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At least 523 records · Page 29

Designing Molten Salt Eutectics: A Combined Thermodynamic Modeling and Machine Learning Approach

Designing stable electrolytes with target properties is an important challenge in realizing next generation energy storage devices. Molten salt eutectics-based electrolytes are known for their stability with minimal parasitic reactions when compared to traditional organic electrolytes and are an attractive option for different battery chemistries. The operating temperature of the molten salt batteries depends on the melting temperature of the eutectic and hence there is a necessity to discover novel low melting temperature molten salt eutectic mixtures for energy storage applications. In this work we develop a high throughput computational screening approach for molten salt mixtures using thermodynamic modeling and machine learning (ML). COSMO-SAC model and ML approaches were independently developed based on the existing experimental data and these models were further used to predict the eutectic melting temperature and composition of several new binary, ternary, and quaternary mixtures. We show that combining ML and thermodynamic modeling strategies is effective in exploring the vast design space of molten salt mixtures.

Thermodynamics↗

Importance of Quantifying the Full-depth Carbon Reservoir of Jamaica Bay Salt Marshes, New York

Constraining uncertainty in the global carbon cycle requires valid assessment of both surface and stored carbon in marine and coastal ecosystems (Blue Carbon) as well as terrestrial carbon (forests, peatlands, and soils) [Pendleton et al., 2012]. Quantifying the global carbon stock of coastal salt marshes, potentially the most efficient carbon-burying ecosystems in the world per area, is a key area of further research in both of these fields Pendleton et al., 2012. One of the largest challenges is that despite the fact that salt marshes often sequester carbon several meters deep, nearly all estimates of salt marsh carbon stocks consider only the upper 1 m of sediment (Windham-Myers et al., 2015) [54]. This is particularly concerning because coastal wetlands are increasingly at risk due to climate change, sea level rise, and anthropogenic disturbance and destruction (Deegan et al., 2012) [15]. Using full-depth measurements from marsh cores, we estimate the carbon stock of five salt marshes in the highly urbanized estuary of Jamaica Bay, New York and argue that partial-depth measurements can underestimate carbon stocks. These estimates use calculated carbon content and probe depth data of these marshes collected between 2000 and 2019, applying this data across the full area of the marsh obtained from satellite imagery. Carbon density measurements are then multiplied by the full-depth volume of the marshes to create an estimate of total carbon stock. In addition to calculating present-day estimates, we compare our carbon stock estimates to historical Jamaica Bay imagery to calculate historical carbon stocks and carbon loss. The carbon stock estimates presented here show a 95% carbon stock loss between 1885 and 2019 in Jamaica Bay and highlight the severe underestimation of carbon stocks without full-depth calculations. These findings have important implications for disappearing salt marshes with regard to the global carbon cycle and the incorporation of belowground carbon into global climate models. The findings are increasingly relevant for advocacy efforts aiming to conserve these marshes with sea level rise.

Tidal wetlands↗

Designing Molten Salt Eutectics

Designing stable electrolytes with target properties is an important challenge in realizing next generation energy storage devices. Molten salt eutectics-based electrolytes are known for their stability with minimal parasitic reactions when compared to traditional organic electrolytes and are an attractive option for different battery chemistries. The operating temperature of the molten salt batteries depends on the melting temperature of the eutectic and hence there is a necessity to discover novel low melting temperature molten salt eutectic mixtures for energy storage applications. In this work we develop a high throughput computational screening approach for molten salt mixtures using thermodynamic modeling and machine learning (ML). COSMO-SAC model and ML approaches were independently developed based on the existing experimental data and these models were further used to predict the eutectic melting temperature and composition of several new binary, ternary, and quaternary mixtures. We show that combining ML and thermodynamic modeling strategies is effective in exploring the vast design space of molten salt mixtures.

