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The Role of Metal Oxides in Li-S Batteries: A High-Areal-Capacity Sulfur Composite Cathode Investigation

Compared to lithium-ion batteries (LIB), lithium-sulfur (Li-S) batteries have low cost and high theoretical specific energy (2510 Wh/kg or about 10 times of the LIB). However, Li-S batteries have several challenges, including large volume expansion, poor utilization of the end products, sluggish kinetics of polysulfides, and crossover, so-called the "shuttle effect". To address these issues, we have introduced metal oxides to the Li-S electrode to develop a metal-oxide-sulfur composite electrode. We aim to use metal oxides to assist the Li-S formation (dissociation) during discharge (charge) cycles. We elect to focus on LIB-based metal oxides to ensure that the added material can contribute storage capacity to the battery. Our cathodes are fabricated by both the conventional slurry casting and air-controlled electrospray. LIB electrode materials, such as Li(Ni 0.6 Mn 0.6 Co 0.2 )O 2 , LiMn 2 O 4 , Li 2 TiO 3 , etc, were incorporated with the sulfur-carbon composite and their charge-discharge performances are compared. We found that the presence of metal oxides increased sulfur utilization with stable cycling performance, even in cells with high areal capacities. To unveil the interactions between lithium metal oxides and sulfur, the cathodes were analyzed by various characterization techniques, including scanning electron microscopy, X-ray diffraction, thermogravimetric analysis, and electrochemistry. The analysis of the role of the oxides will be presented along with the reaction mechanism.

25 ENERGY STORAGE↗

Report of METL Mutual Inductance Level Sensor Development for Use in Liquid Metals – FY2023

A robust mutual inductance level sensor (MILS) for use in high temperature liquid metals has been developed at Argonne National Laboratory (ANL). The current design utilizes mineral insulated cables with a 300-series stainless steel sheath, magnesium oxide insulation, and a single copper conductor. Two coils are wrapped on a common core made of a 300-series stainless steel tube. One coil is energized with an alternating current (AC) source, and this electromagnetically couples with the second coil to generate an induced voltage. The voltage is measured to determine the mutual induction between the coils, and the mutual inductance measurement can be used to determine the level of a nearby liquid metal volume. The MILS can be located in an isolating thimble that is fully sealed to a vessel containing liquid metal for ease of maintenance and replacement. When the primary coil is energized with the AC source, the coil not only electromagnetic (EM) couples with the second coil, but also the surrounding liquid metal. The EM coupling with the surrounding liquid metal reduces the EM coupling with the second coil, producing an inverse-linear relationship between liquid metal level and secondary coil voltage. This has all been demonstrated at the Mechanisms Engineering Test Loop (METL) liquid sodium facility at ANL. The most current iteration of the MILS system is the MILS-MK-II. This sensor system has been commissioned in a non-sodium test stand where calibrations were performed using a sodium analog. The calibrations proved to be highly linear and repeatable. The MILS-MK-II has been installed in the METL expansion tank where high temperature sodium tests have been performed. The MILS-MK-II has been calibrated against a known standard at temperature of 300°C, and the calibrations have proved to be highly linear and repeatable. The calibrated MILS-MK-II has been in operation in the METL facility for several thousands of hours at temperatures around 300°C. The experimental data has been used to develop and validate electromagnetic finite element models in COMSOL Multiphysics, and now these models can be used to advance the development of the sensor system. Next steps will include temperature compensation to allow for operation at various temperatures. Additionally, efforts to incorporate a self-calibration methodology are underway.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Synthetic Metal Atomic Layer Deposition Tool (Final Report)

As part of the Cyclotron Road program, Laminera Inc. worked towards development of atomic layer deposition process customizations and tool modifications to produce synthetic metal films at commercial scale and improve the film quality. Today's state-of-the-art in atomic layer deposited synthetic metal technology is only possible at a research-scale because current tools have practical limitations for scaling industrially and generating high conductivity films. Ultrathin, conformal synthetic metal films have many possible applications such as high surface area nanoporous electrodes for supercapacitors and water desalination devices; protective electrode coatings for electrochemical devices; seed layers for semiconductor device fabrication; or metallic component stabilizing coatings that enable enhanced storage density in next generation hard disk drives. The best synthetic metal conductive and plasmonic properties have been demonstrated using sputtering, which relies on high temperature sputtering with substrate dependent and directional growth limiting usage. This work explored refining process and tool modifications to create ultrathin, conformal, synthetic metal films that can be deposited with high quality over complex three-dimensional surfaces.

