Molten Salt Electrolyte Research Articles

Molecular dynamics simulation of microstructure and thermophysical properties of LiCl–CaCl2eutectic molten salt

AbstractChloride molten salt systems are widely used as electrolytes for molten salt electrolysis because of their relatively low eutectic temperatures and good thermal stability, but there is a serious lack of data on the thermophysical properties of chloride molten salts at elevated temperatures, whereas the nature of the electrolyte is very important for the electrolysis process. In this paper, the variation of the microstructure and thermophysical properties of the binary mixed LiCl–CaCl2molten salt system with temperature and composition is calculated using molecular dynamics (MD) simulations based on the BMH potential. The microscopic conformations observed in LiCl–CaCl2molten salts are mainly irregular, distorted tetrahedra and octahedra, which dynamically coexist, as analyzed by the radial distribution function, coordination number and angular distribution function. In addition, the effects of temperature and composition on the density, ionic self-diffusion coefficient, shear viscosity, and ionic conductivity of the molten salts were investigated, and the relationships of the thermophysical properties of LiCl–CaCl2molten salts with temperature and composition were obtained, which provide fundamental thermophysical data for the molten salt electrolytes.

In situ dual-interface layer enabling lower resistance of Ta-doped Li7La3Zr2O12-based thermal battery

Application of Ta-doped Li7La3Zr2O12 (LLZTO) to thermal battery could solve overflow safety hazards caused by molten salt electrolytes. However, the capacity of large current discharge is obstructed by the large interfacial resistance originating from poor solid–solid contact between LLZTO and cathode. In this work, an in-situ dual-interface layer with favorable conductivity and multi-ionic diffusion between LLZTO and cathode is constructed by introducing connection layer in a simple way. The Ni(BrxCl2-x) layer with favorable conductivity would be established at high temperature during discharge for the reaction between the connection layer and NiCl2 cathode; the ionic (Br-,Cl-,O2–) diffusion layer with significant diffused direction among the connection layer, LLZTO layer and cathode layer occurs simultaneously at high temperature during discharge. Besides, the left connection layer with low melting point could form wettable interface as well. Consequently, the internal resistance of the single cell modified by in-situ dual-interface layer is reduced from 3.72 Ω to 1.70 Ω, accompanying with larger discharge current density (from 25 to 100 mA cm−2) and higher specific energy (from 444 to 1050 Wh kg−1) at 500 °C. Comparing with the typical discharge current of LLZTO which is less than 1 mA cm−2, this report provides a new insight to improve the interfacial resistance for the solid–solid contact at ambient temperature and the application for LLZTO on high-temperature battery.

Recent advances in electrochemical recovery of rare earth elements from NdFeB magnets

Recent advances in electrochemical methods promise a more sustainable recycling of rare earth elements (REEs) from discarded NdFeB permanent magnets. The demand for NdFeB magnets for clean energy applications is rapidly increasing, motivating recycling efforts to diversify REE supply. The main electrochemical steps include the selective dissolution of REE-rich phases at the anode and the reduction of REE ions at the cathode. Pretreatment with demagnetization, mechanical size reduction, and leaching contributes to the release and concentration of REEs. Thermal demagnetization and mechanical crushing make the magnets brittle and improve the penetration of leaching agents. Acid leaching dissolves the REEs, but also dissolves the iron. To facilitate the extraction of REEs at high temperatures, molten salt electrolytes such as chlorides are used, while ionic liquids allow extraction under milder conditions, but with the caveat of possible decomposition during the process. Aqueous solutions have been most thoroughly investigated due to their versatility and affordability. Fluoride-based molten salt electrolytes effectively dissolve RREs and provide a stable environment for hightemperature electrodeposition, improving the efficiency and sustainability of rare earth element recovery. To isolate highpurity REE oxides and metals, additional processing is required using techniques such as solvent extraction, selective precipitation, and electroseparation. Key factors for optimal electrochemical recycling are maximizing selectivity for REEs, minimizing energy consumption and waste generation, and simplifying integration. Although technical challenges remain, recent advances show that electrochemical technologies can improve the sustainability of recycling critical REEs from permanent magnets.

