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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

High-Fidelity Simulation of the Light-to-Dense Stratification Transient in the HiRJET Facility

Density stratification in a large enclosure is a crucial phenomenon to heat transfer and sustainable passive heat removal of a sodium fast reactor during reactivity transients. However, engineering turbulence models were identified to have unsatisfactory performance in predicting propagation of a stratified front. Yet, the scarcity of high-resolution data for stratification hampers the development of models. To explor e applications of leveraging direct numerical simulation (DNS) data to support turbulence model development, this work conducted DNS using NekRS to study a long stratification transient in the High-Resolution Jet (HiRJET) experimental facility. Here, this work considers an experiment run where light fluid is injected into a tank containing a denser fluid with a relative density difference of 1.5%. Formation of the stratified layer is identified as impingement of the buoyant jet promoting mixing of the two fluids. Based on the transient statistics, transport of the concentration can be characterized by regions with dominating effects of turbulent mixing, buoyant dissipation, and molecular diffusion, respectively, as moving away from the elevation of jet impingement. Concentration near the stratified front also exhibits oscillation at Brunt-Väisälä frequency. Preliminary validation of the simulation showed encouraging agreement of the concentration distribution with the reference experiment.

buoyant mixing↗
DOE OSTI2025

Single Crystals of Vanadium Oxides as a Lens for Understanding Structural and Electronic Phase Transformations, Ion Transport, Chemo-Mechanical Coupling, and Electrothermal Neuronal Emulation

Vanadium oxides cystallize in a diverse array of structures and compositions arising from the redox versatility of vanadium, variable covalency of V−O bonds, and myriad coordination geometries. Their open frameworks present abundant interstitial sites that enable insertion of guest-ions. In such compounds, V3d electron and spin localization and disorder couple strongly to structural preferences. The rich structural diversity manifests as a “rugged” free energy landscape with multiple interconvertible polymorphs. Such a landscape sets up structural, electronic, and magnetic transitions that underpin the promise of these materials as ion-insertion battery electrodes; compact primitives for brain-inspired computing, and heterogeneous catalysts. Here, we examine the structural and compositional diversity, electronic instabilities, defect dynamics, structure transformations, mechanical properties, and surface structure of vanadium oxides using single crystals as a distinctive lens. Single crystals enable the measurement of structure−function correlations without the ensemble and orientational averaging inevitable in polycrystalline materials. Their well-defined surfaces further enable examination of facet-dependent reactivity toward molecular adsorbates, ion fluxes, and lattice (mis)matched solids. We provide a comprehensive account of vanadium-oxide single-crystal studies, from delineation of common structural motifs to single-crystal growth techniques, topochemical modification strategies, mechanisms underpinning electronic instabilities, and implementation as electrothermal neurons and battery electrode materials.

Ponis, John [Texas A&M University, College Station↗
DOE OSTI2024

New Instrument for Time-Resolved OH and HO 2 Quantification in High-Pressure Laboratory Kinetics Studies

Here, we have constructed a new time-resolved high-pressure fluorescence assay by gas expansion (HP-FAGE) apparatus, optimized for the detection of OH and HO 2 radicals in complex gas-phase reactions. The new instrument fills a gap in the existing experimental toolkit for chemical kinetics by enabling the quantification of two key reactive species with microsecond time resolution from high-pressure sources, which was previously not attainable. The HP-FAGE is interfaced with a flow reactor, designed for pressures up to 100 bar and temperatures up to 1000 K, in which reactions are initiated by laser photolysis of radical precursors at repetition rates of 1–10 Hz. The HP-FAGE samples gas out of the reactor into a miniature FAGE chamber, where OH is detected by resonant laser-induced fluorescence using a time-delayed probe laser pulse. HO 2 is converted to OH via reaction with NO and then detected by OH fluorescence. The novel FAGE design places the probe region very close to the gas expansion, minimizing the transport time of sampled molecules and resulting in time resolution better than 20 μs for both OH and HO 2 . We calibrate the sensitivity of HP-FAGE, validate its performance with measurements of well-known reaction kinetics (OH + CH 4 , OH + OH, OH + HO 2 , and HO 2 + HO 2 ), and discuss prospects for its future use.

