded by the DOE-EM Minority Serving Institutions Partnership Program (MSIPP) is to determine the suitability of zero valent iron (ZVI) as a separation technology to remove Tc from the off-gas condensate stream to minimize its recycle. While ZVI has been proposed for various remediation applications with Tc, it has not been studied for its suitability for removing Tc from the LAW off-gas condensate. The goal is to identify the optimal conditions for which Tc{sup (VII)} will be reduced to Tc{sup (IV)} species and incorporated into an iron matrix. This paper presents a programmatic overview of our evaluation of commercial ZVI materials for their efficiency towards Tc{sup (VII)} reductive removal from simplified off-gas simulant solutions under aerobic conditions. Tc concentrations in solutions were monitored for up to 30 days to determine efficiency and kinetics of reductive removal of Tc. The best performing candidate materials were selected for further experiments evaluating the effects of (1) variable ionic strength, (2) the presence of chromium and corrosive anions, and (3) ZVI aging on Tc{sup (VII)} reductive removal in batch experiments. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2018

High Ion-Accessible Surface Area CNT-Ultracapacitors for Groundwater Desalination

Fresh water is a vital resource for human survival, as well as a key component for a wide range of industrial and agricultural needs. However, only 0.65% of the world’s water resources are available as fresh water, and the demand on the world’s water reserves continues to rise, with the demand already beginning to outpace the supply in many areas. A water-energy nexus is being reached that requires low -cost and -energy solutions for various degrees of treated water. Public awareness of the problem has also risen, such that in a 2012 survey, 88% of Americans reported concerns about potential water shortages. Approximately two-thirds of the world’s population could suffer water shortages over the next few years. Seawater and other saline water supplies make up around 98% of the world’s accessible water. Properly treated to reduce the levels of salinity, this represents an almost unlimited supply of fresh water. The high energy requirements, capital costs, and maintenance requirements to remove salts and other unwanted compounds, however, are barriers to widespread implementation of salt-to-freshwater facilities. These facilities most commonly use reverse osmosis (RO) systems that suffer from high required pressures and failures of moving parts; additionally, these facilities consume much grid energy and require constant maintenance, leading to high capital and operational costs. The RO process also generates large volumes of highly concentrated bio-hazardous brine that is costly to safely return to the ocean. In contrast to RO, capacitive desalination or capacitive deionization (CDI) has fewer moving parts (a low-pressure pump and several valves), operates at low pressure, and does not generate large quantities of brine that are hazardous to marine life. The capacitive charge/discharge of a CDI system can be cycled almost indefinitely, and the system has low energy requirements because the capacitive discharge electrical current can be co-generated back to the system. RO must remove the water from the salt while CDI removes the salt from the water. This represents a significant difference in the number of molecules which must be moved and energy required to desalinate water. However, CDI has not seen widespread use for large- or small-scale desalination because electrode efficiency has limited the extraction rate below what is useful for most applications. Mainstream demonstrated the following successes during this SBIR program: Performance - We developed an innovative new electrode structure for the high-efficiency removal of ions from salt-contaminated water samples by CDI. Based on prototype electrochemical tests, our CDI consumes as low as 0.71 kW/m 3 of treated water (compared to 2.9 to 3.7 kW/m 3 for RO). Scalability – During Phase II, we increased the electrode size from 3.8 cm 2 single-sided electrodes to 180 cm 2 double-sided electrodes. Using larger acid baths and CVD furnace, we increased electrode fabrication capacity increased by 315 times. Scalable electrochemical CDI stack design and balance of plant – During Phase II, we demonstrated at scalable low-pressure drop stack design and balance of plant for the continuous removal of ions. Corrosion Resistance – Based on accelerated corrosion testing data, our high-quality graphitic electrodes have a significantly improved corrosion resistance. This was 20 times better corrosion resistance than our Phase I electrodes and significantly higher than typical CDI system electrodes. Flexibility –By tuning the pore size of the electrode materials, we demonstrated the removal of key target ionic contaminants, such as sodium chloride, nitrate, and phosphate salts. These ionic contaminants are common in agricultural and industrial wastewater runoff and are difficult to remove by conventional methods, which require excessive use of reagents.