36 MATERIALS SCIENCE↗

U Metal Oxidation with Steam (U)

The Savannah Rive National Laboratory 9SRNL) is evaluating a method to produce uranium oxide (UO 2 ) from uranium metal using steam. The typical methods for making UO 2 yield powders with particle-size ranges of 1 to 50 micron. The goal of the steam oxidation is to produce a depleted uranium (DU) product with a larger particle size that can be used as a surrogate for testing physical and mechanical process techniques to refine uranium and/or plutonium bearing residues. Several studies in the literature indicated that reactions between uranium metal and steam will yield UO 2 as fine powders in the 160 to 500 °C range, but granular materials form above 500°C. Above 880 °C, a hard compact scale forms on the U metal. Furthermore, sintering of UO 2 occurs at about 1300 °C, but it has been stated that the presence of steam enhances the sintering characteristics of UO 2 . Initial studies into the oxidation of DU metal in an atmosphere of argon and steam have been completed. Oxidation of depleted uranium metal in Ar/steam at 600, 710, 700, and 830 °C yielded at UO 2 product with little or no impurity at each temperature. Although not enough sample was available to perform sieve analysis for particle size distribution, SEM images reveal that a significant volume fraction of the products at 710, 770, and 830 °C exceeds 100 microns. The material produced at 600 °C was too fine for programmatic needs. Questions associated with the UO 2 include morphology of product, mechanical strength of the particles, and performance in milling operations. The size of the samples produced in these tests did not allow for quantitative assessment of particle size of mechanical strength. A qualitative assessment of the particles formed at 710, 770, and 830 °C was that the samples produced at 710 and 770 °C were friable, and the sample produced 830 °C had more mechanical strength. Sintering of the samples in Ar/steam at 970 °C appeared to increase the strength of the particles without changing their general particle size characteristics. Due to the small sample sizes, the increase in strength could not be quantified. If the sintering at 970 °C is inadequate, higher sintering temperatures in Ar/steam can be evaluated. Future work will increase scale of the steam oxidation conditions which yield the most-favorable particle-size distributions with sufficient mechanical strength for programming usage. Further consideration will be given to oxidation temperature, steam addition to the reaction vessel, U metal pretreatment, and sintering conditions after oxidation. The UO 2 production could involve a two-step process where particles are formed in steam at lower temperatures (700-850 °C) and then sintered in Ar/steam at elevated temperatures (950-1200 °C). Larger samples (50-100 g each) will provide sufficient UO 2 product for sieve analysis and assessment of mechanical strength relatives to subsequent milling operations.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

MARSAME Radiological Release Report for Metal Items from Technical Area 53, Set 25

Environmental Protection and Compliance, Environmental Stewardship Group (EPC-ES) has evaluated the survey results for metal items from the Los Alamos Neutron Science Center (LANSCE) at Technical Area 53 (TA-53) and found that the metal items described in Table 1 of this report (identified by Radiation Protection [RP] Tracking Numbers) meet the criteria for unrestricted release under Department of Energy (DOE) Order 458.1 Chg 4, Radiation Protection of the Public and the Environment (DOE 2020) and can be recycled. This conclusion is based on the known history of the metal items and radiation survey data (see the completed RP-Form-031 LANSCE Metals Clearance Log [LANL 2021a] for each item in Attachment 1). None of the items in this report are located within radiological areas. Therefore, the items are considered unencumbered and are not subject to the moratorium suspension on metal recycling from DOE facilities. Additionally, Los Alamos National Laboratory (LANL) has determined that there is no practical opportunity for internal DOE reuse of this metal.