calibration↗
DOE OSTI2026

Field-driven ion pairing dynamics in concentrated electrolytes

Here, we investigate ion pairing dynamics in electrolytes driven far from equilibrium using molecular simulations and nonequilibrium rate theory. Focusing on 0.5M LiPF 6 in water and acetonitrile under uniform electric fields, we compute transition path theory observables, including reactive fluxes and mean first-passage times of ion pairing. Moreover, we introduce a dynamical proxy of free-ion population, where its field-induced change is strongly correlated with the nonlinear enhancement of conductivity, yielding an increase of 40% at 50 mV/Å in acetonitrile, compared to that of less than 10% in aqueous electrolytes. Further kinetic analysis elucidates that Onsager’s classical theory substantially overestimates field-induced enhancement of ion pair dissociation in molecular electrolytes. This discrepancy arises from solvent-mediated dynamical pathways and field-induced dielectric decrement that suppress ion pair dissociation within explicit solvents, highlighting that a faithful description of molecular details is essential. Our results provide a molecular interpretation of nonlinear electrolyte transport beyond continuum theories and establish a general framework for quantifying nonequilibrium reaction kinetics in condensed phase systems.

Moon, Seokjin [University of California, Berkeley,↗
DOE OSTI2023

Redox regulation in chloroplast thylakoid lumen: The pmf changes everything, again

Abstract Photosynthesis is the foundation of life on Earth. However, if not well regulated, it can also generate excessive reactive oxygen species (ROS), which can cause photodamage. Regulation of photosynthesis is highly dynamic, responding to both environmental and metabolic cues, and occurs at many levels, from light capture to energy storage and metabolic processes. One general mechanism of regulation involves the reversible oxidation and reduction of protein thiol groups, which can affect the activity of enzymes and the stability of proteins. Such redox regulation has been well studied in stromal enzymes, but more recently, evidence has emerged of redox control of thylakoid lumenal enzymes. This review/hypothesis paper summarizes the latest research and discusses several open questions and challenges to achieving effective redox control in the lumen, focusing on the distinct environments and regulatory components of the thylakoid lumen, including the need to transport electrons across the thylakoid membrane, the effects of pH changes by the proton motive force (pmf) in the stromal and lumenal compartments, and the observed differences in redox states. These constraints suggest that activated oxygen species are likely to be major regulatory contributors to lumenal thiol redox regulation, with key components and processes yet to be discovered.

Plant Sciences↗
NASA NTRS1990

Budgets of reactive nitrogen, hydrocarbons, and ozone over the Amazon forest during the wet season

The atmospheric composition over the Amazon forest during the wet season is simulated with a one-dimensional photochemical model for the planetary boundary layer (PBL) extending from the ground to 2000-m altitude. The model is constrained and evaluated using observations from the Amazon Boundary Layer Experiment 2B field expedition. Results indicate that only about 20 percent of NO(x) emitted by soils is exported to the atmosphere above the forest canopy. The balance is deposited to vegetation before leaving the canopy layer. The small NO(x) flux that escapes from the canopy is nevertheless sufficient to account for the low NO concentrations observed in the PBL. Soil emission can account for only a portion of NO(y) observed over the forest. Organic nitrates of nonbiogenic origin likely account for the balance of NO(y). Enhancements of CO observed in the PBL appear to reflect direct emission of CO by the forest ecosystem. Concentrations of O3 in the PBL are regulated largely by transport from aloft and deposition to the canopy, with little net influence from photochemistry. Ozone is photochemically produced immediately above the forest where NO concentrations are relatively high, but is photochemically consumed in the upper portion of the PBL.

Jacob, Daniel J.↗
DOE OSTI2024

Applying a Phase-Separation Parameterization in Modeling Secondary Organic Aerosol Formation from Acid-Driven Reactive Uptake of Isoprene Epoxydiols under Humid Conditions