Ashwin Ravichandran↗

Molten Salt Lattice Confinement Fusion (LCF) Fast Fission Reactor for Lunar and Planetary Surface Power

Molten salt fission reactors (MSR) have been suggested for lunar and planetary surface power systems. They have the advantage of operating at high temperature, for efficient thermal-electrical conversion, low pressure, long-lived with high nuclear fuel burnup. MSR are often designed to breed fissile 233U from natural 232Th by neutron capture and  decay via: 232Th(n,)233Th(,)233Pa(,)233U Unfortunately, this process requires 233Pa isotope separation and segregation to decay to 233U. This requirement prevents additional neutron capture that interferes with 233U breeding. Instead, Wooley’s sub-critical, fast fission, molten salt reactor would use externally generated tokamak fusion neutrons1,2 to fission all actinides.We propose a simpler fusion-fast-fission sub-critical reactor that generates fast neutrons in situ from lattice confinement fusion (LCF) to fission fertile and fissile actinides. This hybrid reactor doesn't require enriched 235U fissile pins to initiate fis-sion reactions, nor 233Pa separation and segregation during operation. Like Wooley’s, this hybrid reactor “burns” natural uranium (238U) or thorium (232Th) which avoids uranium enrichment and additional fissile material launch safety and security costs. The LCF neutron source is initiated by bremsstrahlung photoneutrons (Fig. 1)3 or isotopic neutron sources in electron-screened lattices (Fig. 2)4,5. Alternatively, the electrolytic Pd-deuterium co-deposition6protocol fast fissions7 both 232Th and 238U. However, an aqueous electrolyte-based system, without pressurization similar to conventional pressurized water fission reactors, is incapable of high temperatures due to the boiling point of the electrolyte slightly over 100 C. Molten salts can be used instead as was demonstrated at the University of Hawaii8 using a variety of Ni and Pd cathodes in lithiated, hydrided and deuterated salts. These salts have melting points often exceeding 500C making them suitable to efficiently produce electrical power9 through either Advanced Stirling Genera-tors (< 100 kWe) or closed-Brayton Cycle (> 100 kWe). This hybrid reactor could power a wide range of lunar or Martian applications from unmanned in-struments, to charging vehicles and entire facilities such as human habitats or in situ resource utilization. The power conversion cycles are Carnot Cycle limited, but generally 30% efficient at best. However, waste heat on the moon or Mars is important to surviving either two-week lunar nights or Martian nights as well as providing process heat for mineral extraction and “living off the land”

Lawrence Forsley↗

Method to produce salts containing actinide halides

A method of producing uranium halides is disclosed in which chlorine gas is introduced into a liquid uranium-nickel alloy. NaCl salt is surrounding the crucible containing the liquid uranium-nickel alloy, producing a eutectic mixture of NaCl—UCl3. Upon chlorination, the metal halide dissolves in the matrix salt forming a solution. Adding the reactant metal, uranium to the nickel, the alloy is able to remain molten throughout processing. The liquid metal alloy may be removed from the salt bath, while the halogen gas continues to enter the system through the sparge until the desired composition of NaCl—UCl3—UCl4 is achieved. The method and system can be used to produce other metal halide salts such as actinide, lanthanide or transition metal halides contained in a matrix salt consisting of alkali and/or alkaline earth halides.

Williamson, Mark A.↗

Anion binding agent lithium salts for battery electrolytes

A method for synthesizing a purified lithium (Li)+ anion binding agent (ABA-F)− salt and the corresponding Li+(ABA-F)− are disclosed. The method includes dissolving a boron-based acid in a polar solvent to form a solution. The solution is refluxed to form an anion binding agent. A stoichiometric amount of a small fluorinated salt, such as LiF, is added to the anion binding agent to form a mixture. The mixture is subsequently crystallized to obtain a substantially pure Li+(ABA-F)− salt. Example purified Li+(ABA-F)− salts include Ox-Li+(ABA-F), m-Li+(ABA-F), and BF3—Li+(ABA-F)−. These purified Li+(ABA-F)− salts provide the benefits of increased battery thermal safety without loss of electrochemical performance.

Orendorff, Christopher↗

MSTEC: Molten Salt Thermophysical Examination Capability

Technical Description – a shielded modular hotcell with an inert argon atmosphere, housing characterization equipment for determining thermophysical and thermochemical properties of high temperature liquids not limited to but focusing on irradiated fuel salts Location – MFC, FCF, rm 35 Compatible Materials: Chloride, fluoride salts Fresh fuel salts and irradiated fuel salts Pyrophoric material - U, Pu metal Gases – H2, HCl, Cl2, HF, F2, NF3 Beryllium containing salts Many others

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Salt Sample Statistical Study