54 ENVIRONMENTAL SCIENCES↗

MARSAME Radiological Release Report for Metal Items from Technical Area 53, Set 26

Environmental Protection and Compliance, Environmental Stewardship Group (EPC-ES) has evaluated the survey results for metal items from the Los Alamos Neutron Science Center (LANSCE) at Technical Area 53 (TA-53) and found that the metal items described in Table 1 of this report (identified by Radiation Protection [RP] Tracking Numbers) meet the criteria for unrestricted release under Department of Energy (DOE) Order 458.1 Chg 4, Radiation Protection of the Public and the Environment (DOE 2020) and can be recycled. This conclusion is based on the known history of the metal items and radiation survey data. None of the items in this report are located within radiological areas. Therefore, the items are considered unencumbered and are not subject to the moratorium suspension on metal recycling from DOE facilities. Additionally, Los Alamos National Laboratory (LANL) has determined that there is no practical opportunity for internal DOE reuse of this metal. Process knowledge indicates that these metal items were unlikely to ever be in direct contact with the beam and thus are unlikely to have become activated. Surface contamination measurements (both total and removable) showed either no detectable radioactivity or activity levels within the range of background. All measurements for volumetric contamination were indistinguishable from background based on calculated decision limits. Additionally, all gamma isotopic surveys conducted for defense-in depth showed no identifiable gamma radiation from beam activation.

54 ENVIRONMENTAL SCIENCES↗

MARSAME Radiological Release Report for Metal Items from TA 53, Set 18

EPC-ES has evaluated the survey results for metal items from the Los Alamos Neutron Science Center (LANSCE) and found that the metal items described in Table 1 of this report (identified by RP Tracking Numbers) meet the criteria for unrestricted release under DOE Order 458.1 Radiation Protection of the Public and the Environment and can be recycled. This conclusion is based on the known history of the metal items and on radiation survey data (see the completed RP-Form-036 LANSCE Metals Clearance Log for each item). None of the items in this report are located within radiological areas. Therefore, the items are considered unencumbered and are not subject to the moratorium suspension on metal recycling from Department of Energy facilities. Additionally, LANL has determined that there is no practical opportunity for internal DOE reuse or recycling of this metal.

54 ENVIRONMENTAL SCIENCES↗

MARSAME Radiological Release Report for Metal Items from TA 53, Set 19

EPC-ES has evaluated the survey results for metal items from the Los Alamos Neutron Science Center (LANSCE) and found that the metal items described in Table 1 of this report (identified by RP Tracking Numbers) meet the criteria for unrestricted release under DOE Order 458.1 Radiation Protection of the Public and the Environment and can be recycled. This conclusion is based on the known history of the metal items and on radiation survey data (see the completed RP-Form-036 LANSCE Metals Clearance Log for each item). None of the items in this report are located within radiological areas. Therefore, the items are considered unencumbered and are not subject to the moratorium suspension on metal recycling from Department of Energy facilities. Additionally, LANL has determined that there is no practical opportunity for internal DOE reuse or recycling of this metal.

54 ENVIRONMENTAL SCIENCES↗

Tuning Catalytically Active Single Sites in Nonstoichiometric, Mixed Metal Oxides for Oxygen Electrocatalysis (Final Technical Report)

The objective of the proposed work is to employ controlled synthesis, advanced characterization, detailed electrochemical testing and theoretical calculations to develop a framework that would guide the design of robust, non-stoichiometric mixed metal oxides for oxygen electrocatalysis. In this research plan, we focus around the idea of tuning the metal ion composition and environment to create single atom centers with the utmost electrocatalytic activity. We hypothesized that tuning the cationic sites in nonstoichiometric mixed metal oxides will lead to single 4d/5d metal surface sites with optimal catalytic activity for low temperature oxygen reduction (ORR) and oxygen evolution (OER) at solid/liquid interfaces. We will focus on different crystal structures of these oxides including Ruddlesden-Popper (R-P) oxides, simple perovskites and pyrochlores due to their flexibility in accommodating different metal cation dopants, and the fact that they represent variations in the cationic arrangements in non-stoichiometric mixed metal oxide structures, which will lead to an understanding of how bulk crystal structure effects catalytic activity and stability of these systems.