Cox, Dr. Philip↗
DOE OSTI2018

Ambient Electrosynthesis of Ammonia: Electrode Porosity and Composition Engineering

Ammonia, a key precursor for fertilizer production, convenient hydrogen carrier, and emerging clean fuel, plays a pivotal role in sustaining life on Earth. Currently, the main route for NH 3 synthesis is by the heterogeneous catalytic Haber–Bosch process (N 2 +3 H 2 →2 NH 3 ), which proceeds under extreme conditions of temperature and pressure with a very large carbon footprint. Herein we report that a pristine nitrogen–doped nanoporous graphitic carbon membrane (NCM) can electrochemically convert N 2 into NH 3 in an acidic aqueous solution under ambient conditions. The Faradaic efficiency and rate of production of NH 3 on the NCM electrode reach 5.2 % and 0.08 g m –2 h –1 , respectively. Functionalization of the NCM with Au nanoparticles dramatically enhances these performance metrics to 22 % and 0.36 gm –2 h –1 , respectively. In conclusion, as this system offers the potential to be scaled to industrial levels it is highly likely that it might displace the century-old Haber–Bosch process.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Deep Eutectic Solvents: A Review of Fundamentals and Applications

Deep eutectic solvents (DESs) are an emerging class of mixtures characterized by significant depressions in melting points compared to those of the neat constituent components. These green materials are promising for applications as inexpensive ’designer’ solvents exhibiting a host of tunable physicochemical properties. Here, a detailed review of the current literature reveals the lack of predictive understanding of the microscopic mechanisms that govern the structure-property relationships in this class of solvents. Complex hydrogen bonding behavior is postulated as the root cause of their melt-ing point depressions and physicochemical properties; to understand these hydrogen bonded networks, it is imperative to study these systems as dynamic entities using both simulations and experiments. This review emphasizes recent research efforts in order to elucidate the next steps needed to develop a fundamental framework for understanding DESs. It covers recent developments in DES research, frames outstanding scientific questions, and identifies gainful research thrusts that would advance the field towards predictive models and fundamental understanding of these solvents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Scope and efficacy of the broad-spectrum topical antiseptic choline geranate

Choline geranate (also described as Choline And GEranic acid, or CAGE) has been developed as a novel biocompatible antiseptic material capable of penetrating skin and aiding the transdermal delivery of co-administered antibiotics. The antibacterial properties of CAGE were analyzed against 24 and 72 hour old biofilms of 11 clinically isolated ESKAPE pathogens (defined as Enterococcus faecium, Staphylococcus aureus, Klebsiella pneumoniae, Acinetobacter baumanii, Pseudomonas aeruginosa, and Enterobacter sp, respectively), including multidrug resistant (MDR) isolates. CAGE was observed to eradicate in vitro biofilms at concentrations as low as 3.56 mM (0.156% v:v) in as little as 2 hours, which represents both an improved potency and rate of biofilm eradication relative to that reported for most common standard-of-care topical antiseptics in current use. In vitro time-kill studies on 24 hour old Staphylococcus aureus biofilms indicate that CAGE exerts its antibacterial effect upon contact and a 0.1% v:v solution reduced biofilm viability by over three orders of magnitude (a 3log10 reduction) in 15 minutes. Furthermore, disruption of the protective layer of exopolymeric substances in mature biofilms of Staphylococcus aureus by CAGE (0.1% v:v) was observed in 120 minutes. Insight into the mechanism of action of CAGE was provided with molecular modeling studies alongside in vitro antibiofilm assays. The geranate ion and geranic acid components of CAGE are predicted to act in concert to integrate into bacterial membranes, affect membrane thinning and perturb membrane homeostasis. Taken together, our results show that CAGE demonstrates all properties required of an effective topical antiseptic and the data also provides insight into how its observed antibiofilm properties may manifest.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

A pseudo-two-dimensional (P2D) model for FeS 2 conversion cathode batteries

Conversion cathode materials are gaining interest for secondary batteries due to their high theoretical energy and power density. However, practical application as a secondary battery material is currently limited by practical issues such as poor cyclability. To better understand these materials, we have, for this study, developed a pseudo-two-dimensional model for conversion cathodes. We apply this model to FeS 2 – a material that undergoes intercalation followed by conversion during discharge. The model is derived from the half-cell Doyle–Fuller–Newman model with additional loss terms added to reflect the converted shell resistance as the reaction progresses. We also account for polydisperse active material particles by incorporating a variable active surface area and effective particle radius. Using the model, we show that the leading loss mechanisms for FeS 2 are associated with solid-state diffusion and electrical transport limitations through the converted shell material. The polydisperse simulations are also compared to a monodisperse system, and we show that polydispersity has very little effect on the intercalation behavior yet leads to capacity loss during the conversion reaction. Finally, we provide the code as an open-source Python Battery Mathematical Modeling (PyBaMM) model that can be used to identify performance limitations for other conversion cathode materials.

