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At least 307 records · Page 17

Reactions of Atomic Thorium and Uranium Cations with SF 6 Studied by Guided Ion Beam Tandem Mass Spectrometry

The fundamental chemistry of the thorium and uranium fluorides continues to be an area of interest because of the use of thorium and uranium fluoride compounds in nuclear fuel systems. Here, we study the reaction of thorium cations with sulfur hexafluoride for the first time and revisit the reaction of uranium cations with sulfur hexafluoride. By using guided ion beam tandem mass spectrometry, we explore the reaction pathways that become accessible well above thermal energies (E ~ 0.04 eV). Overall, we find that both Th + and U + react very efficiently with SF 6 , approaching the collision limit at both thermal and elevated energies. Here, the primary products observed at low energies include Th 1–3 + , UF 1–4 + , and SF 1–4 + , all of which are formed in barrierless, exothermic processes. SF 5 + was also observed, although the pressure dependence of this channel reveals that SF 5 + forms exothermically through secondary reactions, which the energy dependences suggest result from reactions between ThF 2 + and UF 3 + with SF 6 . At higher energies, both AnF 3 + products are observed to decay to AnF + + F 2 and both SF 4 + and SF 2 + exhibit cross sections with endothermic features. For both systems, the rise in SF 4 + can be attributed to a secondary collision between AnF + with SF 6 on the basis of the pressure dependence of the SF 4 + channel at higher energies and the rise in SF 2 + appears to result from the decomposition of SF 3 + to SF 2 + + F.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural Characterization of Uranium Tetrafluoride Hydrate (UF 4 ·2.5H 2 O)

Uranium tetrafluoride is an important intermediate in the nuclear fuel cycle. Facile synthesis of its hydrate, uranium tetrafluoride hydrate (UF 4 ·2.5H 2 O), has recently been reported. The hydrate forms by contacting anhydrous UF 4 with neat H 2 O at room temperature for 24 h or by exposing anhydrous UF 4 to high relative humidity (>90%) conditions for several weeks. These pathways are of clear environmental relevance. Further understanding of the structure and optical spectra of UF 4 ·2.5H 2 O, especially of the water molecules, is therefore necessary. Herein, the structure of UF 4 ·2.5H 2 O was probed using time-of-flight neutron powder diffraction to improve understanding of the crystalline water environments in the structure. The complete structure was elucidated and compared to a previously reported partial structure for UF 4 ·2.5H 2 O and a predicted complete structure from density functional theory. The crystalline structure exhibits three distinct water environments: two of the three water sites are bound to uranium, and the third water is unbound or “free”. Furthermore, the completed structure reveals an extensive hydrogen bonding network involving water–fluorine and water–water interactions. One bound water site participates in hydrogen bonding with nearby fluoride ligands (O–H···F–U), and the second bound water site participates in hydrogen bonding with the unbound water (O–H···O) and a nearby fluoride ligand (O–H···F–U); the unbound water participates in hydrogen bonding with bound water (O–H···O–U). Low-temperature experiments and thermal analysis indicate UF 4 ·2.5H 2 O is thermally stable from 10 to 358 K, undergoes dehydration at higher temperatures, and is nearly dehydrated at 473 K. Structural measurements provide foundational understanding and will inform future investigations of the thermal and environmental stability of UF 4 ·2.5H 2 O.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of Disorder and Defects on Bond Energies in Highly Fluorinated Graphene

Fluorinated graphite materials are of interest for an assortment of applications and can be synthesized under a variety of synthetic conditions from many different types of carbon. Due to such variations, structural disorders in the form of defects and polymorphism are often present. Here, we investigate the impact of local structural variations on the C–F bond dissociation energies (BDEs) in carbon-based fluoride materials using density functional theory (DFT) computational methods. Employing fluorographene (FG) cluster models, we determine the impact of different C–F bonding configurations in the core of each platelet on the equilibrium BDEs for each C–F bond. The introduction of structural disorder decreases the first C–F BDE by approximately 1 eV compared to the canonical arrangement of axial C–F bonds ordered as in a network of cyclohexane “chairs”. Variability of calculated BDEs among the different polymorphs decreases upon subsequent F removal. Common structural tendencies of the adiabatic defluorination pathways for each polymorph are identified. In conclusion, our analysis suggests that at F/C ratios near 1.0, disorder in the local structure can play a significant role in the energetics of the initial carbon fluoride defluorination and that the influence of this configurational disorder diminishes with decreasing F/C ratios.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Insights into Spontaneous Solid Electrolyte Interphase Formation at Magnesium Metal Anode Surface from Ab Initio Molecular Dynamics Simulations

