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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Unconventional Charge Transport in MgCr 2 O 4 and Implications for Battery Intercalation Hosts

Ion transport in solid-state cathode materials prescribes a fundamental limit to the rates batteries can operate; therefore, an accurate understanding of ion transport is a critical missing piece to enable new battery technologies, such as magnesium batteries. Based on our conventional understanding of lithium-ion materials, MgCr 2 O 4 is a promising magnesium-ion cathode material given its high capacity, high voltage against an Mg anode, and acceptable computed diffusion barriers. Electrochemical examinations of MgCr 2 O 4 , however, reveal significant energetic limitations. Motivated by these disparate observations; herein, we examine long-range ion transport by electrically polarizing dense pellets of MgCr 2 O 4 . Our conventional understanding of ion transport in battery cathode materials, e.g., Nernst-Einstein conduction, cannot explain the measured response since it neglects frictional interactions between mobile species and their nonideal free energies. In this work, we propose an extended theory that incorporates these interactions and reduces to the Nernst-Einstein conduction under dilute conditions. This theory describes the measured response, and we report the first study of long-range ion transport behavior in MgCr 2 O 4 . We conclusively show that the Mg chemical diffusivity is comparable to lithium-ion electrode materials, whereas the total conductivity is rate-limiting. Given these differences, energy storage in MgCr 2 O 4 is limited by particle-scale voltage drops, unlike lithium-ion particles that are limited by concentration gradients. Future materials design efforts should consider the interspecies interactions described in this extended theory, particularly with respect to multivalent-ion systems and their resultant effects on continuum transport properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Addition of Chloroform in a Solvent-in-Salt Electrolyte: Outcomes in the Microscopic Dynamics in Bulk and Confinement

Solvent-in-salt electrolytes (SISEs) are a promising alternative to the electrolytes currently used in commercial devices. Despite the SISEs’ advantages, their utilization is not yet realized due to the poor mobility of their chemical species. Here, we explore this problem by adding chloroform to a SISE formed by acetonitrile and a Li-salt. First, we performed illustrative cycling experiments to highlight the potential of this approach. Then, we focused on the description of the microscopic dynamics of the electrolytes and exposed the relevant aspects to be considered for their optimal performance. While the conductivity at low temperatures may be enhanced by the addition of chloroform, only subtle changes occur at room temperature. As revealed by molecular dynamics simulations and quasielastic neutron scattering (QENS) experiments, this effect is related to the preservation of the structure expected for a highly concentrated solution and promotion of the formation of ionic aggregates. These outcomes occur despite the increase in the overall mobility of the chemical species. The dynamics of the electrolytes in porous carbon was also investigated using QENS. In these circumstances, low concentrations of chloroform lead to diffusivities of the molecular species higher than those observed for the bulk electrolytes. As chloroform’s concentration increases, no further changes in the diffusivities are observed. Nonetheless, chloroform is mostly immobilized on the carbon surfaces and this behavior may be intensified at compositions closer to the eutectic mixture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Polysulfide entrapment and retardation in gel electrolyte Li–S batteries: experiments and modeling