Historically there has, at times, been large variability in measured uranium concentration amongst salt samples taken at the same time from the electrorefiner with relative standard deviations ranging from 0.59% up to a high of 114%. This has led to uncertainty in the actual uranium content of the salt. A series of surrogate experiments were performed with gadolinium to study the effects of Li2O, Gd2O3, and Gd metal additions to an LiCl-KCl-GdCl3 salt on the gadolinium content of the salt. These experiments showed no increase in salt sample variability following the additions of the mentioned species, indicating that the carryover of these species from the oxide reduction process may not lead to the historic variability issues.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Measurement of partial vapor pressures of salt mixtures via combined horizontal transpiration and thermogravimetric analysis

A method combining thermogravimetric analysis (TGA) and horizontal transpiration with elemental analysis via inductively coupled plasma mass spectrometry or ion chromatography enabled calculation of partial pressures of individual salts in molten mixtures. TGA quantified total mass loss, while transpiration identified vapor-phase composition. Furthermore, two chloride (NaCl-MgCl 2 , NaCl-MgCl 2 + UCl 3 ) salts and one mixed halide (LiCl-LiF + Li 2 O) salt were analyzed at 750 °C and 550 °C, respectively. NaCl and MgCl 2 vapor pressures were 2.19–2.61 × 10 -4 atm and 2.47–2.48 × 10 -5 atm (dependent upon the identity of the invesitgated mixture); UCl 3 was 1.42 × 10 -7 atm. LiCl and LiF vapor pressures at 550 °C were 1.53 × 10 -6 and 6.32 × 10 -6 atm, respectively. Additionally, the TGA method was validated against values from the literature for unary LiCl and LiF.

36 MATERIALS SCIENCE↗

X‐Ray Absorption Studies of Local Structure of Dilute Ionic Species in Molten Salts

Molten salts are crucial materials with exceptional properties that make them suitable for applications such as heat transfer media, coolants, and liquid fuels in molten salt nuclear reactors and the concentrated solar power industry. Understanding their properties requires unraveling the intricate mysteries of their structure. To achieve this, advanced characterization tools are essential. Among various techniques, X‐ray absorption fine structure (XAFS) stands out as a versatile method capable of studying the structure of molten salts under in situ conditions. This review highlights recent advancements in the application of XAFS for investigating the local structure of molten salts, discusses its limitations and potential improvements, and explores complementary approaches such as simulations, machine learning, and correlative experimental methods.

22 - GENERAL STUDIES OF NUCLEAR REACTORS↗

Low-stress creep behavior of multiple salt caverns under cyclic operations

Here, the use of multiple salt caverns for large-scale underground hydrogen storage offers a strategic solution to the growing demand for efficient and flexible energy storage, due to the inherent low permeability, high mechanical strength, and self-healing properties of the salt formation. Despite these advantages, the long-term geomechanical response of salt caverns under cyclic injection and withdrawal remains a significant challenge for ensuring operational stability. This mechanistic study highlights the critical role of low-stress creep, also known as pressure solution creep, in governing deformation of salt caverns during cyclic operations. Unlike conventional creep mechanisms that dominate under high-stress conditions, low-stress creep becomes particularly relevant under the moderate stress changes induced by repeated injection and withdrawal, which provides a previously underexplored control on cavern closure. Our three-dimensional computational model integrates the low-stress creep mechanism into the Munson–Dawson creep equation across a spectrum of operational scenarios including variations in cavern pressure cycles, injection-withdrawal frequencies, and caprock mechanical property. The low-stress creep components accelerate the cavern creep closure, which is amplified with shorter cycle frequency and larger pressure difference. Sensitivity analyses capture the complex interactions between multiple caverns and surround formations at the field scale that allows for a quantitative assessment of deformation patterns and closure rates over time and thereby informs the design and operation of sustainable underground hydrogen storage system.

Cyclic operation↗

Round Robin Measurements of Molten Salt Properties for LiF-NaF-KF (FLiNaK) and NaCl-KCl Mixtures

The development, operation, and regulation of nuclear reactors that utilize molten salts as fuel or as heat transfer media require knowledge of the thermal properties of the salt systems and quantification of the corresponding uncertainties. Knowledge of molten salt properties is also necessary for applications in material synthesis, processing, separations, solar thermal power generation, and energy storage. A round robin was conducted with national laboratory and university participants from twenty-one laboratories in five countries to compare property measurements, to better understand uncertainties, and to identify possible best practices. Two salt mixtures, each from a common batch, were distributed to participants for evaluation: equimolar NaCl-KCl and 45.0LiF-13.7NaF-41.3KF mol % (FLiNaK). Measurements were performed to determine the major constituent composition, oxygen content, density, thermal expansivity, melting point, and thermal conductivity. Error analysis was performed on each measurement for uncertainty quantification for each type of property that was explored. Finally, the resulting discussion of the methodologies used in this work is meant to lay the groundwork for the development of standard methods and reference materials for future high-temperature property measurements on halide melts.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Chlorine Gas as a Lewis Acid–Base Probe for Molten Salts of Divalent Metal Ions

