THERMODYNAMIC CALCULATION OF n-COMPONENT EUTECTIC MIXTURES

Brunet, Luc; Caillard, J. F.; André, Pascal

doi:10.1142/s0129183104006121

Cited by 17 publications

(8 citation statements)

References 10 publications

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“…The decrease in the melting point of this eutectic relative to the melting point of LiCl (which is lower than T m of KCl) is 258°. Usually, a eutectic mixture is formed when a multicomponent system in a solid state forms a superlattice, which simultaneously releases all its components into a liquid mixture during a low‐temperature transition to a liquid state 33 …”

Section: Factors Affecting the Degree Of Reduction Of Actinoid Oxidesmentioning

confidence: 99%

“…Usually, a eutectic mixture is formed when a multicomponent system in a solid state forms a superlattice, which simultaneously releases all its components into a liquid mixture during a low-temperature transition to a liquid state. 33 The solubility of oxygen in the LiCl melt is about 11.6 mol%, but it decreases significantly with the addition of KCl or CsCl. It is shown that when AE metal chlorides are introduced into the melt, the behavior of the O 2 solubility turns out to be ambiguous: BaCl 2 somewhat reduces the solubility, while SrCl 2 increases it.…”

Section: Experimental Study Of the Uo 2 Reduction Mechanismmentioning

confidence: 99%

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Recoveryof actinidesand fission products from spent nuclear fuel via electrolytic reduction: Thematic overview

Галашев

2021

Intl J of Energy Research

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Summary Spent nuclear fuel (SNF) from modern light water or thermal reactors containing uranium oxide with small concentrations of plutonium and other actinide oxides is converted into metal by the electrolytic reduction. The obtained metal must be subjected to further processing (electrorefining). This review reflects the achievements in development SNF electrolytic processing, concepts of the technological operations, and a model describing the electrochemical process. The technological scheme for the electrochemical reduction of SNF and MOX fuel is considered. The complexity of a carbon anode application in the process of UO2 electrolytic reduction is reflected. The reduction processes of alkali, alkaline earth (AE), and rare earth metal oxides as well as oxide compounds of zirconium are demonstrated. The reduction of lanthanum oxide and oxy‐chloride to the metallic form by adding metallic nickel to the molten salt is discussed. The solubility of Li2O in molten salts is interpreted depending on the amount of dissolved alkali and AE metal chlorides. The considered pyroprocessing technology enables a much greater release of the energy accumulated in uranium ore, and recycling all actinides allows reducing significantly the amount of nuclear waste and the time it must be isolated.

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Section: Factors Affecting the Degree Of Reduction Of Actinoid Oxidesmentioning

confidence: 99%

Section: Experimental Study Of the Uo 2 Reduction Mechanismmentioning

confidence: 99%

Recoveryof actinidesand fission products from spent nuclear fuel via electrolytic reduction: Thematic overview

Галашев

2021

Intl J of Energy Research

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“…6c). Additionally, the eutectic point was estimated at X ED ¼ 0.3 and T ¼ À145 C by calculation based on a thermodynamic relationship between the composition and temperature: 24…”

Section: Eutectic Behavior Of Electrolytesmentioning

confidence: 99%

Nitrile-Assistant Eutectic Electrolytes for Cryogenic Operation of Lithium-Ion Batteries at Fast Charges and Discharges

