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At least 523 records · Page 29

Coherent approach to two-dimensional heterolayered oxychalcogenides using molten hydroxides.

Heterolayered structures consist of two or more different types of layer and can exhibit exceptional physical properties. Rational routes to synthesize new members of such compounds are required because most of these compounds have been discovered unintentionally. So far there is no generic method to vertically stack chemically different layers to form two-dimensional compounds owing to a lack of understanding of the synthesis of these materials. Here we report the use of molten hydroxides as unconventional solutions for the rapid stacking of oxide and chalcogenide layers with precise composition control. In addition, the crystal growth of heterolayered phases can be achieved by the reaction of different components at their diffusion front in molten hydroxides. This approach creates conditions in which the building blocks for each heterolayer can coexist, enabling heterolayered structures and bypassing the challenges of traditional solid-state chemistry methods where short reactant diffusion lengths predominate. This crystal growth methodology for heterolayers is also applicable to systems that do not form congruent melts at high temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanochemistry-driven phase transformation of crystalline covalent triazine frameworks assisted by alkaline molten salts

We report covalent triazine frameworks (CTFs) have shown wide applications in the fields of separation, catalysis, energy storage, and beyond. However, it is a long-term challenging subject to fabricate high-quality CTF materials via facile procedures. Herein, a mechanochemistry-driven procedure was developed to achieve phase transformation of crystalline CTFs assisted by alkaline molten salts. The transformation of CTF-1 from staggered AB to eclipsed AA stacking mode was achieved by short time (30 min) mechanochemical treatment in the presence of molten salts composed of LiOH/KOH, generating high-quality CTF-1 material with high crystallinity, high surface area (625 m 2 g -1 ), and permanent/ordered porosity without carbonization under ambient conditions. This facile procedure could be extended to provide nanoporous three-dimensional CTF materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Computing chemical potentials with machine-learning-accelerated simulations to accurately predict thermodynamic properties of molten salts

The successful design and deployment of next-generation nuclear technologies heavily rely on thermodynamic data for relevant molten salt systems. However, the lack of accurate force fields and efficient methods has limited the quality of thermodynamic predictions from atomistic simulations. Here we propose an efficient free energy framework for computing chemical potentials, which is the central free energy quantity behind many thermodynamic properties. We accelerate our simulations without sacrificing accuracy by using machine learning interatomic potentials trained on density functional theory (DFT) data. Using lithium chloride as our model system, we compute chemical potentials with DFT-accuracy for solid and liquid phases by transmuting ions into noninteracting particles. Notably, in the liquid phase, we demonstrate consistency whether we transmute one ion pair or the entire system into ideal gas particles. By locating the temperature where the chemical potential of solid and liquid phases cross, we predict a melting point of 880 ± 18 K for lithium chloride, which is remarkably close to the experimental value of 883 K. With this successful demonstration, we lay the foundation for high-throughput thermodynamic predictions of many properties that can be derived from the chemical potentials of the minority and majority components in molten salts.

Gibson, Luke D. [Oak Ridge National Laboratory (OR↗

Elemental analysis of air-sensitive frozen molten salt samples using an inert transfer chamber for LIBS/LA-ICP-TOF-MS analysis