25 ENERGY STORAGE↗
NASA NTRS2009

Refractory Materials for Flame Deflector Protection System Corrosion Control: Refractory Ceramics Literature Survey

Ceramics can be defmed as a material consisting of hard brittle properties produced from inorganic and nonmetallic minerals made by firing at high temperatures. These materials are compounds between metallic and nonmetallic elements and are either totally ionic, or predominately ionic but having some covalent character. This definition allows for a large range of materials, not all applicable to refractory applications. As this report is focused on potential ceramic materials for high temperature, aggressive exposure applications, the ceramics reviewed as part of this report will focus on refractory ceramics specifically designed and used for these applications. Ceramic materials consist of a wide variety of products. Callister (2000) 1 characterized ceramic materials into six classifications: glasses, clay products, refractories, cements, abrasives, and advanced ceramics. Figure 1 shows this classification system. This review will focus mainly on refractory ceramics and cements as in general, the other classifications are neither applicable nor economical for use in large structures such as the flame trench. Although much work has been done in advanced ceramics over the past decade or so, these materials are likely cost prohibitive and would have to be fabricated off-site, transported to the NASA facilities, and installed, which make these even less feasible. Although the authors reviewed the literature on advanced ceramic refractories 2 center dot 3 center dot 4 center dot 5 center dot 6 center dot 7 center dot 8 center dot 9 center dot 10 center dot 11 center dot 12 after the review it was concluded that these materials should not be ' the focus of this report. A review is in progress on materials and systems for prefabricated refractory ceramic panels, but this review is focusing more on typical refractory materials for prefabricated systems, which could make the system more economically feasible. Refractory ceramics are used for a wide variety of applications. Figure 2 shows many ofthese applications, their life expectancy or requirement, and the exposure temperature for the refractory ceramic. Note that the exposure temperatures for refractory ceramics are very similar to the exposure conditions for specialty ceramics (rocket nozzles, space vehicle re-entry fields, etc.) and yet the life expectancy or requirement is relatively low. Currently NASA is repairing the refractory lining in the flame trench after every launch - although this is not a direct indication of low life expectancy, it does indicate that the current system may not be sufficiently durable to maximize economy. Better performing refractory ceramics are needed to improve the performance, economy, and safety during and after launches at the flame trenches at Kennedy Space Center (KSC). To achieve this goal a current study is underway to assess different refractory systems for possible use in the flame trenches at KSC. This report will target the potential applicability of refractory ceramics for use in the flame trenches. An overview of the different refractory ceramics will be provided (see Figure I). This will be followed with a brief description of the structure of refractory products, the properties and characteristics of different systems, the methodology for selecting refractories, and then a general design methodology. Based on these sections, future challenges and opportunities will be identified with the objective of improving the durability, performance, economy, and safety of the launch complex. Refractory ceramics are used for a wide variety of applications. Figure 2 shows many ofthese applications, their life expectancy or requirement, and the exposure temperature for the refractory ceramic. Note that the exposure temperatures for refractory ceramics are very similar to the exposure conditions for specialty ceramics (rocket nozzles, space vehicle re-entry fields, etc.) and yet the life expectancy or requirement is relatively low. Currently NASA is repairing the refractory lining in the flame trench after every launch - although this is not a direct indication of low life expectancy, it does indicate that the current system may not be sufficiently durable to maximize economy. Better performing refractory ceramics are needed to improve the performance, economy, and safety during and after launches at the flame trenches at Kennedy Space Center (KSC). To achieve this goal a current study is underway to assess different refractory systems for possible use in the flame trenches at KSC. This report will target the potential applicability of refractory ceramics for use in the flame trenches. An overview of the different refractory ceramics will be provided (see Figure I). This will be followed with a brief description of the structure of refractory products, the properties and characteristics of different systems, the methodology for selecting refractories, and then a general design methodology. Based on these sections, future challenges and opportunities will be identified with the objective of improving the durability, performance, economy, and safety of the launch complex.