In the context of energy applications for salts and, more specifically, in the case of molten salt reactors, the solvation of corrosion species, the nature and behavior of radiation-produced excess electrons, transient radicals, and molecular gas species all depend on the Lewis acid–base behavior of the constituent salt melt. Speciation of dissolved species and their transport properties are also influenced by the ability of the melt to form networks. This article focuses on the structural properties of melts composed of alkaline earth metal ions coupled with the Cl – anion, and the quantum mechanical behavior of Cl 2 , a typical product of the reaction of radiation-produced chlorine radicals in Cl – -based molten salts. We explore the effect of M 2+ Lewis acidity on chlorobasicity, seen in this work as the availability of Cl – ions to chemically react with Cl 2 to produce Cl 3 – .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Single Crystalline Na 0.67 Ni 0.33 Mn 0.67 O 2 Positive Electrode Material via Molten Salt Synthesis for Sodium Ion Batteries

P2-layered Na 0.67 Ni 0.33 Mn 0.67 O 2 (NNMO) has emerged as a promising positive electrode material for sodium ion batteries due to its appealing electrochemical properties. Synthesis of polycrystalline NNMO (PC-NNMO) materials through conventional calcination of solid precursors remains the prevailing method, where heating occurs in a dry environment with air or O 2 . On the other hand, the molten salt method, where precursors are submerged in molten salt medium during calcination, emerged in recent years to be a scalable technique for more controlled crystal growth and uniform morphology in a variety of materials. Here, we utilize the molten salt method to synthesize single crystalline NNMO (SC-NNMO) materials with enhanced electrochemical properties. The SC-NNMO material exhibits an initial specific discharge capacity of 95 mAh g –1 at a 0.1C rate, retaining approximately 88.5% of its capacity after 100 cycles over a wide voltage range of 2.0–4.2 V. Furthermore, SC-NNMO maintains a capacity retention of 83.9% after 300 cycles at a 1C rate compared to 66.6% for PC-NNMO, indicating excellent long-term cycling stability. This stability is further confirmed by the performance of an SC-NNMO//hard carbon full cell, which retains 90.3% of its capacity after 200 cycles at 1C within a voltage window of 1.9–4.1 V. The enhancement in stability of the SC-NNMO sample is attributed to the single crystalline structure suppressing the undesired P2–O2 phase transition at high voltage. This study also presents an easy, efficient, and straightforward molten salt process for SC-NNMO material synthesis, offering valuable insights into the potential application of such methodology for the large-scale, cost-effective production of various sodium-layered transition metal oxide positive electrode materials for SIBs.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Effects of Particle Size and Concentration of Magnesium Oxide on the Lubricating Performance of a Chloride Molten Salt for Concentrating Solar Power

One engineering challenge for the next-generation concentrating solar power (CSP) is to identify appropriate heat transfer and thermal energy storage media. A chloride salt mixture (20 wt % NaCl + 40 wt % MgCl 2 + 40 wt % KCl) in a molten phase is proposed as a potential fluid for carrying the heat as well as lubricating the CSP pump bearings. Due to the hygroscopic nature of MgCl 2 , the presence of magnesium oxide (MgO) particles is inevitable. In order to understand the impact of MgO particles, this study investigated the tribological behavior of the molten chloride salt mixture containing MgO of various particle sizes and concentrations. Tests were conducted at 750 °C in a dry Ar environment using a zirconia ball sliding against a Haynes 244 alloy disc lubricated by the molten salt. There was a clear trend of the increased friction coefficient and wear loss for a larger particle size and/or a higher concentration of MgO. Distinct wear mechanisms were identified for the ceramic ball and alloy disc. Results provide fundamental insights for this new research avenue of molten salt lubrication for CSP.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Design and performance of high-temperature furnace and cell holder for in situ spectroscopic, electrochemical, and radiolytic investigations of molten salts