Spontaneous chemical reactivity at multivalent (Mg, Ca, Zn, Al) electrode surfaces is critical to solid electrolyte interphase (SEI) formation, and hence, directly affects the longevity of batteries. Here, we report an investigation of the reactivity of 0.5 M Mg(TFSI)2 in 1,2-dimethoxyethane (DME) solvent at a Mg(0001) surface using ab initio molecular dynamics (AIMD) simulations and detailed Bader charge analysis. Based on the simulations, the initial degradation reactions of the electrolyte strongly depend on the structure of the Mg(TFSI)2 species near the anode surface. At the surface, the dissociation of Mg(TFSI)2 species occurs via cleavage of the N-S bond for the solvent separated ion pair (SSIP) and via cleavage of the C-S bond for the contact ion pair (CIP) configuration. In the case of the CIP, both TFSI anions undergo spontaneous bond dissociation reactions to form atomic O, C, S, F, and N species adsorbed on the surface of the Mg anode. These products indicate that the initial SEI layer formed on the surface of the pristine Mg anode consists of a complex mixture of multiple components such as oxides, carbides, sulfides, fluorides, and nitrides. We believe that the atomic level insights gained from these simulations will lay the groundwork for the rational design of tailored and functional interphases that are critical for the success of multivalent battery technology.

Agarwal, Garvit↗

Surprising Relationship between Silicon Anode Calendar Aging and Electrolyte Components in a Localized High-Concentration Electrolyte System

Although localized high-concentration electrolytes (LHCEs) have been shown to improve the calendar lifetime of silicon anodes, the roles of the electrolyte constituents in calendar aging are not well understood. Here, in this work, we utilize a voltage hold protocol and an LHCE with varying molar ratios of lithium bis(fluorosulfonyl)imide (LiFSI), tetramethylene sulfone (TMS), and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) to probe the component roles during aging. Interestingly, the estimated calendar lifetime and irreversible lithium losses from the V-hold experiments are independent of the electrolyte formulations. Contrarily, the solid electrolyte interphase (SEI) composition depends on the electrolyte formulation. X-ray photoelectron spectroscopy shows that TMS-coordinated species decompose to form insoluble alkanes and lithium hydroxide (LiOH), while lithium fluoride (LiF) originates from the anion-coordination complex. The SEI composition does not appear to play a significant role in the silicon anode passivity, as measured by parasitic current, suggesting that the SEI-electrolyte interactions dictate the calendar aging mechanisms.

Si anode↗

2D in-Plane Ordered MXene Nanosheets Derived from (Mo 2/3 Er 1/3 ) 2 AlC Rare-Earth i-MAX for Energy Storage Applications