08 HYDROGEN↗

In Situ, Real-Time Diagnostic to Improve the Liquid Metal Jetting Additive Manufacturing Process [Poster]

Liquid Metal Jetting (LMJ) is a metal additive manufacturing technique that involves jetting molten metal droplets at high frequencies to build solid metal parts. As an alternative to industry standard Lazer Powder Bed Fusion (LPBF) and Direct Metal Writing (DMW) techniques, LMJ poses significant advantages including no powder feed stock, no post sintering process, very high deposition rates, and the capability to print various metals. This summer, I was tasked with improving my old system to process at much higher resolution, Increasing the capture rate, and implementing this diagnostic on various LMJ setups. This system provides a vital longitudinal study to understand individual droplets in the LMJ process.

36 MATERIALS SCIENCE↗

Efficient Leaching of Metal Ions from Spent Li-Ion Battery Combined Electrode Coatings Using Hydroxy Acid Mixtures and Regeneration of Lithium Nickel Manganese Cobalt Oxide

Extensive use of Li-ion batteries in electric vehicles, electronics, and other energy storage applications has resulted in a need to recycle valuable metals Li, Mn, Ni, and Co in these devices. In this work, an aqueous mixture of glycolic and lactic acid is shown as an excellent leaching agent to recover these critical metals from spent Li-ion laptop batteries combined with cathode and anode coatings without adding hydrogen peroxide or other reducing agents. An aqueous acid mixture of 0.15 M in glycolic and 0.35 M in lactic acid showed the highest leaching efficiencies of 100, 100, 100, and 89% for Li, Ni, Mn, and Co, respectively, in an experiment at 120 °C for 6 h. Subsequently, the chelate solution was evaporated to give a mixed metal-hydroxy acid chelate gel. Pyrolysis of the dried chelate gel at 800 °C for 15 h could be used to burn off hydroxy acids, regenerating lithium nickel manganese cobalt oxide, and the novel method presented to avoid the precipitation of metals as hydroxide or carbonates. The Li, Ni, Mn, and Co ratio of regenerated lithium nickel manganese cobalt oxide is comparable to this metal ratio in pyrolyzed electrode coating and showed similar powder X-ray diffractograms, suggesting the suitability of α-hydroxy carboxylic acid mixtures as leaching agents and ligands in regeneration of mixed metal oxide via pyrolysis of the dried chelate gel.

Electrochemistry↗

Is Genetic Engineering a Route to Enhance Microalgae-Mediated Bioremediation of Heavy Metal-Containing Effluents?

Contamination of the biosphere by heavy metals has been rising, due to accelerated anthropogenic activities, and is nowadays, a matter of serious global concern. Removal of such inorganic pollutants from aquatic environments via biological processes has earned great popularity, for its cost-effectiveness and high efficiency, compared to conventional physicochemical methods. Among candidate organisms, microalgae offer several competitive advantages; phycoremediation has even been claimed as the next generation of wastewater treatment technologies. Furthermore, integration of microalgae-mediated wastewater treatment and bioenergy production adds favorably to the economic feasibility of the former process—with energy security coming along with environmental sustainability. However, poor biomass productivity under abiotic stress conditions has hindered the large-scale deployment of microalgae. Recent advances encompassing molecular tools for genome editing, together with the advent of multiomics technologies and computational approaches, have permitted the design of tailor-made microalgal cell factories, which encompass multiple beneficial traits, while circumventing those associated with the bioaccumulation of unfavorable chemicals. Previous studies unfolded several routes through which genetic engineering-mediated improvements appear feasible (encompassing sequestration/uptake capacity and specificity for heavy metals); they can be categorized as metal transportation, chelation, or biotransformation, with regulation of metal- and oxidative stress response, as well as cell surface engineering playing a crucial role therein. This review covers the state-of-the-art metal stress mitigation mechanisms prevalent in microalgae, and discusses putative and tested metabolic engineering approaches, aimed at further improvement of those biological processes. Finally, current research gaps and future prospects arising from use of transgenic microalgae for heavy metal phycoremediation are reviewed.

