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Molten salts thermodynamic properties, discussing pure salts corresponding states and binary mixtures conformal solution theories, using model ionic melt
Electric aircraft propulsion has gained a traction over the last decade due to possible high-energy density electrochemistries with reasonable cycle life and identification of non-flammable chemistries that can guarantee much better safety. Commercial Li-ion batteries cannot reach such high capacities because of weight limitations that arise from the widely used intercalation electrodes. Also, use of organic electrolytes make them highly susceptible to fire on exposure to air and humidity. Currently, use of Lithium metal anode along with conversion electrochemistries such as Li-O2 and Li-S are being pursued to achieve such high energy densities. Safer inorganic solid-state electrolytes, recently discovered Water-in-Salt electrolytes, molten salt electrolytes are some of the alternatives being pursued for a safer/non-flammable battery. Of these safer alternatives, molten-salt electrolytes offer some attractive properties: liquid at operating temperatures resulting in better electrode-wetting, stable interface with Li-metal anodes and good ionic conductivity; their only drawback being high operating temperatures. In this talk, we will discuss some of the computational studies, driven via atomistic simulations, of the properties of molten-salt electrolytes including transport mechanism and interface stability. We will also discuss predicting electrochemical properties of these high-temperature electrolytes. Further, we will discuss a thermodynamic approach to predicting new molten-salt eutectics with lower melting points.
Molten salt battery has been developed with theoretical energy density of 5.2 j/kg (650 W-h/lb). Battery, which operates at 150 C, can be used in primary mode or as rechargeable battery. Battery has aluminum anode and chlorine cathode. Electrolyte is mixture of AlCl3, NaCl, and some alkali metal halide such as KCl.
The interaction of molten salts of different Na2O activities and mullite is examined with furnace and burner tests. The more-acidic molten salts form small amounts of Al2O3; the more-basic molten salts form various Na2O-Al2O3-SiO2 compounds. The results are interpreted using the Na2O-Al203-SiO2 ternary phase diagram, and some possible diffusion paths are discussed. The generally higher melting points of Na2O-Al2O3-SiO2 compounds lead to better behavior of mullite in molten salts, as compared to SiO2-protected ceramics such as SiC. Mullite-coated SiC is discussed, and the corrosion behavior is evaluated.
The molten salt or the flux method is used to fabricate a grain oriented YBa2Cu3O(7-x) (123) superconductor. Here we suggest a two-stage approach in using the 'green phase', Y2BaCuO5 (211), as seed crystals in the formation of YBa2Cu3O(7-x). The process uses Y2BaCuO5 formed by molten salt synthesis. The Y2BaCuO5 phase was observed to be stable in water and in most of the salt systems. Salt processing can form a small quantity of anisotropic particles of Y2BaCuO5. This material can form the 123 phase when tape cast and sintered in the presence of the required levels of Ba and Cu.
Fluid flow patterns in molten salt electrolytes were observed in order to determine how mass transport affects the morphology of the metal deposit. Studies conducted on the same metal, both in aqueous electrolytes in which coherent solid electrodeposits are produced, as well as in transparent molten salt electrolytes are described. Process variables such as current density and composition of the electrolyte are adjusted to change the morphology of the electrodeposit and, thus, to permit the study of the nature of electrolyte flow in relation to the quality of the electrodeposit.
Molten or fused salts have been evaluated as possible thermoelectric materials because of the relatively good values of their figures of merit, their chemical stability, their long liquid range, and their ability to operate in conjunction with a nuclear reactor to produce heat. In general, molten salts are electrolytic conductors; therefore, there will be a transport of materials and subsequent decomposition with the passage of an electric current. It is possible nonetheless to overcome this disadvantage by using the decomposition products of the molten-salt electrolyte in a fuel cell. The combination of a thermoelectric converter and a fuel cell would lead to a regenerative system that may be useful.
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.
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.
Al electrodes in molten salt electrolytes, investigating electrochemical kinetics by polarization measurements
The present study seeks to explain the poor quality of solid electrodeposits in molten salts through a consideration of the effects of fluid flow of the electrolyte. Transparent cells allow observation of electrolyte circulation by a laser schlieren optical technique during the electrodeposition of solid zinc from the molten salt electrolyte, ZnCl2 - LiCl-KCl. Experimental variables are current, density, electrolyte composition, and cell geometry. Based on the results of earlier electrodeposition studies as well as reports in the literature, these parameters are identified as having the primary influence on cell performance and deposit quality. Experiments are conducted to measure the fluid flow patterns and the electrochemical cell characteristics, and to correlate this information with the morphology of the solid electrodeposit produced. Specifically, cell voltage, cell current, characteristic time for dendrite evolution, and dendrite growth directions are noted. Their relationship to electrolyte flow patterns and the morphology of the resulting electrodeposit are derived. Results to date indicate that laser schlieren imaging is capable of revealing fluid flow patterns in a molten salt electrolyte.