Gelling the electrolyte in lithium–sulfur (Li–S) batteries provides advantages in terms of safety and mitigating polysulfide shuttling leading to reduced side reactions and dendrite growth on the anode side. In the current study, organic and ceramic crosslinkers have been used to improve the entrapment of polysulfides and prevent them from shuttling to the anode side. However, the performance of gel electrolytes is still far from being on par with liquid electrolytes in terms of raw capacity. The discharge curves exhibit an extended first plateau for gel electrolyte batteries compared to liquid electrolytes, showing that polysulfides are better trapped in the gel system. Yet, in the conversion of soluble polysulfides into insoluble polysulfides, the second plateau was delayed. Qualitative and quantitative analysis of the polysulfide diffusion in the liquid electrolyte and gel electrolyte systems were also conducted to predict the relative diffusivity ratio between the liquid electrolyte and gel electrolyte for simulation. To probe what happens at the end of the discharge, where the mass transport in the gel electrolyte appears to be slow, a modified discharge procedure was used where the cell is first paused after discharge and then discharged a second time before recharging normally. Coin cell tests for two gel electrolytes in addition to liquid electrolyte show up to 7% capacity recovery after the pause, which indicates that the diffusion of species during the pause is responsible for the failure recovery. Additionally, the recovery is higher for gel electrolytes compared to liquid, for higher C-rates, and for longer pause times. To better understand this behavior, a Li–S numerical model with mass transport limited reactions was used to examine the polysulfide diffusion coefficients expected in different electrolyte systems. The model is able to reproduce the trends seen in experiments and yields a higher recovery for smaller Li 2 S 4 diffusion coefficients, suggesting that insufficient Li 2 S 4 mass transport is responsible for failure at the end of discharge. By identifying the effect that gel electrolytes have on the state of the battery during discharge using both experimental and simulation methods, this work is a step towards leveraging the advantages of gel electrolytes and mitigating their weaknesses.

25 ENERGY STORAGE↗
DOE OSTI2022

Radiation effects on the structure and alteration behavior of an SiO 2 –Al 2 O 3 –B 2 O 3 –Na 2 O glass

As borosilicate glasses are used in many countries to immobilize fission products and minor actinides after spent fuel reprocessing before storage in a deep geological repository, assessing that their chemical durability is of paramount importance. Here, pristine and preirradiated (952 MeV, 136Xe) SiO 2 –B2O 3 –Al2O 3 –Na 2 O glasses with the same molar ratios as in the French SON68 and ISG glasses have been subjected to aqueous corrosion in deionized water and in silica-saturated solution to measure the initial and longer term alteration rates. Pristine and preirradiated glasses corrode following the same mechanisms, but the preirradiation has a strong impact on the initial dissolution rate (increase by a factor of 5.6), and on the alteration layer depth in silica-saturated conditions (by two- to threefolds). The later result is related to the formation of a more porous, less passivating gel on the preirradiated glass specimen. Using both experimental spectroscopies (NMR, IR, and SFG) and classical molecular dynamics, the radiation effects on the glass structure and water diffusion have been assessed. After preirradiation, the density and the polymerization degree of the glass decrease, whereas the topological disorder increases. In consequence, water diffusion accelerates. These observations allow to correlate the radiation impact on the alteration behavior to the structural changes.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Investigation of Sub‐Bandgap Emission and Unexpected n‐Type Behavior in Undoped Polycrystalline CdSe x Te 1‐x

Abstract Se alloying has enabled significantly higher carrier lifetimes and photocurrents in CdTe solar cells, but these benefits can be highly dependent on CdSe x Te 1‐x processing. This work evaluates the optoelectronic, chemical, and electronic properties of thick (3 µm) undoped CdSe x Te 1‐x of uniform composition and varied processing conditions (CdSe x Te 1‐x evaporation rate, CdCl 2 anneal, Se content) chosen to reflect various standard device processing conditions. Sub‐bandgap defect emission is observed, which increased as Se content increased and with “GrV‐optimized CdCl 2 ” (i.e., CdCl 2 anneal conditions used for group‐V‐doped devices). Low carrier lifetime is found for GrV‐optimized CdCl 2 , slow CdSe x Te 1‐x deposition, and low‐Se films. Interestingly, all films (including CdTe control) exhibited n‐type behavior, where electron density increased with Se up to an estimated ≈10 17 cm −3 . This behavior appears to originate during the CdCl 2 anneal, possibly from Se diffusion leading to anion vacancy (e.g., V Se , V Te ) and Cl Te generation.