Ranjbar, Saeed (ORCID:0000000256518605)↗

The Most Metal-poor Stars in the Magellanic Clouds Are r-process Enhanced*

The chemical abundances of a galaxy’s metal-poor stellar population can be used to investigate the earliest stages of its formation and chemical evolution. The Magellanic Clouds are the most massive of the Milky Way’s satellite galaxies and are thought to have evolved in isolation until their recent accretion by the Milky Way. Unlike the Milky Way’s less massive satellites, little is known about the Magellanic Clouds’ metal-poor stars. We have used the mid-infrared metal-poor star selection of Schlaufman & Casey and archival data to target nine LMC and four SMC giants for high-resolution Magellan/MIKE spectroscopy. These nine LMC giants with -2.4 ≲ [Fe/H] ≲ -1.5 and four SMC giants with -2.6 ≲ [Fe/H] ≲ -2.0 are the most metal-poor stars in the Magellanic Clouds yet subject to a comprehensive abundance analysis. While we find that at constant metallicity these stars are similar to Milky Way stars in their α, light, and iron-peak elemental abundances, both the LMC and SMC are enhanced relative to the Milky Way in the r-process element europium. These abundance offsets are highly significant, equivalent to 3.9σ for the LMC, 2.7σ for the SMC, and 5.0σ for the complete Magellanic Cloud sample. We propose that the r-process enhancement of the Magellanic Clouds’ metal-poor stellar population is a result of the Magellanic Clouds’ isolated chemical evolution and long history of accretion from the cosmic web combined with r-process nucleosynthesis on a timescale longer than the core-collapse supernova timescale but shorter than or comparable to the thermonuclear (i.e., Type Ia) supernova timescale.

79 ASTRONOMY AND ASTROPHYSICS↗

Signature of a Massive Rotating Metal-poor Star Imprinted in the Phoenix Stellar Stream

The Phoenix stellar stream has a low intrinsic dispersion in velocity and metallicity that implies the progenitor was probably a low-mass globular cluster. In this work we use Magellan/Magellan Inamori Kyocera Echelle (MIKE) high-dispersion spectroscopy of eight Phoenix stream red giants to confirm this scenario. In particular, we find negligible intrinsic scatter in metallicity ($σ$([FE II/H]) = ${0.04}_{-0.03}^{+0.11}$) and a large peak-to-peak range in [Na/Fe] and [Al/Fe] abundance ratios, consistent with the light element abundance patterns seen in the most metal-poor globular clusters. However, unlike any other globular cluster, we also find an intrinsic spread in [Sr II/Fe] spanning ~1 dex, while [Ba II/Fe] shows nearly no intrinsic spread ($σ$([Ba II/H]) = ${0.03}_{-0.02}^{+0.10}$). This abundance signature is best interpreted as slow-neutron-capture element production from a massive fast-rotating metal-poor star (15–20 $M$ ⊙ , $v$ ini /$v$ crit = 0.4, [Fe/H] = -3.8). The low inferred cluster mass suggests the system would have been unable to retain supernovae ejecta, implying that any massive fast-rotating metal-poor star that enriched the interstellar medium must have formed and evolved before the globular cluster formed. Furthermore, neutron-capture element production from asymptotic giant branch stars or magneto-rotational instabilities in core-collapse supernovae provide poor fits to the observations. We also report one Phoenix stream star to be a lithium-rich giant ($A$(Li) = 3.1 ± 0.1). At [Fe/H ] = -2.93; it is among the most metal-poor lithium-rich giants known.

79 ASTRONOMY AND ASTROPHYSICS↗

Magellan/IMACS Spectroscopy of Grus I: A Low Metallicity Ultra-faint Dwarf Galaxy