An inorganic molten salt electrolyte-based Li-CO2 battery with moderate working temperature and enhanced performance.

Herein, a binary inorganic molten salt electrolyte based on lithium bis(fluorosulfonyl)imide (LiFSI) and potassium bis(fluorosulfonyl)imide (KFSI) is applied to Li-CO2 batteries that can operate under 80 °C. Benefiting from the intrinsic nonvolatility, electrochemical stability, raised ionic conductivity, sufficient solubility and safety, the molten electrolyte endows the Li-CO2 battery with a large discharge capacity of 4612 mA h g-1 and superior rate capability. The introduction of the Ru@Super P carbon cathode further optimizes the discharge capacity (9503 mA h g-1), overpotential (1.15 V), and rate capability.

Electrochemical-catalytic NH3 synthesis from H2O and N2 using an electrochemical cell with a Ru catalyst, Pd–Ag membrane cathode, and NaOH–KOH molten salt electrolyte at 250 °C

At 250 °C, using an electrochemical setup with a Ru catalyst, Pd alloy H2-permeable membrane cathode, NaOH–KOH molten salt electrolyte, and Ni anode, NH3 was synthesized from H2O and N2 with 30 mA cm−2 current density of and 25% current efficiency.

The correlation of the liquidus curves and valence electron structures of a ternary lithium halide molten-salt electrolyte for liquid metal batteries.

Liquid metal batteries have received considerable attention owing to their excellent properties. However, an electrolyte with low melting temperature is required to decrease operating temperature for the safety of liquid metal batteries and for saving energy. For revealing the mechanism of low liquefaction temperature, an empirical electron theory of solid molecules was used to study the thermal properties of pure lithium halides and their ternary-phase systems systematically. The theoretical bond lengths, melting points, liquefaction temperatures and mixed energies of pure lithium halides and their ternary phases match the experimental values well. The mechanism of liquefaction temperature for ternary lithium halides depends on their valence electron structures. The liquefaction temperature can be stabilized on a liquidus line or curve through the modulation of the constant number of covalent electrons (nc) and lattice electrons (nl). The liquefaction temperatures on various liquidus lines and curves are positively related to the linear density of valence electron pairs on the strong Li-X bond, bonding factor, and number of valence electrons in the s orbital but are negatively related to the number of valence electrons in the p orbital. With an increase in the linear density of the valence electron pair number and bonding factor, bond strength is enhanced, which increases the resistance of the strong Li-X bond against the break force induced by thermal phonon vibrations, and more thermal phonons with high vibrating energy are required for breaking the strongest Li-X bond at a higher temperature; therefore, the liquefaction temperature increases.

Anodic dissolution of gallium in alkali metal chloride melts

Gallium and gallium based alloys can be potentially used in pyrochemical and pyroelectrochemical reprocessing of spent nuclear fuels, particularly for separating actinides and rare earth fission products. However, the electrochemical behavior of gallium in high temperature molten salt electrolytes is very little studied. The present work was aimed at investigating the processes taking place during anodic dissolution of gallium in fused alkali chlorides (the ternary 6NaCl–9KCl–5CsCl eutectic mixture) and determining the ratio of gallium chloro-species in different oxidation states formed and remained in the melt. The experiments were performed between 550 and 750 °C, and the anodic current density varied from 0.024 to 0.094 A/cm2. Anodic polarization and coulometry were used, and the results obtained demonstrated that two gallium species, Ga(I) and Ga(III), were formed as a result of gallium anodic dissolution. The ratio between these two oxidation states depended on temperature and anodic current density. The method of processing the experimental data and the calculated values of the ratio of gallium ionic forms in the system under various conditions are presented.