14 SOLAR ENERGY↗
DOE OSTI2023

Integrated simulation of U-10Mo monolithic fuel swelling behavior

Here, a separate computational branch has been implemented within the DART (Dispersion Analysis Research Tool) computational code to simulate the swelling behavior of U-10Mo monolithic fuel under the operating conditions of high-power research and test reactors (RTRs). The monolithic branch of the DART code implements a mechanistic rate-theory-based fission-gas-behavior model for the calculation of fission gas swelling, as well as a suite of thermal, physical, and mechanical models to take into account various processes occurring in RTR fuels during irradiation. In order to accurately simulate and eventually predict U-10Mo monolithic fuel irradiation behavior, the code uses materials properties calculated with lower length-scale computational methods, such as gas atom diffusivity and U-Mo surface energy from atomic simulations and grain-morphology-specific recrystallization kinetics (recrystallized fuel volume fractions vs. fission density) predicted using the phase-field method. The remainder of fission gas behavior parameters used in the model were calibrated with measured intergranular bubble size distributions. With this integrated simulation approach, the swelling behavior of U-10Mo monolithic fuel was simulated for various initial grain sizes at different operating conditions and compared with measured data. Furthermore, because limited experimental data exist for parameter calibration detailed sensitivity studies for the important parameters used in the fission gas behavior model were performed in order to examine their impact on both intergranular gas bubble morphology at low fission density, and on total porosity at high fission density.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Strengthening model development and effects of low diffusing solutes to coarsening resistance in aluminum alloys

A modified Orowan strengthening model is proposed to account for finite rod-shaped precipitates with hemispherical caps in aluminum alloy systems. A combined computational and experimental approach is used to study the influences of anisotropic Orowan looping and solute-dislocation interaction on temperature-dependent yield strength. Here, the strengthening model is validated with a dataset containing 297 experimental precipitate geometries, chemistries, temperatures, and strength measurements, and achieves a strong predictive correlation of 0.8713 with experimentally measured yield strengths. Under conditions that are applicable to coarsening, constant particle volume fraction and aspect ratio, the model predicts that short rod precipitates provide far superior strengthening effects compared to plate precipitates. A cast Al-Si-Mg-Cu alloy with rod-shaped Q-phase (Al 3 Cu 2 Mg 9 Si 7 ) precipitates was developed with a novel chemistry exploring the use of low-diffusivity elements (Mn, Ni, V, Zr) to limit precipitate coarsening. The thermodynamic behavior of Mn, Ni, V, and Zr across the Q-phase interface is examined using transmission electron microscopy (TEM), first-principles density-functional theory (DFT) calculations. and atom-probe tomography (APT). DFT calculations utilizing TEM identified Q-phase/Al-matrix interfaces show that Mn, Ni, V, and Zr preferentially segregate to the Q-phase precipitate boundaries which suggests inhibition of precipitate coarsening and higher strengths after temperature exposure. Atom-probe tomography confirms solute atom partitioning/segregation at the Q-phase/Al-matrix interface, found in the modified commercial AS7GU alloy (A356 +0.5%Cu), which supports these observations.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Property Measurements of NaCl-UCl 3 and NaCl-KCl-UCl 3 Molten Salts (Rev.1)

Thermochemical and thermophysical property values of several salt compositions of interest are needed by molten salt reactor (MSR) developers to design, license, and operate their reactors. Thermochemical and thermophysical properties being measured at Argonne include thermal transitions, phase behavior, heat capacity, density, volumetric thermal expansion of the liquid phase, thermal diffusivity, thermal conductivity, and viscosity. Several properties of eutectic compositions in the ternary NaCl-KCl-UCl 3 and binary NaCl-UCl 3 systems that may be used by MSR developers as fuel bearing salts are being measured. A 65.8 mol % NaCl–34.2 mol % UCl 3 mixture and a near-eutectic mixture of 50.9 mol % NaCl–24.4 mol % KCl–24.7 mol % UCl 3 were synthesized and the thermochemical properties of the mixtures were measured by using differential scanning calorimetry (DSC). The measured transition temperatures were compared to transition temperatures predicted using two models. A thermodynamic model of the binary NaCl-UCl 3 system was constructed using data in the Molten Salt Thermal Properties Database–Thermochemical Version 2.0 (MSTDB-TC V2.0). A ternary NaClKCl-UCl 3 system model constructed at Argonne and was described in a previous report. These comparisons can be used to validate the models. Thermophysical property values of molten salts are needed to model how salt retains and transfers heat in an MSR system. These property values are essential to the entire MSR design because molten salt is used as both the fuel and the coolant material in a salt fueled reactor. Heat capacity of the synthesized NaCl-UCl 3 and NaCl-KCl-UCl 3 salt mixtures was measured by using DSC and thermal diffusivity was measured by using laser flash analysis (LFA) at temperatures spanning the typical operating range of an MSR.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Oxygen-deficient ammonium vanadate for flexible aqueous zinc batteries with high energy density and rate capability at -30 °C