In the search for efficient energy storage battery technologies, designing stable electrolytes has been a long-standing challenge. Electrolytes based on molten salt eutectics are known for their stability with minimum parasitic reactions when compared to their widely used organic counterparts. However, the operating temperatures of these molten salt electrolyte-based batteries are dictated by the melting point of the eutectic mixtures. Design and high throughput screening of low melting temperature eutectic molten salt mixtures have been hindered by the lack of computational models. In this work, we develop thermodynamic models to predict the eutectic points of several molten salt mixtures. The framework of the COSMO-SAC model is used for the predictions and is compared with experimental data and other thermodynamic approaches. Rapid thermodynamics-based approaches, as shown in this study, can accelerate the discovery of new materials, complementing experimental techniques.
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 500C 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”
Viewgraphs of the discussion on cathodes for molten-salt batteries are presented. For the cathode reactions in molten-salt cells, chlorine-based and sulfur-based cathodes reactants have relatively high exchange current densities. Sulfur-based cathodes, metal sulfides, and disulfides have been extensively investigated. Primary thermal batteries of the Li-alloy/FeS2 variety have been available for a number of years. Chlorine based rechargable cathodes were investigated for the pulse power application. A brief introduction is followed by the experimental aspects of research, and the results obtained. Performance projections to the battery system level are discussed and the presentation is summarized with conclusions.
The applications of chronopotentiometry to the study of electrochemical behavior of three technologically important areas of refractory metals, actinides, and oxyanions in molten salts are critically reviewed. Chronopotentiometry is a very versatile diagnostic tool to understand the reaction mechanism of the electrode processes for the electrochemical reduction/oxidation of these electroactive species in molten salt solutions. Well adherent, compact, and uniformly thick coatings of refractory metals may be electrodeposited from their solutions in molten salts.
Current Li-ion batteries are designed for a small operating window of 5 °C to 55 °C. Modifications to the electrolyte for operation in Mars atmosphere extended this range on the lower bound to ~ -40 °C. These operating-temperature ranges are far from those presented in high-temperature environments, such as the Venus surface, where temperatures are around 450 °C. Protecting the state-of-the-art Li-ion batteries require insulations that decreases the volumetric capacity and limiting the operational time-window. These unique challenges require a paradigm shift in materials used for designing high-temperature batteries. Molten salt electrolyte-based batteries offer a plausible route to designing high-temperature batteries. ZEBRA batteries are known to be one of the safest energy storage devices operating at 270-350 °C. Nitrate based eutectics, operating at 150 °C have also been used in Li-O2 batteries. In this study, we will examine molten-salt electrolyte transport and electrochemical properties using first-principles computations and benchmark against experiments. Further, we will present thermodynamics-based models for designing and predicting melting point of molten salt mixtures. Based on these computational tools, new molten salt mixtures designed with desired operating temperatures and electrochemical windows will be presented. Implications of these new eutectics in the context of high-temperature environment exploration will also be discussed.
A development program is being conducted at Advanced Thermal Batteries (ATB) to create a low discharge rate, long life, molten salt battery for a NASA Venus surface probe. Battery goals are 60 days continuous operation at +25V +0/-6 volts and -25V +6/-0 Volts under severe environments of 465°C, 92 atm pressure, and corrosive sulfur dioxide in a super critical carbon dioxide atmosphere. Conveniently, molten salt thermal battery electrochemistry starts to operate efficiently at 330°C. However, a major barrier to direct application of existing thermal battery technology is the high self-discharge rate, resulting in lifetimes in only minutes, not days. The best performance to date, which meets the required voltage regulation, has been a lithium silicon (LiSi) alloy anode discharging through all three voltage plateau versus an iron monosulfide (FeS) cathode. In order to perform reproducibly, additional engineering controls within the battery design are required to limit cell–to–cell parasitic discharge mechanisms. Results of these trials have improved the efficiency and manufacturability of the design.
Metal-coated graphite fibers are being considered as a thermal conductivity enhancement filler material for molten salts in solar dynamic thermal energy storage systems. The successful metal coating chosen for this application must exhibit acceptable wettability and must be compatible with the molten salt environment. Contact angle values between molten lithium fluoride and several metal, metal fluoride, and metal oxide substrates have been determined at 892 C using a modification of the Wilhelmy plate technique. Reproducible contact angles with repeated exposure to the molten LiF indicated compatibility.