MXenes have become one of the most versatile families of two-dimensional (2D) materials due to their high conductivity, hydrophilicity, and remarkable electrochemical performance. This has stimulated intense efforts to design and synthesize MXenes, including structurally unique in-plane ordered 2D MXenes called i-MXenes. Here, we have synthesized the quaternary rare earth (RE)-based i-MAX phase (Mo 2/3 Er 1/3 ) 2 AlC using an arc melting method, and the corresponding 2D i-MXene was then obtained through a LiF/HCl soft etching process. Literature studies have shown that Al and the RE element are etched out during the etching process, leading to the formation of pure vacancy-ordered Mo1.33C 2D i-MXene. However, our investigation reveals that upon exposure to a fluorine solution, the i-MAX phase forms RE fluoride impurities, which are challenging to remove through HCl−DI water washing and persist in the final product, resulting in impure Mo 1.33 C@Er i-MXene. These results were confirmed by various characterizations such as X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, and scanning transmission electron microscopy. Although the Mo 1.33 C@Er electrode showed a 24-fold increase in specific capacitance compared to its parent i-MAX phase, it still exhibited a high charge-transfer resistance arising from the insulating nature of RE fluoride byproducts, which adversely influence the overall capacitance behavior of the synthesized 2D Mo 1.33 C@Er i-MXenes. This study contributes to identifying pathways for the preparation of pure 2D i-MXenes from RE-based i-MAX phases and developing improved synthesis methods. With additional process optimization, the 2D i-MXene holds a strong potential for electrochemical energy storage applications. Additionally, the electronic structures of Mo 1.33 C were theoretically studied using first-principles density functional theory calculations, which revealed that pristine Mo 1.33 C is metallic, and this metallic nature is preserved even with −O, −F, and mixed functionalization.

chemical structure↗

Topological Considerations in Electrolyte Additives for Passivating Silicon Anodes with Hybrid Solid–Electrolyte Interphases

Unlike most anodes used in high energy density batteries, lithiated Si does not form long-lasting passivating solid-electrolyte interphases (SEI) during formation or on charge due to SEI delamination, reconstruction, or dissolution. As a result, electrolyte degradation is continuous and results in a permanent loss of the Li inventory, shortening the useful life of the battery. Here, in this study, we show that perfluoroether electrolyte additives featuring either sulfonyl fluorides or trifluorovinyl ethers, when introduced in prescribed amounts to locally superconcentrated electrolytes, exhibit preferential reactivity at Si during formation due to their higher reduction potential than salts and solvents, creating a hybrid SEI that is simultaneously enriched with LiF and organics tethered to the reactive functionality. While both reactive motifs are effective in creating a hybrid SEI, perfluoroether additives bearing sulfonyl fluorides show more substantial integration. More important, however, is the combined influence of additive topology on anchoring efficacy and tether flexibility between anchoring sites on SEI resiliency. Top-performing Si|LFP cells featuring ditopic additive-enriched SEI improve capacity retention by as much as 45% over 100 cycles when compared to additive-free cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A fluorinated cation introduces new interphasial chemistries to enable high-voltage lithium metal batteries

Abstract Fluorides have been identified as a key ingredient in interphases supporting aggressive battery chemistries. While the precursor for these fluorides must be pre-stored in electrolyte components and only delivered at extreme potentials, the chemical source of fluorine so far has been confined to either negatively-charge anions or fluorinated molecules, whose presence in the inner-Helmholtz layer of electrodes, and consequently their contribution to the interphasial chemistry, is restricted. To pre-store fluorine source on positive-charged species, here we show a cation that carries fluorine in its structure is synthesized and its contribution to interphasial chemistry is explored for the very first time. An electrolyte carrying fluorine in both cation and anion brings unprecedented interphasial chemistries that translate into superior battery performance of a lithium-metal battery, including high Coulombic efficiency of up to 99.98%, and Li 0 -dendrite prevention for 900 hours. The significance of this fluorinated cation undoubtedly extends to other advanced battery systems beyond lithium, all of which universally require kinetic protection of highly fluorinated interphases.

25 ENERGY STORAGE↗

Structural characterization of tin in toothpaste by dynamic nuclear polarization enhanced 119 Sn solid-state NMR spectroscopy