Secondary organic aerosol (SOA) from acid-driven reactive uptake of isoprene epoxydiols (IEPOX) contributes up to 40% of organic aerosol (OA) mass in fine particulate matter. Our previous work showed substantial conversions of particulate inorganic sulfates to surface-active organosulfates (OSs) by IEPOX decreases aerosol acidity and creates a viscous organic-rich shell that poses as a diffusion barrier, inhibiting additional reactive uptake of IEPOX. In this study, to account for this “self-limiting” effect, a phase-separation box model was developed to evaluate parameterizations of IEPOX reactive uptake against time-resolved chamber measurements of IEPOX-SOA tracers, including 2-methyltetrols (2-MT) and methyltetrol sulfates (MTS), at ~ 50% relative humidity. The phase-separation model was most sensitive to mass accommodation coefficient, IEPOX diffusivity in the organic shell, and ratio of the third-order reaction rate constants forming 2-MT and MTS (k MT /k MTS ). In particular, k MT /k MTS had to be lower than 0.1 to bring model predictions of 2-MT and MTS in closer agreement with chamber measurements, while prior studies reported values larger than 0.71. The model-derived rate constants favor more particulate MTS formation due to 2-MT likely off-gassing at ambient-relevant OA loadings. Incorporating this parametrization into chemical transport models is expected to predict lower IEPOX-SOA mass and volatility due to the predominance of OSs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1996

Studies of Radiation-Driven and Buoyancy-Driven Fluid Flows and Transport

It is well known that radiative heat transport influences many types of buoyant flows due to its effect on the temperature and thus density field in the fluid medium. It is of interest to study gaseous flows driven solely by radiation in the absence of buoyancy, particularly because of its application to astrophysical flows that are well known from astronomical observations and numerical simulation. However, no laboratory-scale experiments of this phenomenon have ever been conducted. To study the possibility of obtaining such flows in the laboratory, an apparatus was built to produce large temperature differences (Delta (T)) up to 300 K in a gas confined between flat parallel plates. SF6 was used as the radiatively-active gas because its Planck absorption length is much shorter than that of any other common non-reactive gas. The NASA-Lewis 2.2 second drop tower was used to obtain reduced gravity in order to suppress buoyancy effects. To image the resulting flows, a laser shearing interferometer was employed. Initial results indicate the presence of flow that does not appear to be attributable to the residual flow resulting from buoyancy influences before the drop. For Delta(T) greater than 70 K, slight deformations in the interferometer fringes seen at lower Delta(T) became large unsteady swirls. Such behavior did not occur for radiatively-inactive gases, suggesting that a flow driven solely by radiation was obtained in SF6 and to a lesser extent in CO2. This was more pronounced at higher pressures and plate spacings, consistent with our scaling predictions.

Ronney, Paul D.↗
NASA NTRS1994

Studies of Radiation-Driven and Buoyancy-Driven Fluid Flows and Transport

It is well known that radiative heat transport influences many types of buoyant flows due to its effect on the temperature and thus density field in the fluid medium. It is of interest to study gaseous flows driven solely by radiation in the absence of buoyancy, particularly because of its application to astrophysical flows that are well known from astronomical observations and numerical simulation. However, no laboratory-scale experiments of this phenomenon have ever been conducted. To study the possibility of obtaining such flows in the laboratory, an apparatus was built to produce large temperature differences (Delta T) up to 300 K in a gas confined between flat parallel plates. SF6 was used as the radiatively-active gas because its Planck absorption length is much shorter than that of any other common non-reactive gas. The NASA-Lewis 2.2 second drop tower was used to obtain reduced gravity in order to suppress buoyancy effects. To image the resulting flows, a laser shearing interferometer was employed. Initial results indicate the presence of flow that does not appear to be attributable to the residual flow resulting from buoyancy influences before the drop. For Delta T greater than 70 K, slight deformations in the interferometer fringes seen at lower Delta T became large unsteady swirls. Such behavior did not occur for radiatively-inactive gases, suggesting that a flow driven solely by radiation was obtained in SF6 and to a lesser extent in CO2 This was more pronounced at higher pressures and plate spacings, consistent with our scaling predictions.