Calle, Luz Marina↗
DOE OSTI2023

Chromium Tolerant, Highly Active and Stable Electrocatalytic Internal Surface Coating for Cathode of Commercial SOFCs (Final Report)

This project is aimed to develop a chromium (Cr) tolerant, highly active, and stable coating layer on the internal surfaces of the porous composite cathode from commercially available SOFCs. Such coating layer was developed using the additive manufacturing process of Atomic Layer Deposition (ALD) and has been applied on the cathode consisting of either an electronic conductor of LaxSr 1-x MnyO 3-δ (LSM) or mixed ionic and electronic conducting La x Sr 1-x Co y Fe 1-y O 3-δ (LSCF). PI's work has demonstrated that the internal surface of cathode from the commercial cells, can be further tailored using ALD coating to dramatically enhance the cell performance. For instance, ALD layer consisting heterostructured nano composite of nano-Pt and nano-(Mn 0.8 Co 0.2 ) 3 O 4 oxide on the internal surface of porous LSM/YSZ cathode from SOFCs, has resulted in the large reduction of the cell polarizations resistance by up to 53%, and enormous increase of power density over 370%. For the cells with LSCF/Sm 2 O 3 doped CeO 2 (SDC) cathode, the conformal layer of nano-composite consisting of superjacent CoOx and subjacent minimum amount of Pt nano-grains has resulted in the power density enhancement by 126% for the large scale industry tubular cells at 750°C, and both the performance enhancement and nanostructure of the ALD layer are stable over ~ 2000 h continuous operation performed at industry test station. In the meanwhile, those ALD coating layer developed by PI's work is also inherently Cr-tolerant, and could act as physical barrier for preventing Cr diffusion into the cathode backbone, so as to mitigate the Cr poisoning effect on the cathode. In this project, the impact of Cr on the performance of those ALD coated commercial cells has been evaluated. Based on evolution of the cell performance, the ALD coating layer chemistry and ALD coating layer thickness has been optimized to maximize the overall Cr tolerance, cell power density and cell longevity. Different ALD coating has been applied onto the internal surface of LSM/YSZ and LSCF/SDC backbone respectively. The architecture/scaffold structures on the internal surface of different cathode, designed by this project, was catalogued and analyzed using High Resolution Transmission Electron Microscopy (HRTEM), and cell power/durability performance are assured via comprehensive electrochemical performance testing in the industry operation relevant conditions. The impact of the electrochemical operation current density, the water humidity, the cell operation temperature, and cell operation duration on the Cr tolerance of ALD coated cells has been systematically investigated. There is completely different nanostructure degradation mechanisms between LSM and LSCF cells induced by Cr contamination. For the LSCF/SDC baseline cell, With the Cr source, there is no apparent Sr surface segregation phase even for the baseline cell operated for 3000 h at 750 °C. With the Cr source, there is significant amorphous (SrCr)Ox phase accumulated in the original pore region. For the commercial baseline cells, Cr contaminants on the LSM electrode severely impacted the entire cell's electrochemical performance and nanostructure degradation. Those degradations include (1). Peak power density loss of 64 % after 109 h of operation. The dramatic increase in Rp (2). They are cracking at LSM/SSZ interface, LSM grains. SSZ remains intact but with (CrMn)Ox. By contrast, ALD coating (MnCo)Ox/Pt dramatically improves the Cr resistance, as follows (1). ALD-coated cell with a power density is 280-380 % of the baseline cell, depending on the ALD layer thickness. (2). For a cell with a 20 nm thick ALD layer, there is a large performance enhancement (> 200 % power density) induced by ALD coating of Cr-tolerant Mn 0.8 Co 0.2 Ox. (3). For a cell with a 20 nm thick ALD layer, after 168 h at 750 °C power density of the ALD-coated cell is ~ 600% of that baseline cell upon operation with Cr contamination for 109 h. The ALD coating on the internal surface of cathode developed by this project integrated multi-functions. Those multi-functions include (1). Dramatically improving the cell power density for the commercial cells; (2). Dramatically improving contamination resistance of the cathode, for being an excellent protection coating layer sealing off Cr contamination. (3). Dramatically increasing the cell longevity by potentially preventing the microstructure evolution and grain coarsening of the cathode. Overall, this project will provide a simple solution to simultaneously enhance power density and increase the reliability, robustness, and endurance of commercial SOFCs, over the entire operating temperature range of 650-800 °C. For the inherently functional SOFC, the ALD coating of LSM based cathode mitigate the Cr-contamination. Power density of ALD-coated cell is ~ 600% of that baseline cell upon operation with Cr contamination. In addition to SOFCs, the novel on-demand design approach and creation of multifunctional heterogeneous architecture on the electrode surface presented in this work opens further research for their application in other types of fuel cells, batteries, and sensors for which electrochemical reactions on the surface are similarly critical.