Modelling Ca2+ Mobility and Dynamics in Solvent-Free Molten Salt Electrolytes for Calcium Batteries

Multivalent elements based batteries using earth-abundant minerals is a route with promises, not only from a performance but also from a supply and cost point of view; this is not the last true for calcium (Ca) batteries since Ca is the fifth most abundant element in the Earth's crust [1,2,3]. There is, however, no functional electrolyte available yet for Ca batteries, calling for early modelling to be made to map the influence of different Ca-salts and salt concentrations on electrolyte physicochemical properties such as density, viscosity, ionic conductivity, charge carrier dynamics and diffusivity [3, 4]. One particular route little trodden is molten salt electrolytes (MSEs), materials that consist of ions with different valences in direct contact with each other due to the complete absence of any solvent. In practice, MSEs are multicomponent salt mixtures with reduced melting points with respect to the ingoing components and furthermore they also expand the operating temperature range upwards as compared to conventional liquid electrolytes. Moreover, MSEs have high ionic conductivities due to their intrinsically high ionic content and ionic mobility. Additionally, MSEs exhibit wide electrochemical stability windows, non-flammability, and non-toxicity [5, 6]. We have investigated MSEs composed of Ca(FSI)2, LiFSI, NaFSI, and KFSI, by molecular dynamics (MD) simulations. Apart from the basic properties, we focus on the relative dynamical properties of the different cations in the MSEs in order to obtain a fundamental understanding of the systems’ behaviour, both globally and locally, but for natural reasons with special emphasis on the Ca2+ ions.

Neodymium Metal Production Via Chloride Based Molten-Salt Electrolysis

The extraction and purification of metals such as aluminum has relied on the electrowinning process for decades. The Hall-Héroult process, developed in 1885, utilizes a molten salt electrolyte to electrochemically produce aluminum metal (Al) and carbon dioxide (CO2).1–3 Similar molten salt techniques exist for a variety of other metals including the rare earth metal Neodymium (Nd). Neodymium has seen significant increases in demand from increased production of wind turbines, electric vehicles, and hard disk drives that use neodymium–iron–boron (Nd–Fe–B) permanent magnets. 4,5 The current procedure for neodymium processing uses a neodymium and lithium fluoride molten salt electrolyte with a sacrificial carbon anode to convert neodymium oxide (Nd2O3) and carbon to neodymium metal and CO2.4,6 As an unfortunate byproduct of the fluoride containing molten salt, perfluorocarbons (PFCs) can also be produced simultaneously. The formation of PFCs combined with the emission of other greenhouse gases (CO,CO2) makes the current process dangerous and undesirable from an environmental standpoint. Due to this, few places currently produce neodymium metal and virtually none is produced in the United States, creating supply chain risks with dire consequences.5 An alternative molten salt process has been proposed where rather than directly converting neodymium oxide to neodymium metal, the oxide is first converted to chloride salt form by reaction with hydrochloric acid. The neodymium salt is then dissolved into a chloride salt based melt and neodymium is electroplated via the below set of reactions.7,8 Cathode: 2NdCl3 + 6e- → 2Nd(solid) + 6Cl- Anode: 6Cl- → 3Cl2 + 6e- Overall: 2NdCl3 → 2Nd(solid) + 3Cl2 This process has several distinct advantages. The chlorine reaction eliminates the need for a sacrificial anode material as well as the production of carbon dioxide. The chloride based molten salt also eliminates the formation of PFCs. The chlorine is then recycled to make more hydrochloric acid for use in converting neodymium oxide to chloride.This talk focuses on recent advances to improve purity and lower energy consumption (kWh/kg). We evaluate anode and cathode behavior during this neodymium chloride molten salt process. Over-potential and stability of various anode materials are investigated in order to minimize energy consumption and ensure long life of process materials. A new stable analytic cathode is demonstrated which is lowers chlorine over-potential by more than 200 mV at current density of 250 mA/cm2.The effect of various plating conditions such as current density and substrate material are investigated to determine impact on deposit quality, coulombic efficiency, and metal purity. Highly porous Nd deposits are known to form in chloride molten salt but are undesirable due to the energy required to separate out the high volume fraction of salt remaining in the solid sponge. Effects of temperature and electrolyte composition on deposit morphology are investigated and improvements toward densifying the sponge to minimize post electrolysis purification are reported. This proof of concept work aims to develop a safe, sustainable and environmentally friendly path towards large scale production of rare earth elements. Reactor design and cathode efficiency results are based upon work supported by the U.S. Department of Energy’s Office of Energy Efficiency and Renewable Energy under the Advanced Manufacturing Office, Award Number DE-EE0009434. Anode design work was supported through the Critical Materials Institute, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Advanced Manufacturing Office. The views expressed herein do not necessarily represent the views of the U.S. Department of Energy or the United States Government. Portions of this work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. T. R. Beck, Electrochem. Soc. Interface, 23, 36–37 (2014).G. G. Botte, Electrochem. Soc. Interface, 23, 49–55 (2014).W. E. Haupin, J. Chem. Educ., 60, 279–282 (1983).M. F. Chambers and J. E. Murphy, Electrolytic production of neodymium metal from a molten chloride electrolyte.B. Sprecher, R. Kleijn, and G. J. Kramer, Environ. Sci. Technol., 48, 9506–9513 (2014).V. S. Cvetković et al., Met. 2020, Vol. 10, Page 576, 10, 576 (2020).R. Akolkar, J. Electrochem. Soc., 169, 043501 (2022).D. Shen and R. Akolkar, J. Electrochem. Soc., 164, H5292–H5298 (2017).