Aqueous zinc batteries (AZBs) have received significant attention owing to environmental friendliness, high energy density and inherent safety. However, lack of high-performance cathodes has become the main bottleneck of AZBs development. Here, oxygen-deficient NH 4 V 4 O 10–x ·nH 2 O (NVOH) microspheres are synthesized and used as cathodes for AZBs. The experimental test and theoretical calculations demonstrate that the oxygen vacancies in the lattice lower the Zn 2+ diffusion energy barrier, which enables fast Zn 2+ diffusion and good electrochemical performance in a wide temperature range. The suppressed side reactions also can help to improve the low temperature performance. NVOH shows a high energy density of 372.4 Wh kg –1 and 296 Wh kg –1 at room temperature and –30 °C, respectively. Moreover, NVOH maintains a 100% capacity retention after 100 cycles at 0.1 A g –1 and ~94% capacity retention after 2600 cycles at 2 A g –1 and –30 °C. Investigation into the mechanism of the process reveals that the capacity contribution of surface capacitive behaviors is dominant and capacity attenuation is mainly caused by the decay of diffusion-controlled capacity. As a result, flexible AZBs can steadily power portable electronics under different bending states, demonstrating its great potential in wide-temperature wearable device.

25 ENERGY STORAGE↗
DOE OSTI2021

Building and experimenting with an agent-based model to study the population-level impact of CommunityRx, a clinic-based community resource referral intervention

CommunityRx (CRx), an information technology intervention, provides patients with a personalized list of healthful community resources (HealtheRx). In repeated clinical studies, nearly half of those who received clinical “doses” of the HealtheRx shared their information with others (“social doses”). Clinical trial design cannot fully capture the impact of information diffusion, which can act as a force multiplier for the intervention. Furthermore, experimentation is needed to understand how intervention delivery can optimize social spread under varying circumstances. To study information diffusion from CRx under varying conditions, we built an agent-based model (ABM). This study describes the model building process and illustrates how an ABM provides insight about information diffusion through in silico experimentation. To build the ABM, we constructed a synthetic population (“agents”) using publicly-available data sources. Using clinical trial data, we developed empirically-informed processes simulating agent activities, resource knowledge evolution and information sharing. Using RepastHPC and chiSIM software, we replicated the intervention in silico, simulated information diffusion processes, and generated emergent information diffusion networks. The CRx ABM was calibrated using empirical data to replicate the CRx intervention in silico. We used the ABM to quantify information spread via social versus clinical dosing then conducted information diffusion experiments, comparing the social dosing effect of the intervention when delivered by physicians, nurses or clinical clerks. The synthetic population (N = 802,191) exhibited diverse behavioral characteristics, including activity and knowledge evolution patterns. In silico delivery of the intervention was replicated with high fidelity. Large-scale information diffusion networks emerged among agents exchanging resource information. Varying the propensity for information exchange resulted in networks with different topological characteristics. Community resource information spread via social dosing was nearly 4 fold that from clinical dosing alone and did not vary by delivery mode. This study, using CRx as an example, demonstrates the process of building and experimenting with an ABM to study information diffusion from, and the population-level impact of, a clinical information-based intervention. While the focus of the CRx ABM is to recreate the CRx intervention in silico, the general process of model building, and computational experimentation presented is generalizable to other large-scale ABMs of information diffusion.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Atomistic processes of surface-diffusion-induced abnormal softening in nanoscale metallic crystals