A novel inert sample transfer system was developed and employed to enable, for the first time, the analysis of air-sensitive salt samples in a two-volume ablation cell using simultaneous laser-induced breakdown spectroscopy (LIBS) and laser ablation (LA)-inductively coupled plasma (ICP)-time-of-flight (TOF)-mass spectrometry (MS) analysis. Molten salts are of growing interest as a medium for advanced nuclear reactors and nuclear fuel reprocessing technologies continue to be developed around their use. However, compositional analysis of molten salt samples can be challenging because of their air-sensitive nature and varying solubilities leading to inaccurate measurements when digested. LA-based analysis provides an alternate method to digestion and can provide rapid elemental information with little sample preparation. In this study, LIBS and LA-ICP-TOF-MS were used to analyze the Ce content in frozen salt samples taken from a series of electrochemical experiments. Calibrations were built for each technique, and the resulting limits of detection for Ce were estimated to be 107 and 58 µg g −1 for LIBS and LA-ICP-TOF-MS, respectively. Test samples from the electrochemical experiments were analyzed using these calibrations. The results matched bulk digestion-based ICP-optical emission spectroscopy values, and daily trends in Ce concentration changes were identified. Additionally, the LIBS and LA-ICP-TOF-MS analysis was demonstrated for identifying microgram per gram levels of components and detecting trace contaminants. The impurities detected by LIBS included Al, Mg, Ca, and Na. The impurities detected by LA-ICP-TOF-MS included W, Ag, Al, Fe, Ni, Mo, Nd, Sm, Th, and U.

Andrews, Hunter B. [Oak Ridge National Laboratory ↗

Molten Salt Synthesis of Increased (100)-Facet and Polycrystalline Nickel Oxide Nanoparticles for the Oxygen Evolution Reaction: Impact of Facet and Crystallinity on Electrocatalysis

Nickel oxide nanocubes with increased (100) surface facet presence (NiO(100)) were synthesized through a molten salt synthesis procedure to probe their oxygen evolution reaction (OER) activity in order to investigate the relationship between the surface facet and OER performance. While altering the synthesis parameters to decrease NiO(100) particle sizes and agglomeration, a polycrystalline NiO nanoparticle system formed from using Li2O as a Lux-Flood base (labelled Li2O-MSS NiO, where MSS stands for molten salt synthesis). This novel synthesis was further elaborated and the obtained materials were also tested for OER activity. After thorough structural characterization to determine crystallinity, lattice spacings, and elemental distribution, their OER activity was compared versus high surface area NiO(111) nanosheets in a three-electrode rotating disk electrode (RDE) system. The activity trend of (111) > Li2O-MSS > (100) was observed. This decrease in activity of the nanocube and polycrystalline samples was explained by differences between theoretical and experimental conditions, differences in ink rheology and resulting catalyst layer properties, and significant agglomeration seen in the imaging of the sample. Methods for improving the OER activity of these samples are discussed in the conclusion of this study.

08 HYDROGEN↗

Comparison of fixed charge and polarizable models for predicting the structural, thermodynamic, and transport properties of molten alkali chlorides

Results from extensive molecular dynamics simulations of molten LiCl, NaCl, KCl, and RbCl over a wide range of temperatures are reported. Comparison is made between the “Polarizable Ion Model” (PIM) and the non-polarizable “Rigid Ion Model” (RIM). Densities, self-diffusivities, shear viscosities, ionic conductivities, and thermal conductivities are computed and compared with experimental data. In addition, radial distribution functions are computed from ab initio molecular dynamics simulations and compared with the two sets of classical simulations as well as experimental data. Here, the two classical models perform reasonably well at capturing structural and dynamic properties of the four molten alkali chlorides, both qualitatively and often quantitatively. With the singular exception of liquid density, for which the PIM is more accurate than the RIM, there are few clear trends to suggest that one model is more accurate than the other for the four alkali halide systems studied here.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Operational Modes of a 2.0 MWth Chloride Molten-Salt Pilot-Scale System