We present a chemodynamical study of the Grus I ultra-faint dwarf galaxy (UFD) from medium-resolution (R ~ 11,000) Magellan/IMACS spectra of its individual member stars. We identify eight confirmed members of Grus I, based on their low metallicities and coherent radial velocities, and four candidate members for which only velocities are derived. In contrast to previous work, we find that Grus I has a very low mean metallicity of $\langle$[Fe/ H]$\rangle$ = -2.62 ± 0.11 dex, making it one of the most metal-poor UFDs. Grus I has a systemic radial velocity of -143.5 ± 1.2 km s -1 and a velocity dispersion of σ rv = $2.5_{-0.8}^{+1.3}$ km s -1 , which results in a dynamical mass of M 1/2 (r h ) = $8^{+12}_{-4}$ x 10 5 M ⊙ and a mass-to-light ratio of M/L V = $440_{-250}^{+650}$ M ⊙ /L ⊙ . Under the assumption of dynamical equilibrium, our analysis confirms that Grus I is a dark-matter-dominated UFD (M/L > 80 M ⊙ /L ⊙ ). However, we do not resolve a metallicity dispersion (σ [Fe/H] < 0.44 dex). Our results indicate that Grus I is a fairly typical UFD with parameters that agree with mass–metallicity and metallicity-luminosity trends for faint galaxies. This agreement suggests that Grus I has not lost an especially significant amount of mass from tidal encounters with the Milky Way, in line with its orbital parameters. Intriguingly, Grus I has among the lowest central densities (ρ 1/2 ~ $3.5^{+5.7}_{-2.7}$ x 10 7 M ⊙ kpc -3 ) of the UFDs that are not known to be tidally disrupting. Models of the formation and evolution of UFDs will need to explain the diversity of these central densities, in addition to any diversity in the outer regions of these relic galaxies.

79 ASTRONOMY AND ASTROPHYSICS↗

Modeling Molecular Hydrogen in Low-metallicity Galaxies

We use a suite of hydrodynamics simulations of the interstellar medium (ISM) within a galactic disk, which includes radiative transfer, a nonequilibrium model of molecular hydrogen, and a realistic model for star formation and feedback, to study the structure of the ISM and H 2 abundance as a function of local ISM properties. We show that the star formation rate and structure of the ISM are sensitive to the metallicity of the gas with a progressively smoother density distribution with decreasing metallicity. In addition to the well-known trend of the H I–H 2 transition shifting to higher densities with decreasing metallicity, the maximum achieved molecular fraction in the ISM drops drastically at Z ≲ 0.2 Z ⊙ as the formation time of H 2 becomes much longer than a typical lifetime of dense regions of the ISM. We present accurate fitting formulae for both volumetric and projected ƒ H 2 measured on different scales as a function of gas metallicity, UV radiation field, and gas density. We show that when the formulae are applied to the patches in the simulated galaxy, the overall molecular gas mass is reproduced to better than a factor of ≲1.5 across the entire range of metallicities and scales. We also show that the presented fit is considerably more accurate than any of the previous ƒ H 2 models and fitting formulae in the low-metallicity regime. The fit can thus be used for modeling molecular gas in low-resolution simulations and semi-analytic models of galaxy formation in the dwarf and high-redshift regimes.

79 ASTRONOMY AND ASTROPHYSICS↗

Friction and wear of selected metals and of carbons in liquid natural gas

Friction and wear experiments were conducted with hemispherically tipped (4.76-mm radius) rider specimens in sliding contact with a rotating disk submerged in liquid natural gas (LNG). The program included metal combinations and carbon-metal combinations. These experiments revealed that the metal combinations were not lubricated by the LNG. Carbons had much lower wear in LNG than in liquid hydrogen or in liquid nitrogen. (Wear of carbon in liquid hydrogen was 100 times that in LNG.) The friction coefficients obtained in LNG (0.6 for metal-metal and 0.2 for carbon-metal) are similar to those obtained in liquid hydrogen.

Wisander, D. W.↗

Effect of adsorbed films on friction of Al2O3-metal systems

The kinetic friction of polycrystalline Al2O3 sliding on Cu, Ni, and Fe in ultrahigh vacuum was studied as a function of the surface chemistry of the metal. Clean metal surfaces were exposed to O2, Cl2, C2H4, and C2H3Cl, and the change in friction due to the adsorbed species was observed. Auger electron spectroscopy assessed the elemental composition of the metal surface. It was found that the systems exposed to Cl2 exhibited low friction, interpreted as the van der Waals force between the Al2O3 and metal chloride. The generation of metal oxide by oxygen exposures resulted in an increase in friction, interpreted as due to strong interfacial bonds established by reaction of metal oxide with Al2O3 to form the complex oxide (spinel). The only effect of C2H4 was to increase the friction of the Fe system, but C2H3Cl exposures decreases friction in both Ni and Fe systems, indicating the dominance of the chlorine over the ethylene complex on the surface

Pepper, S. V.↗