et al. 2014

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The charge/discharge characteristics of lithium ion batteries at low temperature (LT ¼ À20 C) are enhanced by using ethylene carbonate (EC)-based electrolytes with the help of assistant solvents of nitriles. Conventional liquid electrolytes (e.g. a mixture of EC and dimethyl carbonate (DMC), abbreviated as L ED ) cannot support a satisfactory capacity at low temperature as well as at high rates even if electric vehicles require low-temperature operation. Introducing propionitrile or butyronitrile (Pn or Bn) into L ED (resulting in L EDPn or L EDBn ) as a co-solvent increases significantly the high-rate capacities at À20 C. For example, L EDPn delivers 62% of the available capacity at 1 C and 46% at 3 C with a 2.7 V cut-off while the control L ED provides just 6% and 4% at the same rates. Successful operation at À20 C with nitrileassistant electrolytes results from high ionic conductivity, low viscosity and freezing point depression caused by the eutectic behavior of the carbonates (EC/DMC) and Pn. Based on the phase diagram of Pn with EC/DMC, we expect a meaningful battery operation up to À110 C, probably lower, at the eutectic composition. Broader contextLithium ion batteries for electric vehicles should provide required energy within limited spaces with guaranteed safety, delivering enough power to satisfy the requirements of electric motors, be charged within a short time period so that drivers can endure and be operated in a wide range of temperature including the cryogenic range up to À20 C and more severely À30 C. The inferior charge and discharge characteristics of LIBs at low temperatures are one of the most serious problems that should be overcome by research and development. The disability of LIBs at low-temperature operations is caused by the limited ionic transport properties of the electrolyte, sluggish Li + desolvation with slow charge transfer kinetics and phase transition of the electrolyte, leading to severe ohmic and concentration polarization. In this work, we present nitrile-assistant carbonate-based eutectic electrolytes showing signicantly enhanced charge and discharge characteristics at À20 C and high rates up to 3 C. The successful operation at À20 C with the nitrile-assistant electrolytes results from high ionic conductivity, low viscosity and freezing point depression caused by the eutectic behavior of the carbonates and nitriles. Fig. 8 Comparison of discharge capacities at À20 C obtained with different cut-off voltages. Pouch full cells were discharged up to 3.0 V or 2.7 V. The discharge capacity values (Q dCh ) were normalized by the value obtained at room temperature with 0.2 C.This journal is

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“…The most well-known thermodynamic model for predicting eutectic phase behavior is the simplest: the van't Hoff equation, also called the Schröder-van Laar equation. [10][11][12] The van't Hoff equation assumes ideal mixing, which means it does not take any excess mixing properties into account. Excess mixing properties are usually modeled via a regular solution model, 13,14 however, these are mainly applied for only binary mixtures.…”

Section: Introductionmentioning

confidence: 99%

Large Decrease in Melting Point of Benzoquinones via High-n Eutectic Mixing Predicted by a Regular Solution Model

Baclig

Ganapathi

et al. 2022

Preprint

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Decreasing the melting point (Tm) of a mixture is of interest in cryopreservatives, molten salts, and battery electrolytes. One general strategy to decrease Tm, exemplified by deep eutectic solvents, is to mix components with favorable (negative) enthalpic interactions. We demonstrate a complementary strategy to decrease Tm by mixing many components with neutral or slightly positive enthalpic interactions, using the number of components (n) to increase the entropy of mixing and decrease Tm. In theory, under certain conditions this approach could achieve an arbitrarily low Tm. Furthermore, if the components are small redox-active molecules, such as the benzoquinones studied here, this approach could lead to high energy density flow batteries. Finding the eutectic composition of a high-n mixture, however, is challenging due to the large compositional space. We demonstrate with differential scanning calorimetry measurements that 1,4-benzoquinone derivatives exhibit eutectic mixing that decreases their Tm, despite slightly positive enthalpies of mixing (0-5 kJ/mol). We show how the enthalpies of mixing can be used in a regular solution model (assuming immiscible solids and only binary interactions) to predict the eutectic composition and temperature. By investigating all 21 binary mixtures of a set of seven 1,4-benzoquinone derivatives with alkyl substituents (Tm’s between 44-120 °C), we demonstrate that the eutectic melting point of a mixture of all seven achieves a large decrease in Tm to -6 °C, and that the regular solution model shows improvement over an ideal solution model in predicting the eutectic properties.

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THERMODYNAMIC CALCULATION OF n-COMPONENT EUTECTIC MIXTURES

Cited by 17 publications

References 10 publications

Recoveryof actinidesand fission products from spent nuclear fuel via electrolytic reduction: Thematic overview

Recoveryof actinidesand fission products from spent nuclear fuel via electrolytic reduction: Thematic overview

Nitrile-Assistant Eutectic Electrolytes for Cryogenic Operation of Lithium-Ion Batteries at Fast Charges and Discharges

Large Decrease in Melting Point of Benzoquinones via High-n Eutectic Mixing Predicted by a Regular Solution Model

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