Ronney, Paul D.↗
NASA NTRS1994

Contributions of a Tunable Diode Laser Instrument (ATLAS) to the Stratospheric Ozone Depletion Question

The Airborne Tunable Laser Absorption Spectrometer - ATLAS - was designed and built at the NASA Ames Research Center and operates on the NASA ER-2 high altitude research aircraft. ATLAS has taken part in a number of important polar and mid-latitude research campaigns, since 1987, focused on various aspects of stratospheric ozone chemistry and dynamics. The chief measurement carried out by the ATLAS second harmonic diode laser spectrometer is of the important atmospheric tracer N2O. Using N2O as an inert tracer we have been able to gain significant new information on polar vortex dynamics and on the correlations of several important long-lived tracers in the stratosphere. The correlation of N2O with NOy (total reactive nitrogen) has been shown to be linear for a great variety of unperturbed stratospheric conditions, and the breakdown of this correlation has been used to detect denitrification by PSCs in the polar vortex, especially in the Antarctic spring. Denitrification is an important step in the process of ozone hole formation in the austral spring. Correlations of N2O with CFCs and CH4 have led to improved estimates of atmospheric lifetimes of these important molecules. Finally the correlation of N2O with CO2, the latter now being measured with great precision by a new instrument on the ER-2, has led to a significant new tool for studying horizontal and vertical mixing in the lower stratosphere, a tool which is very useful in assessing the potential effects of high speed civil transport aircraft in the lower stratosphere. A new, light-weight version of ATLAS is currently being built for unmanned high altitude aircraft, specifically the new Perseus vehicle. We will give a brief description of this effort.

Loewenstein, Max↗
DOE OSTI2026

Membrane Degradation in PEM Fuel Cells: Part I. Modeling Gas Crossover and the Pt Band

Understanding chemical degradation of the proton-exchange membrane in fuel cells is crucial for extending their lifetimes. Herein, various degradation reactions reported in literature are organized and analyzed, including direct radical generation and an indirect (Fenton) pathway. To understand the transport of dissolved H 2 and O 2 crossover gases as they relate to membrane degradation, an agglomerate-scale model is introduced, treating gas, ionomer, and catalyst as discrete phases. The model reveals a key phenomenon: at working potentials, dissolved gases are mostly consumed at the interface between the catalyst layer and the membrane, leaving little gas to cross the membrane. Under open-circuit conditions, dissolved gases are not consumed and can then cross the membrane. This explains high H 2 O 2 concentrations and degradation rates seen in experiments but not captured in previous models. Following mixed-potential theory, crossover gases supply the hydrogen-oxidation and oxygen-reduction reactions, which occur simultaneously on individual Pt particles comprising the Pt band in the membrane, forming reactive species (H 2 O 2 , OH·). Results show crossover gas almost entirely reacts on the Pt band, allowing little to reach the opposite electrode. Furthermore, the micro-scale geometry of the catalyst-layer/membrane interface impacts the gas crossover at working potentials, indicating that cell construction affects membrane durability.

Johnson, Evan F. [Lawrence Berkeley National Labor↗
NASA NTRS2005

Reactions of Air Transport Flight Crews to Displays of Weather During Simulated Flight

Display of information in the cockpit has long been a challenge for aircraft designers. Given the limited space in which to present information, designers have had to be extremely selective about the types and amount of flight related information to present to pilots. The general goal of cockpit display design and implementation is to ensure that displays present information that is timely, useful, and helpful. This suggests that displays should facilitate the management of perceived workload, and should allow maximal situation awareness. The formatting of current and projected weather displays represents a unique challenge. As technologies have been developed to increase the variety and capabilities of weather information available to flight crews, factors such as conflicting weather representations and increased decision importance have increased the likelihood for errors. However, if formatted optimally, it is possible that next generation weather displays could allow for clearer indications of weather trends such as developing or decaying weather patterns. Important issues to address include the integration of weather information sources, flight crew trust of displayed weather information, and the teamed reactivity of flight crews to displays of weather. Past studies of weather display reactivity and formatting have not adequately addressed these issues; in part because experimental stimuli have not approximated the complexity of modern weather displays, and in part because they have not used realistic experimental tasks or participants. The goal of the research reported here was to investigate the influence of onboard and NEXRAD agreement, range to the simulated potential weather event, and the pilot flying on flight crew deviation decisions, perceived workload, and perceived situation awareness. Fifteen pilot-copilot teams were required to fly a simulated route while reacting to weather events presented in two graphical formats on a separate visual display. Measures of flight crew reactions included performance-based measures such as deviation decision accuracy, and judgment-based measures such as perceived decision confidence, workload, situation awareness, and display trust. Results demonstrated that pilots adopted a conservative reaction strategy, often choosing to deviate from weather rather than ride through it. When onboard and NEXRAD displays did not agree, flight crews reacted in a complex manner, trusting the onboard system more but using the NEXRAD system to augment their situation awareness. Distance to weather reduced situation awareness and heightened workload levels. Overall, flight crews tended to adopt a participative leadership style marked by open communication. These results suggest that future weather displays should exploit the existing benefits of NEXRAD presentation for situation awareness while retaining the display structure and logic inherent in the onboard system.