36 MATERIALS SCIENCE↗
NASA NTRSDate not supplied

Computationally Guided Development of Components for High Energy Density Solid-State Lithium-Sulfur Batteries

All electric vertical take-off and landing vehicles (eVTOL) for urban air mobility (UAM) concepts face numerous challenging technical barriers before their introduction into the consumer marketplace. The most challenging of these technical barriers to overcome is developing an energy storage system capable of meeting the rigorous aerospace safety and performance criteria1. The performance metrics for eVTOL craft, such as specific energy, specific power, and safety, exceed those of electric automobiles by a factor of two to four. Current state-of-the-art (SOA) lithium-ion batteries are incapable of meeting the key performance criteria of energy and safety for eVTOL. Therefore, next generation advanced chemistries and designs must be developed to meet required performance metrics for electric aviation2. Beyond lithium-ion chemistries, such as lithium-sulfur, show promise in their high energy, while limitations exist in their power and cyclability due to low electrical conductivity and high intermediate solubility in organic liquid electrolytes. Several strategies to overcome the low electrical conductivity involve the use of selenium as a dopant in the active sulfur material, along with the incorporation of 2-dimensional electron-conducting holey-graphene to improve the composite cathodes electronic conductivity. Furthermore, combining this chemistry with a solid-electrolyte avoids the components’ dissolution issues3. However, the development of composite solid-state cathodes is non-trivial as several components must be intimately mixed so that the active component has sufficient access to both electrons and lithium ions to undergo full electrochemical conversion. Mathematical modeling of battery components can assist experimental design through a robust and rigorous combination of computational modeling techniques covering multiple length scales. The objective is to leverage modern computational materials methods combined with battery multiphysics tools to develop radically advanced compatible cathode and electrolyte materials, build and test solid state lithium-sulfur cells and packs. A NASA-based cross-organizational team of high-powered experts combined integrated computational predictive modeling, fundamental chemistry analysis, advanced material science, and battery cell development to tackle this very challenging, multidisciplinary problem. This presentation will show a multiscale computational modeling approach that has produced a novel particle dynamics method called Solid Electrolyte Sphere Approximation Model (SESAM). SESAM modeling targets the 1-10 µm scale structures and provides electromechanical and grain interactions for predictive design guidelines for the manufacturing of solid-state components. Parameters such as particle size and volume fraction of the constituent materials were modeled and experimentally fabricated to optimize electrochemical performance through improved microstructure design. Experimental feedback was provided through ionic and electronic conductivity assessment and structural analysis of developed materials and cell components.

battery↗
DOE OSTI2020

Mobility of Radionuclides in Fractured Carbonate Rocks: Lessons from a Field-Scale Transport Experiment

Current research on radionuclide disposal is mostly conducted in granite, clay, saltstone, or volcanic tuff formations. These rock types are not always available to host a geological repository in every nuclear waste-generating country, but carbonate rocks may serve as a potential alternative. To assess their feasibility, a forced gradient cross-borehole tracer experiment was conducted in a saturated fractured chalk formation. The mobility of stable Sr and Cs (as analogs for their radioactive counterparts), Ce (an actinide analog), Re (a Tc analog), bentonite particles, and fluorescent dye tracers through the flow path was analyzed. The migration of each of these radionuclide analogs (RAs) was shown to be dependent upon their chemical speciation in solution, their interactions with bentonite, and their sorption potential to the chalk rock matrix. The brackish groundwater resulted in flocculation and immobilization of most particulate RAs. Nevertheless, the high permeability of the fracture system allowed for fast overall transport times of all aqueous RAs investigated. This study suggests that the geochemical properties of carbonate rocks may provide suitable conditions for certain types of radionuclide storage (in particular, brackish, high-porosity, and low-permeability chalks). Nevertheless, careful consideration should be given to high-permeability fracture networks that may result in high radionuclide mobility.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2023