Stannous fluoride (SnF 2 ) is an effective fluoride source and antimicrobial agent that is widely used in commercial toothpaste formulations. The antimicrobial activity of SnF 2 is partly attributed to the presence of Sn(II) ions. However, it is challenging to directly determine the Sn speciation and oxidation state within commercially available toothpaste products due to the low weight loading of SnF 2 (0.454 wt% SnF 2 , 0.34 wt% Sn) and the amorphous, semi-solid nature of the toothpaste. Here, we show that dynamic nuclear polarization (DNP) enables 119 Sn solid-state NMR experiments that can probe the Sn speciation within commercially available toothpaste. Solid-state NMR experiments on SnF 2 and SnF 4 show that 19 F isotropic chemical shift and 119 Sn chemical shift anisotropy (CSA) are highly sensitive to the Sn oxidation state. DNP-enhanced 119 Sn magic-angle turning (MAT) 2D NMR spectra of toothpastes resolve Sn(II) and Sn(IV) by their 119 Sn chemical shift tensor parameters. Fits of DNP-enhanced 1D 1 H → 119 Sn solid-state NMR spectra allow the populations of Sn(II) and Sn(IV) within the toothpastes to be estimated. This analysis reveals that three of the four commercially available toothpastes contained at least 80% Sn(II), whereas one of the toothpaste contained a significantly higher amount of Sn(IV).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rare earth metals production using alternative feedstock that eliminates HF

This work reports the successful production of rare earth (RE) metal using Na-RE-F. Presently, RE metals are primarily produced using RE-fluoride due to its higher air and moisture stability compared to RE-chloride. However, its preparation requires the use of corrosive and hazardous chemicals, such as hydrofluoric acid (HF) or ammonium bifluoride (NH 4 HF 2 ). The present study demonstrates that Na-RE-F is an alternative salt to the typically used RE-fluoride. The Na-RE-F for this work is produced via a scalable hydrometallurgical approach using three different RE salts as feedstock, including acetate, nitrate, and chloride. HF is neither used nor generated during the salt preparation process. Furthermore, the Na-RE-F powder dries in air (without dry HF), and only water evolves during the drying process. Analyses of the Na-RE-F show that NaF liberates as a flux during the heating process, which lowers the salt reduction temperature to <900 °C, thus minimizing or eliminating the need for additional flux. Calciothermic reduction of the Na-RE-F salt is successfully employed to obtain RE metal. This work represents a safer, greener, and more widely deployable approach for producing the RE metals needed for permanent magnets which support the transition to a cleaner society through the decarbonization of the transportation industry.

36 MATERIALS SCIENCE↗

Lithium metal-mediated electrochemical reduction of per- and poly-fluoroalkyl substances

Per- and poly-fluoroalkyl substances (PFAS) have substantial environmental and health hazards. Unfortunately, current degradation routes require high temperatures or corrosive conditions and/or lead to incomplete defluorination and the generation of shorter alkyl chains. Inspired by the lithium-metal battery literature, here we develop an electrochemical degradation process that leverages reactive metals and highly reducing environments. Here, we show that electrodeposited lithium metal can enable 95% degradation and 94% defluorination of perfluorooctanoic acid to LiF without forming any shorter C 2 –C 6 PFAS as end products. Using computational simulations, we find that electron transfer from lithium to perfluorooctanoic acid leads to rapid C–F bond cleavage, fluoride formation and carbon chain fragmentation. We expand the scope to other PFAS compounds and demonstrate substantial degrees of degradation on over 22 different PFAS, plus complete mineralization to inorganic fluorides. Finally, we use the mineralized F − as a fluorine source for the synthesis of fluorinated non-PFAS compounds to complete a circular fluorine loop from waste to valuable product.

Sarkar, Bidushi [Univ. of Chicago, IL (United Stat↗

Barrier reinforcement for enhanced perovskite solar cell stability under reverse bias

Stability of perovskite solar cells (PSCs) under light, heat, humidity and their combinations have been notably improved recently. However, PSCs have poor reverse-bias stability that limits their real-world application. Here we report a systematic study on the degradation mechanisms of p-i-n structure PSCs under reverse bias. The oxidation of iodide by injected holes at the cathode side initialize the reverse-bias-induced degradation, then the generated neutral iodine oxidizes metal electrode such as copper, followed by drift of Cu+ into perovskites and its reduction by injected electrons, resulting in localized metallic filaments and thus device breakdown. A reinforced barrier with combined lithium fluoride, tin oxide and indium tin oxide at the cathode side reduces device dark current and avoids the corrosion of Cu0. It dramatically increases breakdown voltage to above -20 V and improved the T90 lifetime of PSCs to ~1,000 h under -1.6 V. The modified minimodule also maintained over 90% of its initial performance after 720 h of shadow tests.