Bliss, James P.↗
DOE OSTI2021

Aircraft measurements of aerosol and trace gas chemistry in the eastern North Atlantic

The Aerosol and Cloud Experiment in the Eastern North Atlantic (ACE-ENA) investigated properties of aerosols and subtropical marine boundary layer (MBL) clouds. Low subtropical marine clouds can have a large effect on Earth's radiative budget, but they are poorly represented in global climate models. In order to understand their radiative effects, it is imperative to understand the composition and sources of the MBL cloud condensation nuclei (CCN). The campaign consisted of two intensive operation periods (IOPs) (June–July 2017 and January–February 2018) during which an instrumented G-1 aircraft was deployed from Lajes Field on Terceira Island in the Azores, Portugal. The G-1 conducted research flights in the vicinity of the Atmospheric Radiation Measurement (ARM) Eastern North Atlantic (ENA) atmospheric observatory on Graciosa Island. An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and Ionicon proton-transfer-reaction mass spectrometer (PTR-MS) were deployed aboard the aircraft, characterizing chemistry of non-refractory aerosol and trace gases, respectively. The eastern North Atlantic region was found to be very clean, with an average non-refractory submicrometer aerosol mass loading of 0.6 µg m −3 in the summer and 0.1 µg m −3 in the winter, measured by the AMS. Average concentrations of the trace reactive gases methanol and acetone were 1–2 ppb; benzene, toluene and isoprene were even lower, <1 ppb. Mass fractions of sulfate, organics, ammonium and nitrate in the boundary layer were 69 %, 23 %, 7 % and 1 % and remained largely similar between seasons. The aerosol chemical composition was dominated by sulfate and highly processed organics. Particulate methanesulfonic acid (MSA), a well-known secondary biogenic marine species, was detected, with an average boundary layer concentration of 0.021 µg m −3 , along with its gas-phase precursor, dimethyl sulfide (DMS). MSA accounted for no more than 3 % of the submicron, non-refractory aerosol in the boundary layer. Examination of vertical profiles of aerosol and gas chemistry during ACE-ENA reveals an interplay of local marine emissions and long-range-transported aged aerosol. A case of transport of biomass burning emissions from North American fires has been identified using back-trajectory analysis. In the summer, the non-refractory portion of the background CCN budget was heavily influenced by aerosol associated with ocean productivity, in particular sulfate formed from DMS oxidation. Episodic transport from the continents, particularly of biomass burning aerosol, periodically increased CCN concentrations in the free troposphere. In the winter, with ocean productivity lower, CCN concentrations were overall much lower and dominated by remote transport. These results show that anthropogenic emissions perturb CCN concentrations in remote regions that are sensitive to changes in CCN number and illustrate that accurate predictions of both transport and regional aerosol formation from the oceans are critical to accurately modeling clouds in these regions.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1996

Chemical Characteristics of Continental Outflow Over the Tropical South Atlantic Ocean from Brazil and Africa