Batteries Worth Their Salt: Targeting Next Generation Stationary Storage with Molten Salt Electrolytes

There is an imminent need for batteries capable of meeting the evolving demands of a growing stationary storage landscape, one rich in renewable energy sources and challenged with unprecedented global electrification. Key to our future electrical grid, desirable large-scale, long-duration batteries must not only meet demands for high power and energy density, but they must be safe, cost-effective, and should be sustainably sourced from earth-abundant materials. Here, we will highlight our research and development of low temperature molten salt batteries that employ active materials such as sodium, aluminum, iron, chloride, and iodide. We will demonstrate the promise of our approach through a low-temperature (100°C) molten sodium battery that comprises a molten sodium anode, a solid-state NaSICON ceramic separator, and a low-cost molten metal-halide salt catholyte. These batteries, with remarkable voltages greater than 3.1V, are capable of months of cycling as well as high current charge and discharge behavior, greater than 50mA/cm2. Here, we will not only highlight these performance metrics, but we will describe how we used specialized electrochemical and chemical characterization technique to understand the impacts of molten salt electrolyte composition, electrochemistry, and interfacial interactions on battery performance. By understanding the connections between specific electrochemical phenomena and battery chemistry, we have learned to improve battery performance through tuning of properties, such as molten salt Lewis acidity and current collector composition. This scientifically-motivated battery design approach continues to enable agile innovation and advances to realize the potential of molten salt batteries as a new, impactful stationary storage technology.Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.

Electrodeposition Behavior of Al-Au Alloys in AlCl3-NaCl-KCl-Aucl Molten Salt

Quartz Crystal Microbalance (QCM) has been used as a highly sensitive mass sensor. This study aims to form porous gold thin films on QCM elements and apply them to highly sensitive gas sensors by attaching selective media. Physical vapor deposition and chemical etching are known methods for forming porous Au thin films. In this study, the electrochemical formation of porous gold films in AlCl3-NaCl-KCl molten salts containing AuCl was investigated. There are few reports about electrodeposition and dissolution potentials of Au in the molten salt electrolyte. As a first step in this study, voltammogram measurements and constant potential electrolysis were performed in the electrolyte, and electrodeposition potentials of Au and Al-Au alloys were discussed.An electrolyte in this study is a mixture of 61 mol% AlCl3- 26 mol% NaCl- 13 mol% KCl molten salt. The mixture salt was melted at 443 K and AuCl was added to the molten salt. A glassy carbon plate (GC) and a pure Al wire were used as the working electrode and reference electrode, respectively. The GC plate and Au mesh were used as the counter electrode for voltammogram measurement and constant potential electrolysis, respectively. Voltammogram measurements were carried out at potential range from -0.1 to 2.4 V vs. Al/Al(Ⅲ). Constant potential electrolysis was performed in the range from -0.2 to 0.3 V with an electric charge density of 40 C cm-2. The electrodeposits were observed by scanning electron microscopy (SEM) and determined the composition of Al and Au by energy dispersive X-ray spectroscopy (EDS).Au ions concentration in the electrolyte was 2.5 mmol dm-3. In voltammogram measurements, a small cathodic current was observed at about 0.8 V, then gradually increased from 0.2 V. In the potential lower than 0 V, a drastical increase of cathodic current was observed, which was attributed to Al electrodeposition. When the potential was reversed, large anodic current flowed from 0 V and a small current peak was also observed at 0.2 V. These were considered to correspond to the dissolution of Al and Al-Au alloys, respectively. Furthermore, a relatively large anodic current peak was observed at about 2 V, which was expected to be due to the dissolution of Au. From the results of constant potential electrolysis, the Au concentration in the electrodeposits at -0.1 V and -0.2 V was less than 1 at%. At 0 V, the Au concentration in the electrodeposit increased sharply to 84 at%, and at 0.3 V it increased moderately to 89 at%. From SEM observation, the morphology of the electrodeposits at -0.1 V and -0.2 V was dense, while that at potentials more than 0 V was sponge-like.AcknowledgementsThis work was supported by JST SICORP and JPMJSC2108.