degradation mechanisms↗

Lasing Below 170 nm Using an Oscillator FEL

The short wavelength operation of free-electron laser (FEL) oscillators is limited by the availability of high-reflectivity, thermally stable, and radiation-resistant FEL mirrors in the VUV wavelength. We report our recent work to extend the shortest lasing wavelength of the oscillator FEL to 168.6 nm using a storage ring FEL. This progress has been made possible by developing a new FEL configuration with substantially reduced undulator harmonic radiation on the FEL mirror, a thermally stable FEL optical cavity, and a new type of high-reflectivity fluoride-based multilayer coating with a protective capping layer. Using these fluoride-based mirrors, we have demonstrated storage ring FEL lasing from 168.6 to 179.7 nm with excellent beam stability. Employing this VUV FEL in Compton scattering, we have produced the first 120 MeV gamma rays at the High Intensity Gamma-ray Source (HIGS). Furthermore, operating the HIGS in this new high-energy region will create many new opportunities for photonuclear physics research, in particular, the low-energy QCD research.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Constant-potential molecular dynamics simulations of molten salt double layers for FLiBe and FLiNaK

We report the results of constant-potential molecular dynamics simulations of the double layer interface between molten 2LiF–BeF 2 (FLiBe) and 23LiF–6NaF–21KF (FLiNaK) fluoride mixtures and idealized solid electrodes. Employing methods similar to those used in studies of chloride double layers, we compute the structure and differential capacitance of molten fluoride electric double layers as a function of applied voltage. The role of molten salt structure is probed through comparisons between FLiBe and FLiNaK, which serve as models for strong and weak associate-forming salts, respectively. In FLiBe, screening involves changes in Be–F–Be angles and alignment of the oligomers parallel to the electrode, while in FLiNaK, the electric field is screened mainly by rearrangement of individual ions, predominantly the polarizable potassium cation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The importance of laser wavelength for driving inertial confinement fusion targets. II. Target design

We describe details of radiation-hydrodynamics simulations of directly driven targets for inertial confinement fusion using laser drivers with different laser wavelengths. Of particular interest here are comparisons of frequency-tripled glass (laser wavelength 351 nm) lasers with the argon fluoride (193 nm) and krypton fluoride (248 nm) excimer lasers and the effects that these laser wavelengths have on the target designs. We explore the effect these drivers have on the compromise involved between lowering laser plasma instabilities (LPIs) or hydrodynamic instabilities while providing high gains and seek to quantify this trade-off. Short-wavelength drivers have significant advantages, primarily in using less power and energy to drive targets. Additionally, they expand the allowed operating regime that is constrained by LPI avoidance and the production of higher pressures needed for more hydrodynamically stable targets. Potential disadvantages to shorter drive wavelengths, such as increased imprint, are examined and found to be unimportant.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Evaluation of Corrosion Behavior of Various Fe- and Ni-Based Alloys in Molten Li 2 BeF 4 (FLiBe)

Reliable performance of structural alloys is essential for the successful implementation of Generation-IV fluoride salt–cooled high-temperature reactors (FHRs). Most FHR designs are considering molten salt (2LiF-BeF 2 ), or FLiBe, as a primary coolant or fuel carrier. The main corrosion mechanism for alloys exposed to molten fluoride salts is the selective dealloying of active alloying elements. Alloy composition has a significant effect on their high-temperature mechanical properties, but also affects their corrosion behavior. Although Hastelloy-N and its variants show good corrosion resistance compared to higher Cr-containing Ni- or Fe-based alloys, the mechanical properties of these alloys degrade quickly at temperatures above ~600°C. Twelve Ni-based or Fe-based alloys were selected due to their high temperature stability or their low Cr alloy composition and tested for their corrosion behavior in FLiBe. The results show that the mode and the extent of alloy degradation by selective dissolution mechanism corelates well with the overall alloy composition, and not just the concentration of active elements. It was found that there was good correlation between weight loss of the tested alloys and the ratio of major active elements (Cr, Mn) to that of the more noble alloying elements (Ni, Mo).