The chemical characteristics of air parcels over the tropical South Atlantic during September - October 1992 are summarized by analysis of aged marine and continental outflow classifications. Positive correlations between CO and CH3CL and minimal enhancements of C2CL40, and various ChloroFluoroCarbon (CFC) species in air parcels recently advected over the South Atlantic basin strongly suggest an impact on tropospheric chemistry from biomass burning on adjacent continental areas of Brazil and Africa. Comparison of the composition of aged Pacific air with aged marine air over the South Atlantic basin from 0.3 to 12.5 km altitude indicates potential accumulation of long-lived species during the local dry season. This may amount to enhancements of up to two-fold for C2H6, 30% for CO, and 10% for CH3Cl. Nitric oxide and NO(x) were significantly enhanced (up to approx. 1 part per billion by volume (ppbv)) above 10 km altitude and poorly correlated with CO and CH3Cl. In addition, median mixing ratios of NO and NO(x) were essentially identical in aged marine and continental outflow air masses. It appears that in addition to biomass burning, lightning or recycled reactive nitrogen may be an important source of NO(x) to the upper troposphere. Methane exhibited a monotonic increase with altitude from approx. 1690 to 1720 ppbv in both aged marine and continental outflow air masses. The largest mixing ratios in the upper troposphere were often anticorrelated with CO, CH3Cl, and CO2, suggesting CH, contributions from natural sources. We also argue, based on CH4/CO ratios and relationships with various hydrocarbon and CFC species, that inputs from biomass burning and the northern hemisphere are unlikely to be the dominant sources of CO, CH4 and C2H6 in aged marine air. Emissions from urban areas would seem to be necessary to account for the distribution of at least CH4 and C2H6. Over the African and South American continents an efficient mechanism of convective vertical transport coupled with large-scale circulations conveys biomass burning, urban, and natural emissions to the upper troposphere over the South Atlantic basin. Slow subsidence over the eastern South Atlantic basin may play an important role in establishing and maintaining the rather uniform vertical distribution of long-lived species over this region. The common occurrence of values greater than 1 for the ratio CH3OOH/H2O2 in the upper troposphere suggests that precipitation scavenging effectively removed highly water soluble gases (H2O2, HNO3, HCOOH, and CH3COOH) and aerosols during vertical convective transport over the continents. However, horizontal injection of biomass burning products over the South Atlantic, particularly water soluble species and aerosol particles, was frequent below 6 km altitude.

Talbot, R. W.↗
DOE OSTI2022

A review of coarse mineral dust in the Earth system

Mineral dust particles suspended in the atmosphere span more than three orders of magnitude in diameter, from <0.1 µm to more than 100 µm. This wide size range makes dust a unique aerosol species with the ability to interact with many aspects of the Earth system, including radiation, clouds, hydrology, atmospheric chemistry, and biogeochemistry. This review focuses on coarse and super-coarse dust aerosols, which we respectively define as dust particles with a diameter of 2.5–10 µm and 10–62.5 µm. We review several lines of observational evidence indicating that coarse and super-coarse dust particles are transported farther than previously expected and that the abundance of these particles is substantially underestimated in current global models. We synthesize previous studies that used observations, theories, and model simulations to highlight the impacts of coarse and super-coarse dust aerosols on the Earth system, including their effects on dust-radiation interactions, dust-cloud interactions, atmospheric chemistry, and biogeochemistry. Specifically, coarse and super-coarse dust aerosols produce a net positive direct radiative effect (warming) at the top of the atmosphere and can modify temperature and water vapor profiles, influencing the distribution of clouds and precipitation. In addition, coarse and super-coarse dust aerosols contribute a substantial fraction of ice-nucleating particles, especially at temperatures above –23 °C. They also contribute a substantial fraction to the available reactive surfaces for atmospheric processing and the dust deposition flux that impacts land and ocean biogeochemistry by supplying important nutrients such as iron and phosphorus. Furthermore, we examine several limitations in the representation of coarse and super-coarse dust aerosols in current model simulations and remote-sensing retrievals. Because these limitations substantially contribute to the uncertainties in simulating the abundance and impacts of coarse and super-coarse dust aerosols, we offer some recommendations to facilitate future studies. Overall, we conclude that an accurate representation of coarse and super-coarse properties is critical in understanding the impacts of dust aerosols on the Earth system.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Analysis of an all-solid state nanobattery using molecular dynamics simulations under an external electric field