Abstract Ultrahigh surface-to-volume ratio in nanoscale materials, could dramatically facilitate mass transport, leading to surface-mediated diffusion similar to Coble-type creep in polycrystalline materials. Unfortunately, the Coble creep is just a conceptual model, and the associated physical mechanisms of mass transport have never been revealed at atomic scale. Akin to the ambiguities in Coble creep, atomic surface diffusion in nanoscale crystals remains largely unclear, especially when mediating yielding and plastic flow. Here, by using in situ nanomechanical testing under high-resolution transmission electron microscope, we find that the diffusion-assisted dislocation nucleation induces the transition from a normal to an inverse Hall-Petch-like relation of the strength-size dependence and the surface-creep leads to the abnormal softening in flow stress with the reduction in size of nanoscale silver, contrary to the classical “alternating dislocation starvation” behavior in nanoscale platinum. This work provides insights into the atomic-scale mechanisms of diffusion-mediated deformation in nanoscale materials, and impact on the design for ultrasmall-sized nanomechanical devices.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Explosive Soot Challenge (Final Report)

This project assembled a broad ensemble of modeling and experimentation tools to study the morphological and optical properties of detonation soots in explosive fireballs. A gram-scale hemispherical high explosive was studied in a low-pressure controlled environment using in-situ experimentation with diffusely illuminated visible absorption spectroscopy, particle sizing through light scattering techniques, and post-test collections with subsequent morphological analysis. Hydrocode modeling was performed to replicate the detonation flow observations, and subsequent aerosol kinetics models provided particle size distributions and extinction coefficients from the hydrocode results. Experimentally observed soot morphologies agreed with expectation from the literature - a bimodal distribution was found, brought upon by the particles growing to a size where their inertia and fluid wakes are non-negligible. The aerosol kinetics model did not replicate the observed bimodal size distribution for lack of a coagulation kernel to represent the behavior. To recover particulate optical properties, a spectrally resolved absorption spectroscopy method termed Spectral diffuse back-illuminated extinction imaging (SBI-EI) was developed and implemented on two explosive types. Inverting the absorption spectra using a Kramers-Kronig consistent method yielded the complex index of refraction for the soots produced by the explosives. This method resulted in an unrealistic index of refraction for one of the two explosives, and this is suspected to be due to the model neglecting scattering brought upon by the large particle sizes observed. In addition to the core work, three additional studies were performed in parallel. These investigated the impact of scattering on diffuse absorption spectroscopy, studied how soots oxidate and sublimate in a well-controlled shock tube, and laid the theoretical groundwork for a new collision kernel to replicate the bimodal size distribution from the observations. Summaries of these efforts are included at the end of this report.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗
DOE OSTI2021

Revealing High-Temperature Reduction Dynamics of High-Entropy Alloy Nanoparticles via In Situ Transmission Electron Microscopy

Understanding the behavior of high-entropy alloy (HEA) materials under hydrogen (H 2 ) environment is of utmost importance for their promising applications in structural materials, catalysis, and energy-related reactions. Herein, the reduction behavior of oxidized FeCoNiCuPt HEA nanoparticles (NPs) in atmospheric pressure H-2 environment was investigated by in situ gas-cell transmission electron microscopy (TEM). The reduction reaction front was maintained at the external surface of the oxide. During reduction, the oxide layer expanded and transformed into porous structures where oxidized Cu was fully reduced to Cu NPs while Fe, Co, and Ni remained in the oxidized form. In situ chemical analysis showed that the expansion of the oxide layer resulted from the outward diffusion flux of all transition metals (Fe, Co, Ni, Cu). Revealing the H-2 reduction behavior of HEA NPs facilitates the development of advanced multicomponent alloys for applications targeting H 2 formation and storage, catalytic hydrogenation, and corrosion removal.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

A study of damage-free in-situ etching of GaN in metalorganic chemical vapor deposition (MOCVD) by tertiarybutylchloride (TBCl)