The limit of traditional solar-salt thermal stability is around 600 °C with ambient air as the cover gas. Nitrate molten salt concentrating solar power (CSP) systems are currently deployed globally and are considered to be state-of the art heat transfer fluids (HTFs) for present day high-temperature operation. However, decomposition challenges occur with these salts for operation beyond 600 C. Although slightly higher limits may be possible with solar salt, to fully realize SunShot efficiency goals of $15/kWhth HTFs and an LCOE of 6¢/kWh, molten-salt technologies working at higher temperatures (e.g., 650 °C to 750 °C) will require an alternative salt chemistry composition, such as chlorides. In this investigation a 2.0MWth Pilot-scale CSP plant design is developed to assess thermodynamic performance potential for operation up to 720 C. Here, an Engineering Equation Solver (EES) model is developed with respect to 14 state-points from the base of a solar tower at the Sandia National Laboratories, National Solar Thermal Test Facility (NSTTF), to solar receiver mounted 120 ft. above the ground. The system design considers a ternary chloride ternary chloride (20%NaCl/40%MgCl/40%KCl by mol%) salt as the HTF, with 6 hrs. of storage and a 1 MWth primary salt to sCO2 heat exchanger. Preliminary system modelling results indicate a minimum non-dimensional Cv of 60 required for both cold and hot-side throttle recirculation valves for the operational pump operating between speeds of 1800 and 2400 RPM. Further receiver comparison study results suggest that the ternary salt requires an average 15.2% higher receiver flux with a slightly lower calculated receiver efficiency when compared to a binary carnelite salt to achieve a 2.0 MWth desired input power design.

associated liquids↗

A high temperature cell for investigating interfacial structure on the molecular scale in molten salt/alloy systems

In this work, we describe the design and development of an in situ neutron reflectometry cell for high temperature investigations of structural changes occurring at the interface between inorganic salts, in their molten state up to 800 °C, and corrosion resistant alloys or other surfaces. In the cell, a molten salt is confined by an annular ring of single crystal sapphire constrained between the sample substrate and a sapphire plate using two gold O-rings, enclosing a liquid salt volume of 20 ml, along with a dynamic cell volume to accommodate expansion of the liquid with heating. Further, as a test case for the cell, we report on an in situ neutron reflectometry measurement of the interface between a eutectic salt mixture of MgCl 2 –KCl (32:68 molar ratio) and a single crystal sapphire substrate at 450 °C, resulting in the formation of a 60 Å layer having a scattering length density of 1.72 × 10 –6 Å –2 . While the origin of this layer is uncertain, it is likely to have resulted from the salt reacting with an existing impurity layer on the sapphire substrate.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Development and testing of a solar flux heating freeze recovery system for molten salt parabolic troughs

A major obstacle preventing commercialization of molten salt parabolic trough plants is freeze protection and recovery of the solar field. One of the most common nitrate salt compositions under consideration allows for solar field outlet temperatures up to 565°C and begins solidifying above 240°C. Using molten salt directly in the solar field can significantly reduce thermal energy storage costs and the higher temperature compared to oil heat transfer fluids can power a more efficient power cycle, but the very high freezing point is cause for concern. This work builds on a previous modeling effort investigating different methods for melting Solar Salt frozen in the solar field, which suggested the viability of a novel solar heating method to lower costs of the freeze protection system. In this work higher fidelity models are developed to better investigate the melting process with a more detailed 3D geometry which includes the insulated bellows. The thermal-fluid model of the melting process is updated to include temperature dependent density and data for solid phase properties. In addition, a finite element model is developed to resolve thermal stresses at the point with highest thermal gradients. Results with the new model confirm the viability of using controllable solar flux heating to thaw salt frozen in the solar field without damaging the receiver; however, the presence of non-illuminated sections significantly slows down the melting process. Solar heating simulations with pauses off-sun of 120 and 60 s require 18.5 and 11.9 h to melt salt from a night-time temperature of 10°C with 1000 W m2 DNI, which results in maximum thermal stresses of 48.2 and 53.5 MPa, respectively. Adding 150 W m−1 to the solar heating simulation with a 60 s pause off-sun decreases both the melt time and thermal stresses due to the more uniform heating, suggesting a combined heating method may be the best option.