Present Li-ion battery (LIB) technology requires strong improvements in performance, energy capacity, charging-time, and cost to expand their application to e-mobility and grid storage. Li-metal is one of the most promising materials to replace commercial anodes such as graphite because of its 10 times higher specific capacity. However, Li-metal has high reactivity with commercial liquid electrolytes; thus, new solid materials are proposed to replace liquid electrolytes when Li-metal anodes are used. We present a theoretical analysis of the charging process in a full nanobattery, containing a LiCoO 2 cathode, a Li 7 P2S 8 I solid-state electrolyte (SSE), a Li-metal anode as well as Al and Cu collectors for the cathode and anode, respectively. In addition, we added a Li 3 P/Li 2 S film as a solid electrolyte interphase (SEI) layer between the Li-anode and SSE. Thus, we focus this study on the SEI and SSE. We simulated the charging of the nanobattery with an external voltage by applying an electric field. We estimated temperature profiles within the nanobattery and analyzed Li-ion transport through the SSE and SEI. Here, we observed a slight temperature rise at the SEI due to reactions forming $PS_{3}^{–}$ and $P_{2}S_{7}^{4}$$^{–}$ fragments at the interfaces; however, this temperature profile changes due to the charging current under the presence of the external electric field ε = 0.75 V Å –1 . Without the external field, the calculated open-circuit voltage (OCV) was 3.86 V for the battery, which is within the range of values of commercial cobalt-based LIBs. This voltage implies a spontaneous fall of available Li-ions from the anode to the cathode (during discharge). The charge of this nanobattery requires overcoming the OCV plus an additional voltage that determines the charging current. Thus, we applied an external potential able to neutralize the OCV, plus an additional 1.6 V to induce the transport of Li + from the cathode up to the anode. Several interesting details about Li + transport paths through the SSE and SEI are discussed.

25 ENERGY STORAGE↗
DOE OSTI2021

Performance of HALEU and HEU-Fueled Nuclear Thermal Propulsion Reactors

Interplanetary spaceflight may be significantly improved by rockets that utilize nuclear thermal propulsion (NTP) instead of the chemically propelled rockets in use today. To be efficient, NTP reactors must be light, which presents unique design opportunities and challenges to reactor designers. One such opportunity is the enrichment of the nuclear fuel that powers the NTP reactor. The use of high-enriched uranium (HEU) instead of high-assay low-enriched uranium (HALEU) will result in a lower mass of fuel required but may present additional challenges beside the mass considerations, such as proliferation concerns, availability, public acceptance and authorization basis. Whether or not a NTP reactor fueled with HEU is significantly lighter than its HALEU counterpart is unclear and an assessment has been performed here as part of the Mars Transportation Assessment Study. This report assesses the impact of reducing the fuel enrichment form HEU (93 wt.% 235U) to HALEU fuel (19.5 wt.% 235U) on reactor design outcomes for a conceptual NTP reactor. Two reactor designs, one fueled with HEU and the other with HALEU, were prepared based on a multi-stage design process. The neutronics and thermal-hydraulics characteristics of these reactors are compared and contrasted to illustrate the impacts of fuel enrichment. Despite differences in fuel and moderator mass, the overall mass difference between the HALEU and HEU cores was only 9%. The required core size and assembly dimensions are nearly equivalent. This finding is based on a rapid design process that targeted core volume minimization. Each features some neutronics advantages - depletion is much less significant in the HEU core, but the Doppler reactivity feedback is stronger in the HALEU core. Additional discussions are made about the possible benefits of other design changes, including the possibility of utilizing a fast-spectrum reactor. Given the scope of this assessment the findings discussed in this report are not exhaustive and are only providing an initial comparison of the most obvious design and performance parameters.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Effect of Framework Composition and NH 3 on the Diffusion of Cu + in Cu-CHA Catalysts Predicted by Machine-Learning Accelerated Molecular Dynamics

Cu-exchanged zeolites rely on mobile solvated Cu + cations for their catalytic activity, but the role of the framework composition in transport is not fully understood. Ab initio molecular dynamics simulations can provide quantitative atomistic insight but are too computationally expensive to explore large length and time scales or diverse compositions. We report a machine-learning interatomic potential that accurately reproduces ab initio results and effectively generalizes to allow multinanosecond simulations of large supercells and diverse chemical compositions. Biased and unbiased simulations of [Cu(NH 3 ) 2 ] + mobility show that aluminum pairing in eight-membered rings accelerates local hopping and demonstrate that increased NH 3 concentration enhances long-range diffusion. The probability of finding two [Cu(NH 3 ) 2 ] + complexes in the same cage, which is key for SCR-NOx reaction, increases with Cu content and Al content but does not correlate with the long-range mobility of Cu + . Supporting experimental evidence was obtained from reactivity tests of Cu-CHA catalysts with a controlled chemical composition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