Synthesis and thermophysical property determination of NaCl-PuCl3 salts

Currently, a knowledge gap exists in the available data and understanding of thermophysical properties relating to fresh fuel salts, especially those containing plutonium. These data are necessary for designing, constructing, and licensing future commercial molten-salt reactors. Thermophysical properties, such as melting temperature, salt stability, density, and heat capacity were ascertained using NaCl-PuCl3 (36 mol% PuCl3) and a more sodium rich composition containing 25 mol% PuCl3. The NaCl-PuCl3 salt mixture was synthesized for this study and contained 63.4 mol% NaCl, 36.3 mol% PuCl3 and was 99.7% pure. Upon heating, the NaCl–PuCl3 eutectic was stable at temperatures up to 800 °C. The onset of melting occurred at 451 ± 3 °C, and the enthalpy of fusion was determined to be 23.0 ± 1.4 kJ/mol. Heat capacity measurements in the liquid phase ranged from 107.7 to 91.3 J/mol.K, with an average value of 104.6 ± 11.4 J/mol.K between 500 and 650 °C. Three independent trials of the molten NaCl-PuCl3 salt found the density to be ?(T) = 3.8589 – 9.5342·10-4 T(°C). In addition, ab initio molecular dynamic simulations to calculate density and heat capacity values are included.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

High-Temperature Ceramic-Carbonate Dual-Phase Membrane Reactor for Pre-combustion Carbon Dioxide Capture (Final Scientific/Technical Report)

Arizona State University, in collaboration with University of South Carolina, worked on a project aimed at development of a new high temperature, high pressure CO 2 perm-selective membrane reactor for water-gas-shift reaction (WGS) with simulated gasifier syngas to produce a high concentration H 2 stream with CO 2 capture. The membrane reactor is made of a CO 2 semi-permeable ceramic-carbonate dual-phase (CCDP) membrane with high CO 2 perm-selectivity/permeance and thermal/mechanical stability for application in WGS reaction. The objectives of this project were to (1) synthesize the chemically/thermally stable tubular CCDP membranes with CO 2 permeance and selectivity (with respect to H 2 , CO or H 2 O) larger than 6.5×10-7 mol/m2·s·Pa and 500, respectively; (2) establish CCDP membrane reactor setup and study high pressure CO 2 permeation and WGS reaction with CO 2 capture using the setup; and (3) identify conditions for WGS in the CCDP membrane reactor that produce CO 2 and H 2 streams with purity of >99% and >90% respectively at CO conversion >95% and overall carbon capture >90%. The work in this project included both membrane development and membrane reactor process study. The membrane development efforts were focused on investigating a H 2 S resistant and highly oxygen-ionic conducting metal oxide material and membrane for CO 2 separation, fabrication of tubular samaria-doped-ceria/molten-carbonate CCDP membrane with high mechanical strength, and experimental and modeling study of high-pressure CO 2 permeation of the CCDP membranes. Mathematical models were developed to describe WGS in the CCDP membrane reactor without a catalyst or packed with a commercial high temperature WGS catalyst. Experiments on WGS in the CCDP membrane reactor with the commercial WGS catalyst, guided by the model analysis, were performed to identify optimum conditions for achieving the CO conversion, carbon capture, and the purity of the H 2 and CO 2 streams mentioned above. At 30 atm feed pressure, 750°C operation temperature, space velocity of 250 h-1, and with steam sweep, a single-stage CCDP membrane reactor with average CO 2 permeation flux of 0.5 cm3(STP)/min.cm2 can achieve CO 2 conversion of 95% and overall carbon capture of 94%, and produce CO 2 and H 2 streams with dry-based purity of >99% and 92% respectively. The project also included process design and techno-economic analysis (TEA) for a CCDP membrane reactor process for WGS reaction with CO 2 capture for a 550 MW coal-fired IGCC power plant, and its comparison with the conventional fixed-bed reactor system for WGS with follow-up CO 2 capture by an amine absorption process. The target performance for the reactor for WGS with CO 2 capture includes CO conversion >95%, hydrogen stream purity >90%, CO 2 stream purity >95%, and total carbon capture >90%. The CCDP membrane developed in this project can achieve the performance target, without subsequent CO 2 capture process at the optimum conditions identified in this project. The outcome of the process design and TEA analysis shows that the membrane reactor for WGS with in-situ CO 2 capture has an operating cost about 40% lower than that for the conventional fixed-bed reactor with a separate amine absorption process for CO 2 capture. However, the capital cost of the membrane reactor process is about twice that of the conventional process because of the higher cost of the CCDP membrane. Modeling analysis shows that a membrane reactor using a CCDP membrane with higher CO 2 permeance (about three times the current value) can deliver the targeted performance for WGS reaction with CO 2 capture at a much higher space velocity and lower membrane surface area to catalyst volume ratio, leading to a smaller catalyst amount and/or membrane area and hence significantly reduced membrane reactor capital costs.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2019