Electrolytic Reduction of UO2 Microspheres Synthesized Via Internal Gelation Method

Pyroprocessing is the combination of process steps to extract and recycle actinides from fission products in spent nuclear fuels in high-temperature molten salt media. Pyroprocessing has been studied extensively over the past decades. One of the key sub-processes is the electrolytic reduction of uranium oxides. The electrolytic reduction process originated from the FFC Cambridge process, an approach for electrochemically reducing titanium dioxide into titanium metal in molten CaCl2. In the electrolytic reduction of uranium oxides, the uranium oxide feed is applied as the cathode in LiCl-Li2O molten salt electrolyte at 650°C. LiCl appears more promising than conventional CaCl2 owing to the lower melting point (878 K), and higher decomposition voltage (3.46 V at 923 K). Additionally, Li2O is expected to speed up the reduction via an additional chemical reduction pathway with the participation of Li metal, and prevents the direct dissolution of the Pt anode.This work aims to study the morphology effect of the oxide feed on the reduction kinetics and the incorporation of impurities during the electrolytic reduction process. The electrolytic reduction of UO2 is carried out on sintered UO2 pellets, as well as various UO2 microspheres synthesized via internal gelation. The introduction of uranium oxide microspheres holds several advantages. The spheres provide a higher surface area, which is expected to improve the overall reduction efficiency of uranium oxide during electrolysis. In addition, it is easier to handle the feed during loading and unloading of the cathode basket compared to powder feeds.The potentiostatic and galvanostatic electrolysis of UO2 is performed, and the comparison between the electrolytic reduction of UO2 pellets and microspheres is investigated. The SEM micrographs in figure 1show the morphology change of a UO2 pellet to uranium metals particles. A significant morphology change between the flat surface of the sintered UO2 feed and the reduced U particles is observed at the surface. Further characterization is performed using XRD and TGA to identify the products of the electrolytic reduction process qualitatively and quantitatively. Results show that galvanostatic electrolysis shows a better reduction efficiency compared to potentiostatic electrolysis, applied both below and above the Li formation onset potential. Overall, there is barely un-reacted UO2 visible in the XRD patterns of the reduced feed after galvanostatic electrolysis. U metal and UO are identified in the XRD patterns depending on electrolysis parameters. The presence of UO can be as an intermediate of UO2 reduction during electrolysis, which is a rare compound to be reported in literature. Overall, the reduction of microspheres does improve the overall reduction efficiency compared to the conventional pellet feeds. Figure 1