This paper reports a study of the effect of NH 3 flow rate and reactor temperature on the tertiarybutylchloride (TBCl) etching of patterned GaN-on-sapphire templates. It is found that a reduced NH 3 flow rate and an elevated reactor temperature can eliminate islands or dots on the surface, while at the same time, enhance the etching around dislocations. TBCl etching was also performed on planar bulk GaN templates with much lower dislocation density. We find an atomically flat and layer-by-layer etching behavior within the region free of dislocations. Surface kinetics analysis reveals a short diffusion length of etching products. Room-temperature photoluminescence (PL) and x-ray photoelectron spectroscopy (XPS) measurements confirm that TBCl etching is capable of removing the damage and impurities induced by plasma etching without introducing additional damage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

The Triple Component Interface of Ni–Co–Ce: Growth, Chemical State, and Stability of NiCo Bimetallic Particles on Reducible CeO 2 (111) Thin Films

The growth of NiCo particles at low coverages over reducible CeO 2 (111) thin films producing a triple interface between Ni-Co-Ce was investigated by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS), which was compared to that of monometallic Ni and Co particles. XPS data show that deposition of either Ni or Co on CeO 2 at 300 K causes a partial reduction of Ce 4+ cations to Ce 3+ ions. At 0.3 monolayer (ML), XPS detects Co 2+ on CeO 2 . However, both Ni 0 and Ni 2+ are present as major species at 300 K and annealing causes a significant increase of Ni 2+ in Ni particles. Deposition of 0.3 ML Co over 0.3 ML Ni on CeO 2 at 300 K induces reduction of Ni 2+ to metallic Ni and Ni 0 was found as predominant species. Unlike for Co/CeO 2 , metallic Co was also present over the Co-Ni/CeO 2 surface in addition to Co 2+ . Further, this behavior indicates the formation of NiCo bimetallic particles with the possibility of Co diffusion to the interface of Ni/ceria. With heating, the intermixing of Ni and Co atoms in bimetallic particles on CeO 2 was facilitated. Furthermore, oxidation of both metals and ceria occurred as a result of the diffusion of lattice oxygen from the bulk of ceria to the surface. A slight increase in Ni 2+ was observed after heating Co-Ni/CeO 2 to 500 K or higher. Co became Co 2+ with heating to 800 K. Our STM results confirm the formation of NiCo bimetallic particles on CeO 2 at 300 K and further suggest that the addition of Co can help inhibit the sintering of Ni particles at higher temperatures. Bimetallic particles were also obtained by depositing Ni over existing Co particles on CeO 2 . However, our XPS data demonstrate that the deposition order of Co and Ni plays a role in the chemical state of these two metals in bimetallic particles, likely attributed to the difference in their compositions at the bimetallic particle surface as well as the metal-support interface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Collapse of Jahn-Teller phonons in La 1−x Sr x MnO 3 with weak magnetoresistance

Perovskite manganites are quantum materials exhibiting competing interactions inducing colossal magnetoresistance (CMR). The prevailing theory of CMR highlights the essential role of electron-phonon coupling (EPC), but mounting evidence suggests the underlying mechanism is more complicated. Here, we investigate phonons and spin-phonon coupling in ferromagnetic CMR manganites La 1−x Sr x MnO 3 (x=0.2,0.3) with relatively small CMR associated with melting of the magnetic order above room temperature. High-resolution neutron scattering experiments combined with density functional theory (DFT) show that the low-temperature ferromagnetic phase is conventional: neutron scattering from phonons agrees with DFT predictions and magnons follow sinusoidal dispersions. Fluctuating magnetic moments and low-energy phonons remain conventional in the high-temperature paramagnetic phase, indicating the Mn and La/Sr sublattices are not strongly perturbed by melting of ferromagnetism. In contrast, the Jahn–Teller-active optical oxygen vibrations collapse entirely above the Curie temperature, despite low CMR in these compositions, with some of the lost spectral weight reappearing as quasielastic scattering. We attribute this highly anomalous behavior to giant EPC in the charge and/or orbital channel. It drives cooperative diffusive motion of quasistatic carrier-trapping oxygen sublattice distortions once ferromagnetism disappears. We hypothesize the magnitude of magnetoresistance correlates with the rate of diffusion rather than with the strength of Jahn–Teller EPC.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Determination of Molecular Structure and Dynamics of Molten Salts by Advanced Neutron and X-ray Scattering Measurements and Computer Modeling