14 SOLAR ENERGY↗

Density of molten oxides measured in an aero-acoustic levitator

Knowing the thermophysical properties of high-temperature melts can aid the design of melt processes and validate atomic structural models, such as those used in studying glass formation. Property measurements on such melts are challenging, however, due to container-related contamination and heterogeneous nucleation. Containerless processing techniques that employ levitation can be used to avoid these obstacles. In that context, we demonstrate here the application of silhouette imaging to measure the density of molten oxides in an aero-acoustic levitation instrument (AAL). The AAL combines gas jet levitation with actively controlled acoustic positioning to enable full optical access to samples ca. 2–4 mm in diameter, which are laser beam heated and melted. The cross sections of molten drops are imaged using a monochromatic light source and narrowband-filtered camera. Melt volume is calculated from the cross sections and used to find density at several temperatures ranging 1530–1920 K, including up to 350 K of supercooling. We report densities for CaAl 2 O 4 , Ca 12 Al 14 O 33 , CaSiO 3 , their Fe 2 O 3 -bearing analogs, and 83TiO 2 -17RE 2 O 3 (RE = La or Nd). These provide important benchmarks of the capabilities, measurement uncertainties, and future outlook for this technique.

36 MATERIALS SCIENCE↗

Structure of molten ytterbium aluminum garnet

Rare earth aluminum garnets are important materials in optical, dielectric, and thermal barrier applications. To advance the understanding of their melt processing and glass forming ability, we report the atomic structure of molten Yb 3 Al 5 O 12 over 1770–2630 K, which spans the equilibrium and supercooled liquid regimes. The melt density at T m = 2283 K is 5.50 g cm –3 , measured via silhouette imaging of electrostatically levitated drops over 1010–2420 K. Four separate structure measurements were made with aerodynamically levitated melts using x-ray and neutron diffraction with isotope substitution of Yb ( 172 Yb, 174 Yb, or nat Yb). Empirical potential structure refinement models were developed, which are in excellent agreement with the experiments. Coordination environments for Al–O are predominantly 4- and 5-coordinate, with a mean coordination of n AlO = 4.43(8), while Yb–O environments mostly range from 5- to 8-coordinate, with n YbO = 6.26(8). The cation–oxygen polyhedra are connected primarily by corner-sharing, with edge-sharing constituting up to ~1/3 of the connectivity among polyhedra with Yb or higher-coordinated Al–O. Structurally, the –Al–O– network in molten Yb 3 Al 5 O 12 appears conducive to glass formation: n OAl = 1.85(3), there are 1.86 AlO x –AlO x connections per Al atom (e.g., a mixture of Q 3 and Q 4 units), and the modal ring size is six cations. These characterize a network that is somewhat less constrained compared to SiO 2 glass, yet Yb 3 Al 5 O 12 cannot be quenched into crystal-free glass. Here, aluminum garnet compositions with larger rare earth cations do form glass, so these characterizations help reveal the structural characteristics corresponding to the limit of glass forming ability in rare earth aluminates.

36 MATERIALS SCIENCE↗

Composition-transferable machine learning potential for LiCl-KCl molten salts validated by high-energy x-ray diffraction

Unraveling the liquid structure of multicomponent molten salts is challenging due to the difficulty in conducting and interpreting high-temperature diffraction experiments. Here, motivated by this challenge, we developed composition-transferable Gaussian approximation potential (GAP) for molten LiCl-KCl. A DFT-SCAN accurate GAP is active-learned from only ~1100 training configurations drawn from 10 unique mixture compositions enriched with metadynamics. The GAP-computed structures show strong agreement across high-energy x-ray diffraction experiments, including for a eutectic not explicitly included in model training, thereby opening the possibility of composition discovery.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Corrosion of AISI 310 and 316 in Molten Hydroxide Under Steam Electrolysis Conditions

Steam electrolyzers, utilizing molten hydroxide electrolyte, offers potential for improvement in electrochemical efficiency, cost reduction, use of conventional materials of construction and process scale up for large scale hydrogen production. Stainless steels, used for the fabrication of cell components (current collector, gas separator, wet seals, and manifolds) experience accelerated corrosion in the presence of molten hydroxide electrolyte in both oxidizing (anodic) and reducing (cathodic) atmospheres. In this study, the corrosion behavior of AISI 310 and 316 in hydroxide melt has been studied at 600°C for 50 h. Melt immersion tests revealed formation of the porous lithium iron oxide at the melt-oxide interface for both AISI 310 and 316. Inductively coupled plasma optical emission spectrometry (ICP-OES) analysis showed the presence of Cr in the electrolyte melt obtained from samples exposed to oxidizing atmosphere. Thermochemical analysis was performed to validate the experimental results.