Molten Salt Based High Entropy Electrolytes for Calcium Batteries

Calcium (Ca) is in principle a very attractive metal anode for rechargeable batteries due to the large abundance of calcium in the Earth’s crust, its low electrochemical potential, and its low cost1. Until rather recently2, however, stable plating and stripping of Ca and hence rechargeability of Ca-batteries was deemed impossible, due to the stable phases formed at the electrolyte/electrode interface, completely blocking Ca2+ transfer3.Since this pivotal breakthrough, Ca-batteries have attracted more interest, but they are still in their very infancy and new battery designs – such as using novel electrolyte concepts – are needed to achieve stable cycling of Ca metal anodes, and this preferably at room temperature.Here we report on the use of molten salt electrolytes, i.e. binary and multi-component systems of inorganic cations and anions, and more specifically on their physico-chemical and electrochemical properties as a function of composition with special emphasis on the compositional entropy. By using completely solvent-free electrolytes issues associated with organic electrolytes and solvents, such as the blocking of Ca2+ transfer and electrolyte flammability3, are avoided. Furthermore, they should/do not induce any large polarization, as opposed to ionic liquid-based electrolytes4.In more detail, using the Ca(FSI)2 salt in combination with the analogous Li-, Na-, and KFSI salts in equimolar compositions, all with melting temperatures (significantly) above 100 °C, we can create electrolytes melting at ca. 60-75 °C for the ternary systems, which is further reduced to ca. 55 °C for the quaternary system. These lowered melting temperatures are achieved by increased entropy of mixing, reducing the Gibbs free energy. This can for example be illustrated by Raman spectroscopy via comparing the spectra of “as cast” electrolytes with the spectra for the ones “aged” for one week (Figure 1). Here the FSI anion band at 772 cm-1 (νsS-N-S)5 shows that the electrolytes partially (re-)crystallize/micro-separate for the ternary systems, but stay more stable for the quaternary system, which we, at least partially, attribute to an entropy effect. Reference s M. E. Arroyo-De Dompablo, A. Ponrouch, P. Johansson, and M. R. Palacín, Chem . Rev., 120, 6331–6357 (2020).A. Ponrouch, C. Frontera, F. Bardé, and M. R. Palacín, Nat. Mater., 15, 169–172 (2016).D. Aurbach, R. Skaletsky, and Y. Gofer, J . Electrochem Soc., 138, 3536–3545 (1991).Q. Pang et al., Nature, 608, 704–711 (2022).K. Matsumoto, T. Oka, T. Nohira, and R. Hagiwara, Inorg . Chem ., 52, 568–576 (2013). Figure 1

Study on the Influence of CaO on the Electrochemical Reduction of Fe2O3 in NaCl-CaCl2 Molten Salt.

The presence of calcium-containing molten salts in the electrolysis of oxides for metal production can lead to the formation of CaO and, subsequently, the generation of intermediate products, affecting the reduction of metals. To investigate the impact of CaO on the reduction process, experiments were conducted using a Fe2O3-CaO cathode and a graphite anode in a NaCl-CaCl2 molten salt electrolyte at 800 °C. The electrochemical reduction kinetics of the intermediate product Ca2Fe2O5 were studied using cyclic voltammetry and I-t curve analysis. The phase composition and morphology of the electrolysis products were analyzed using XRD, SEM-EDS, and XPS. The experimental results demonstrate that upon addition of CaO to the Fe2O3 cathode, Ca2Fe2O5 is formed instantly in the molten salt upon the application of an electrical current. Research conducted at different voltages, combined with electrochemical analysis, indicates that the reduction steps of Ca2Fe2O5 in the NaCl-CaCl2 molten salt are as follows: Ca2Fe2O5 ⟶ Fe3O4 ⟶ FeO ⟶ Fe. The presence of CaO accelerates the electrochemical reduction rate, promoting the formation of Fe. At 0.6 V and after 600 min of electrolysis, all of the Ca2Fe2O5 is converted into Fe, coexisting with CaCO3. With an increase in the electrolysis voltage, the electrolysis product Fe particles visibly grow larger, exhibiting pronounced agglomeration effects. Under the conditions of a 1 V voltage, a study was conducted to investigate the influence of time on the reduction process of Ca2Fe2O5. Gradually, it resulted in the formation of CaFe3O5, CaFe5O7, FeO, and metallic Fe. With an increased driving force, one gram of Fe2O3-CaO mixed oxide can completely turn into metal Fe by electrolysis for 300 min.