The design and development of fully functional Molten-Salt Reactors (MSR) require detailed knowledge of the molten salt properties in order to understand and predict the salt’s behavior. Fundamental properties of interest include molecular structure, speciation, and dynamics (such as diffusion coefficients) of salt components and dissolved corrosion and fission products. Computer modeling is necessary to predict changes in physical and chemical properties due to irradiation, burning of dissolved fuel, and corrosion. The modeling requires experimental data, and advanced neutron and x-ray scattering and spectroscopy provide the most reliable and direct determination of the structure (Pair-Distribution Functions, PDF), and dynamics of ions in the melt. This project dealt with both fluoride and chloride salts. The PDFs have been measured by a combination of neutron and x-ray diffraction. We utilized the techniques of isotope substitutions, a very powerful tool available for neutron-scattering, to extract the details of the liquid structure. Although similar measurements have been done before, modern advanced neutron and x-ray-scattering techniques allow collecting the data at much higher resolution and in a wider range of temperatures. Importantly, we were among the first to study fluoride salts by neutron scattering. The importance of impurities and their effects on salt properties have become apparent recently and so new methods of salt purification were developed. We took advantage of these developments to produce reliable data, which have been used for computer simulations of both clean salts and those with added fission and corrosion products most relevant for MSRs. Ab initio molecular dynamics simulations have been performed to understand the multi-component liquid solution, in particular solubility of impurities and thermodynamic interactions in relation to the ionic-cluster structure of the fluid. We applied machine learning to regress from the simulation and experimental data in order to develop a fast-acting model that can handle molten salt with an arbitrary (≥ 10) number of chemical elements and be able to predict chemical potential as a function of composition and temperature. This project resulted in a number of experimental and computer-simulation publications, a patent application, and numerous conference presentations (American Physical Society, American Chemical Society, and The Electrochemical Society among others). Multiple students and postdocs participated and collaborated on aspects of this project. This project seeded new collaborations between MIT and other institutions, such as the University of Massachusetts Lowell, the University of Illinois Urbana-Champaign, the University of California Berkeley, and Oak Ridge and Los Alamos National Labs. As such, this project has had a broad and lasting impact beyond its original scientific scope.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Self-Diffusivity Measurement of Eutectic F 7 LiNaK with and without Additives Using Quasi-Elastic Neutron Scattering

The atomic scale relaxation dynamics of eutectic F 7 LiNaK (46.5 LiF–11.5 NaF–42 KF mol %, Li-7 enriched) were measured using quasi-elastic neutron scattering (QENS) over a temperature range of 500–750 °C. Here, the effect of adding 0.988 mol % cerium, 0.499 mol % cesium, and 1.21 mol % zirconium individually to the dynamics of F 7 LiNaK was also investigated. The relaxation process in both pure and doped F 7 LiNaK molten salts was fit with a stretched exponential function and the temperature dependence follows an Arrhenius behavior over a wavevector transfer range of 0.4 Å –1 < Q < 0.9 Å –1 . The measured activation energy for self-diffusion is E a = 0.77 ± 0.02 eV/atom for pure molten F 7 LiNaK. The QENS response with additives added to F 7 LiNaK was also fit with a stretched exponential and the associated Arrhenius behavior was characterized with activation energies of E a = 0.88 ± 0.01 eV/atom for zirconium (1.21 mol %), E a = 1.02 ± 0.02 eV/atom for cerium (0.988 mol %), and E a = 0.71 ± 0.03 eV/atom for cesium (0.499 mol %). The measured diffusivities are compared to those simulated with a neural network force field model by Lee et al. [Lee, S.-C. Comparative Studies of the Structural and Transport Properties of Molten Salt FLiNaK Using the Machine-Learned Neural Network and Reparametrized Classical Forcefields. J. Phys. Chem. B 2021, 125(37), 10562–10570].

FLiNaK↗