To facilitate the development of molten salt reactor technologies, a fundamental understanding of the physical and chemical properties of molten salts under the combined conditions of high temperature and intense radiation fields is necessary. Optical spectroscopic (UV–Vis–near IR) and electrochemical techniques are powerful analytical tools to probe molecular structure, speciation, thermodynamics, and kinetics of solution dynamics. In this paper, we report the design and fabrication of three custom-made apparatus: (i) a multi-port spectroelectrochemical furnace equipped with optical spectroscopic and electrochemical instrumentation, (ii) a high-temperature cell holder for time-resolved optical detection of radiolytic transients in molten salts, and (iii) a miniaturized spectroscopy furnace for the investigation of steady-state electron beam effects on molten salt speciation and composition by optical spectroscopy. Initial results obtained with the spectroelectrochemical furnace (i) and high-temperature cell holder (ii) are reported.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Fuel Salt Qualification and Associated Fuel Cycle Opportunities & Issues

NRC staff have defined fuel qualification as a process which provides high confidence that the physical and chemical behavior of fuel is sufficiently understood so that it can be adequately modeled for both normal and accident conditions, reflecting the role of the fuel design in the overall safety of the facility. Uncertainties are defined so that calculated fission product releases include the appropriate margins to ensure conservative calculation of radiological dose consequences. The Advisory Committee on Reactor Safeguards (ACRS) has accepted the methodology described in NUREG/CR-7299 as an acceptable method for fuel qualification for molten salt reactors. The fuel salt qualification process described in NUREG/CR-7299 is based upon understanding the role that the fuel salt plays in achieving the fundamental safety functions, which in-turn is based on the fuel salt thermophysical and thermochemical properties.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Design Basis Document / Owner’s Technical Specification for Nitrate Salt Systems in CSP Projects (Final Technical Report)

The number of commercial coal, gas, and nuclear projects built over the past 100 years number in the thousands. As such, there is a large database, available to a wide range of commercial engineering contractors, on proven designs. In essence, unsuccessful designs have, through generations of iterations, been identified and then deleted from further consideration. In contrast, the number of commercial parabolic trough projects using nitrate salt for the thermal storage media is perhaps 60. Further, the number of commercial central receiver projects using nitrate salt as the working fluid is on the order of 20, including estimates for China. Given the relative immaturity of salt technology, and commercial pressures to successfully bid new solar projects into a mature electricity market, solar projects often promise more than has been delivered. The Design Basis Document / Owner’s Technical Specification is a first step in the iteration process. The report describes the successful features of commercial projects, outlines a range equipment and system failures in projects that didn’t operate as intended, and provides a draft set of design changes intended to correct the known problems. The product of the study is 3 volumes of technical material; one volume is on parabolic trough technologies; a second is on central receiver technologies, and the third is on potential design changes to parabolic trough and central receiver projects. The 3 volumes, which total some 590 pages, can be found at https://www.solardynllc.com/csp-plant-technologies. One of the principal topics in the report is the use of functional or prescriptive specifications. Functional specifications describe what the equipment needs to do, consistent with the minimum legal requirements of the local jurisdictions. The details of how this is to be accomplished is developed by the engineering contractor. Prescriptive specifications, which are developed by the Owner, prescribe to the engineering contractor how the functional requirements are to be met. This arrangement ensures that the favorable experience from a previous project is repeated. One example is the design code for the hot salt tank in central receiver projects. The closest design basis is API Standard 650 Welded Steel Tanks for Oil Storage. However, the maximum design temperature in API 650 is 260 °C. As such, solar projects have typically adopted a hybrid Code approach, in which allowable material stresses are taken from ASME Section II Materials. Further, since the tanks experience daily changes in temperature and in (static) pressure, and since portions of the tank can operate at stresses beyond the elastic range, the low cycle fatigue life of the tank is conducted using the rules of Section VIII Division 2. However, in a recent study by NREL, the principal damage mechanism was identified as creep rather than fatigue. Further, design stresses permitted under Section VIII Division 2, corresponding to a fatigue life of 30 years, result in projected creep lifetimes of only 2 to 5 years. An alternate design approach, prescribed by the Owner, would be based on Code sections intended for high temperature service in the creep regime. A candidate is Section III Division 5. Granted, this is a nuclear code section, and it’s use would not likely be mandated by local jurisdictions. However, the effects of creep have been deemed to be of sufficient importance that one nuclear project developer, and one central receiver project developer, have stipulated in the tank design specification that the equipment be designed to the requirements of Section III Division 5.

14 SOLAR ENERGY↗