Understanding the Interactions of Seawater Ions with Amidoxime through X-Ray Crystallography

Insoluble polymer substrates functionalized with the amidoxime (R-C(NH 2 )=NOH) functional group have been demonstrated as a technically feasible platform for extracting uranium from seawater, a potential source of extremely abundant uranium for use as nuclear fuel. While it is possible to isolate macroscopic amounts of uranium from the ocean with a positive energy return on investment using these materials, both the economic and energetic costs are many times greater than those of terrestrial uranium mining. Currently, the major contribution to this cost is the production of the sorbent itself, so being able to recycle the sorbent even a small number of times will have a huge impact on lowering the cost of their use. However, amidoxime resins show capacity fading when stripped by strong acids, presently limiting their recyclability. Both alternative extractants and alternative elution chemistries are under development with promising results but are yet at too early a stage to make predictions about their ultimate success. Given the potentially huge impact of a successful recycling process on the viability of seawater extraction of uranium, there is a strong need to pursue additional routes to elution chemistry. During the course of this project, we studied the interactions of amidoxime-containing small molecules with the abundant metal ions in seawater, including Li, Na, K, Mg, Ca, Fe, Cu, and V, to understand the interactions of [UO 2 ] 2+ with amidoxime. By using small molecules with multiple adjacent functional groups, we crystallized the resulting metal complexes and used single crystal X-ray diffraction (SCXRD) as our primary tool for structural characterization. We also investigated the use of solutions of hydroxylammonium salts in weak acids as eluents for stripping and recycling amidoxime-based sorbents. The replacement of strong acids, which react with and destroy the amidoxime functional groups, with weak acids based on hydroxylammonium, a reagent that is actually used to make the amidoxime groups, is expected to avoid capacity loss on recycling and possibly even regenerate functionality that was lost due to exposure to the marine environment.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

On-Demand Designing of Cathode Internal Surface Architecture for Dramatic Enhancement of SOFC Performance and Durability

This project is aimed to design and modify the internal surfaces of porous composite cathode from currently commercially viable Solid Oxide Fuel Cells (SOFCs), using additive manufacturing process of Atomic Layer Deposition (ALD). The material systems being investigated are commercial composite electrodes complex three-dimensional topographies. In term of the chemistry of the ALD layer applied on the internal surface of the porous cathode, this project has employed commercially relevant electrolyte, electrocatalyst and noble metal materials set. Such materials are fully compatible with the commercial fuel cells, and this project has developed special nanostructure on the surface of the commercial composite cathodes. The formation of the designed nanoarchitecture on the surface of SOFC cathode has been achieved through precise control of ALD parameters and their effect on overall cell performance and resultant electrochemical reaction mechanism of cathodes has been investigated through full cell electrochemical performance testing and nanostructure characterization by transmission electron microscopy (TEM). Under the support of this award, following has been achieved: (1). For cathode materials in solid oxide fuel cells (SOFCs), such as perovskite mixed conductor La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-x (LSCF), cation surface segregation and consequently losing conductivity and active sites for the oxygen reduction reaction (ORR) are problematic. To mitigate the cation segregation and enhance SOFC durability, further decorating the internal backbone surface using the desired electrocatalysts could be a promoting approach. Commonly, the cation segregation such as Sr is very volatile, so the effective surface decoration is ideally conformal. Nevertheless, the conformal surface coating would inevitably alter the ORR pathways that initially take place on the surface of the backbone. To reveal the impact of the conformal coating on both the catalytic activity and the conductivity of the cathode, the unary electrocatalyst of Pt or CoO x , was applied to the LSCF/SDC composite electrode of inherently functional SOFCs, respectively. Both ALD coating layers evolve strong interaction with the LSCF composite cathode. Upon operations, the Pt coating layer remains conformal on LSCF grain surfaces but turns into discrete particles on SDC grain surfaces. Meanwhile, CoO x conformal coating grows to be the discrete nanograins on both the LSCF and SDC grains. ALD coating of the cathode alone reduces the ohmic resistance up to 28 % for the entire cells. The increased conductivity induced by the ALD coating of Pt or CoO x is ascribed to different mechanisms. For the inherent functional SOFCs, the present study presents a novel and feasible approach to apply a conformal, dense coating layer on the surface of a mixed conductor, simultaneously increasing the conductivity and durability of the SOFC cathode. (2). High resistance of the oxygen electrode still significantly hinders the state-of-the-art Solid Oxide Fuel Cells (SOFCs). In particular, for an oxygen electrode consisting of mixed electronic and ionic conductors, such as perovskite lanthanum strontium cobalt ferrite (LSCF), it deteriorates due to its low chemical stability of the grain surface. Such degradation is often associated with the segregation of cations. To prevent the cation surface segregation and its resultant perovskite phase decomposition, we demonstrate a conformal ultra-thin (7-10 nm) surface heterogeneous coating layer consisting of subjacent discrete Pt nanoparticles capped with a superjacent fully dense conformal CoO x layer. The performance studies indicate the ALD coating reduces the cell series resistance by up to 40 %. The conformal CoO x layer consists of randomly orientated but single-layered nanograins, with high-density intergranular and surface grain boundaries serving as the electrochemical reaction sites and facilitating mass transport. The conformal coating layer appears to have successfully suppressed the Sr outward diffusion and confined the Sr enriched layer to a ~ 2 nm interface perovskite phase between the coating layer and the LSCF grain surface. Moreover, this ultra-thin Sr enriched perovskite layer presumably possesses high oxygen vacancy and high ionic conductivity and further imposes tensile strain to the LSCF grain surfaces. With the combination of a conformal CoO x nanoionics, Sr enriched layer, and its strained interface, the ALD coating induced surface layer is estimated to have a conductivity of ~ 1.27x10 4 S/cm, which is over two orders magnitude of that from LSCF at 750 ºC.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2022