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Initial Neutronics Investigation of a Chlorine Salt-Based Breeder Blanket

Tritium breeding blankets within D-T-fueled fusion reactors contain lithium compounds and typically require neutron multiplier materials to achieve a tritium breeding ratio (TBR) consistent with self-sustaining operation. Liquid breeder blankets have some advantages over solid blankets, and previous blanket studies have investigated liquid metal as well as liquid salt–based blankets. Liquid salts have reduced magnetohydrodynamic effects as compared to liquid metals, but typically have a lower TBR. Recently, advanced fission reactor concepts have considered chloride-based salts in their design, and there is a significant amount of research work occurring to study these salts. Chloride salts have previously been considered for fusion reactors, but studies have typically found lower breeding ratios than for fluoride salts, such as 2(LiF)-BeF 2 (flibe) so they have not been further developed. In this work, we use a one-dimensional cylindrical radiation transport model of a conceptual tokamak fusion reactor to investigate the neutronics feasibility of using a chloride salt–based blanket that uses chlorine enriched in 37 Cl, which has both a low capture cross section and a substantial (n,2n) cross section. It is found that chloride salts (LiCl mixed with BeCl 2 and/or PbCl 2 ) can potentially achieve a ~3% to 5% higher TBR than fluoride molten salts, notably flibe, in the absence of a solid multiplier. Including a solid multiplier, however, does narrow this advantage, with TBRs estimated within ~1% of flibe with a 2-cm Be multiplier. Chloride salts can also reach lower melting points than flibe, potentially improving the scope for the use of reduced activation ferritic-martensitic steel as a structural material. There is substantial uncertainty in the calculations driven by limited thermochemical data for the Cl salts, plus cross-section uncertainties. The production of 36 Cl through 35 Cl(n,g) and 37 Cl(n,2n) has the potential to challenge the waste disposal rating of the blanket. Calculations indicate that, while this is not an immediate showstopper, this case depends upon the exact waste disposal rating criteria used for 36 Cl. Further work could reduce these uncertainties with improved thermochemical data, higher-fidelity modeling for downselected salts, and more refined waste disposal calculations and regulatory guidance. Lastly, it must be recognized that, as for all molten salts, corrosion and chemistry can present appreciable technical challenges that require further assessment in developing a practical blanket concept, and also that the enrichment of chlorine presents an additional technical and supply chain challenge.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Computational Fluid Dynamics Analysis of the Molten Salt Tritium Transport Experiment Test Section

Tritium, a radionuclide produced through neutron capture by lithium and other elements (beryllium and fluoride) in molten salts, presents unique challenges to radionuclide release. This is true for both fusion energy breeder blankets and molten salt fission reactors. The fundamental understanding of tritium transport is crucial to the safe design and operation of these reactors. The Molten Salt Tritium Transport Experiment (MSTTE), currently under construction at Idaho National Laboratory, aims to investigate tritium transport phenomena using a forced-convection fluoride salt loop. This loop is designed to study various transport mechanisms, such as permeation through metals and gas-liquid interactions, and is intended to support future research on tritium extraction units. A critical aspect of the MSTTE loop design is ensuring a fully developed velocity profile before the fluid reaches the permeation test section where measurements are made. This study employs computational fluid dynamics to model the salt flow behavior within the MSTTE permeation test section. A realizable k-ε turbulent model with enhanced wall treatment is used to simulate the single-phase, vertical upward flow of molten salt FLiNaK under isothermal conditions. The simulation results indicated flow distortion and underdeveloped profiles at all planned flow rates within the test section due to the 85-deg sharp bend. To address this issue, a reduced diameter with a reducer and expander and a flow conditioner are investigated to achieve fully developed flow. The analysis showed that the flow conditioner successfully corrected the flow profile, achieving fully developed behavior at a flow rate of 50 liters per minute (LPM). In conclusion, this research enhances our understanding of flow dynamics in molten salt systems and contributes to optimizing tritium transport control technologies.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