corrosion↗

The Electrochemical Behavior of Tellurium Tetrachloride in LiCl-KCl Eutectic Molten Salt at 450 ºC

Cyclic voltammetry CV), square wave voltammetry (SWV), and electrochemical impedance spectroscopy measurements were carried out in 1 and 5 wt% TeCl 4 containing LiCl-KCl eutectic molten salt at 450 °C using tungsten and glassy carbon as working electrodes. Reduction of Te(IV) to Te(0) occurred in three steps at potentials more negative than -0.4 V Ag/AgCl . The Te(0) was further reduced to Te 2- at more negative potentials. Formation of Te 2- was observed at potentials more negative than -2.2 V Ag/AgCl . Diffusivities of Te 4+ , Te 2+ , and Te 2- and their formal potentials were estimated from the CV data. The diffusion coefficients of Te 4+ , Te 2+ and Te 2- were 0.9 × 10 -5 , 3.8 × 10 -5 , and 1.5 × 10 -5 cm 2 s -1 , respectively in the 1 wt% TeCl 4 containing LiCl-KCl molten salt. The diffusivity of Te species generally decreased with increase in the concentration of TeCl 4 .

Electrochemistry↗

Communication—Mg 2+/0 as a Reliable Reference Electrode for Molten Chloride Salts

In this report, we describe the use of the Mg 2+/0 couple as a reference in molten MgCl 2 -NaCl. We demonstrate that this redox couple provides a robust and reliable reference potential over a range of melt temperatures (500 °C–675 °C). Finally, we demonstrate the construction of a simple molten magnesium reference electrode, for operation at temperatures greater than the melting point of magnesium (650 °C).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Long-Term Stability of Mullite and Magnesia-encased Ag|Ag + Reference Electrodes in Molten MgCl 2 -KCl-NaCl

In this study, the stability of Ag|Ag + molten chloride reference electrodes was studied using mullite and magnesia tubes as reference electrode membrane materials in molten MgCl 2 -KCl-NaCl for continuous immersion up to 31 d. Two electrochemical methods were used to characterize the long-term performance of the reference electrodes at 500 °C in an inert atmosphere using a Mg rod as the working electrode: open circuit potential (OCP) and onset of Mg(II) reduction as measured by cyclic voltammetry (CV). There was only a 3% difference between the average OCP measured versus the mullite and MgO reference electrodes. Potential drift was higher for mullite (−1.34 mV d −1 ) than MgO (0.22 mV d −1 ). But both drift rates were very low compared to the OCP data standard deviation, indicating that no significant drift was measured for us to 31 d.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Determination of Kinetic Properties of Ni(II) Ions in Molten LiF-NaF-KF via Voltammetry

Kinetic properties of Ni(II) in eutectic LiF-NaF-KF (FLiNaK) molten salt were determined at T = 748–823 K using cyclic voltammetry (CV), square wave voltammetry (SWV), and chronoamperometry (CA) measurements using a glassy C working electrode, Ni(II)/Ni reference electrode, and Ni counter electrode. Reduction of Ni(II) to Ni(s) was determined to be a single step, two-electron transfer process. Diffusivity values were calculated using the Berzins and Delahay equation and semi-integral electroanalysis from the CV measurements as well as using the Cottrell equation from the CA measurements. Diffusivity of Ni(II) in molten FLiNaK at T = 748–823 K was determined to be 3.27 × 10 –7 –3.04 × 10 –6 cm 2 s –1 with an activation energy of 62–104 kJ mol –1 . The estimated kinetic properties varied appreciably among methodologies possibly due to inherent assumptions in theory regarding reversibility and unit activity during Ni metal deposition on the working electrode.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