High-Temperature 2D Optical Relaxation Visualizes Enhanced Oxygen Exchange Kinetics at Metal-Mixed Conducting Oxide Interfaces

Solid-state heterointerfaces are of interest for emergent local behavior that is distinct from either bulk parent compound. One technologically relevant example is the case of mixed ionic/electronic conductor (MIEC)–metal interfaces, which play an important role in electrochemistry. Metal–MIEC composite electrodes can demonstrate improved catalytic activity vs single-phase MIECs, improving fuel cell efficiency. Similarly, MIEC surface reaction kinetics are often evaluated using techniques that place metal current collectors in contact with the surface under evaluation, potentially altering the response vs the native surface. Here, techniques enabling direct and local in situ observation of the behavior at and around such heterointerfaces are needed. Here, we develop a spatially resolved optical transmission relaxation (2D-OTR) method providing continuous evaluation of local, high-temperature, controlled atmosphere defect kinetics across a ~1 cm2 sample area simultaneously in a contact-free manner. We apply it to observe the spatial variance of oxygen incorporation and evolution rates at ~525–620 °C, in response to step changes in oxygen partial pressure, on MIEC SrTi 0.65 Fe 0.35 O 3–x films as a function of distance from porous Pt and Au layers. Using this model geometry, we find significant enhancements in kinetics adjacent to the metals that decay over a few millimeter distance. To extract kinetic parameters, we fit the short-term optical data (initial portion of relaxations) with an exponential decay function appropriate for surface-exchange-limited kinetics, yielding apparent surface exchange coefficients (k chem ) with spatial resolution, decreasing with distance from the metal. To understand the kinetic processes governing the complete (long-term) optical relaxations, we performed COMSOL simulations, which demonstrated that a combination of laterally varying k chem and in-plane diffusion controls the observed kinetics over the full time range. Further support for spatially varying kchem comes from demonstrations of changing surface and bulk chemistry vs distance from the metal–MIEC interface, by X-ray photoelectron and optical absorption spectroscopies, respectively. Although microporous Pt and Au are not excellent electrodes in isolation, both metals exert a synergistic effect on the oxygen surface exchange rate in the presence of the mixed conducting film.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Investigation of background electron emission in the LUX detector

Dual-phase xenon detectors, as currently used in direct detection dark matter experiments, have observed elevated rates of signals from electron emission processes in the low energy region. While this background negatively impacts detector performance in various ways, its origins have only been partially studied. In this paper, we report a systematic investigation of the electron pathologies observed in the LUX dark matter experiment. We characterize different electron populations based on their emission intensities and their correlations with preceding energy depositions in the detector. By studying these electron backgrounds under different experimental conditions, we identified the possible mechanisms that may contribute to the electron emission. We report the observed electron event rate in LUX after background rejection, and discuss how such backgrounds can be further mitigated in ongoing and future xenon-based dark matter experiments.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