How cell design affects the performance of sodium-antimony-bismuth liquid metal batteries

Low-cost sodium-based liquid metal batteries are attractive candidates for grid-scale stationary energy storage. In this study, the performance of Na//SbBi9 test cells with molten salt electrolyte LiCl–NaCl–KCl (61-3-36 mol%) is evaluated for different cell designs. Cells with a metal foam hosting the negative electrode (5–6 Ah nominal capacity) and cells without foam are investigated. Additionally, the amount of electrolyte and the material used as positive current collector (PCC) are varied. The self-discharge current is only ∼0.35 mA/cm2 and depends reasonably on electrode distance and operating temperature. Contact resistances are 10 mΩ in total and thus smaller than the ohmic resistance of the electrolyte. The cell voltage is not affected by cell design, operating temperature, or cell age. Long-term cycling tests show a capacity decrease, which can be attributed to evaporation of Na. An additional capacity loss observed in cells with stainless steel PCC can be avoided by using Mo as PCC.

An Efficient and Stable Lithium‐Oxygen Battery Based on Metal‐Organic Framework Separator Operating at 160 °C

AbstractA lithium oxygen battery (LOB) with molten salt electrolyte operating at elevated temperature has aroused great interest because it enables fast reaction kinetics. However, there is still a lack of open literature on the separator (membrane) of this kind of LOB. Metal‐organic framework (MOF) materials are widely used as components of separators in many kinds of energy storage devices, due to their regular crystalline and well‐defined pore structures. In this work, a MOF material, zirconium (II) 1,4‐benzenedicarboxylate after lithiation (UiO‐66‐SO3Li) with a narrow pore size (6 Å), is used as a key component of the separator for LOB operating at elevated temperature. A “rolling dough” method is adopted to prepare the separator, which achieves 100% material utilization. The LOB with this membrane operates at 160 °C and delivers a specific capacity of 5.1 mAh cm−2 with an overpotential as low as 40 mV at 0.1 mA cm−2 and a prolonged cycle life, 180 cycles with a high coulombic efficiency of 99.9% at 0.5 mA cm−2. This MOF‐based membrane provides efficient Li+ transfer and restricts discharge product migration during battery operation, which is promising for the development of LOB in large‐scale practical applications.

Low melting alkali-based molten salt electrolytes for solvent-free lithium-metal batteries

Low melting alkali-based molten salt electrolytes for solvent-free lithium-metal batteries

A continuous multiphase model for liquid metal batteries

Liquid metal batteries (LMBs) are a promising candidate for large-scale stationary storage of renewably generated energy. Their Earth-abundant electrode materials and highly conductive molten salt electrolytes confer the low costs and high power densities required for grid-scale storage. LMB operation involves a complex interplay between mass transport mechanisms, and as a result their performance potential and operational limits are not fully understood. In this study, a multiphase numerical model is presented that simulates the charge and discharge processes of an LMB based on the Na-Zn couple. The model computes the changes in electrode and electrolyte volume, and resolves the spatial variations in the chemistry of the electrolyte that accompany the interfacial reactions. Volume change and species redistribution were found to be important in predicting the maximum theoretical capacity of the cell when neglecting other transport mechanisms.

Molecular Dynamics Simulation of the Effect of Zr, B, C, W, Ti, Hf, Nb, and Ta Elements on the K3AlF6-Na3AlF6-AlF3 Molten Salt System

The criticality of the physicochemical properties of the K3AlF6-Na3AlF6-AlF3 molten salt system to electrolytic aluminum production is a topic of great interest. In this study, molecular dynamics simulations were conducted to investigate the impact of Zr, B, C, W, Ti, Hf, Nb, and Ta on various properties including the radial distribution function, coordination number, viscosity, and conductivity of the 23.4K3AlF6-54.6Na3AlF6-22AlF3 molten salt electrolyte under conditions of 1173 K and standard atmospheric pressure. Significant and noteworthy discoveries were yielded by the simulations. A decrease in the coordination between Al-F and conductivity was brought about by the inclusion of B2-. Likewise, higher Zr4+ content resulted in a decrease in the coordination number between Al-F and viscosity. The impact of carbon was insignificant, while the presence of tungsten reduced the coordination number between Al-F. On the other hand, titanium, hafnium, niobium, and tantalum facilitated the decomposition of Al-F ligands, leading to an increased coordination between Al-F and the ions in the electrolyte. These findings provide valuable insights for future investigations on inert anodes containing Zr, B, Ti, Hf, Nb, and Ta. By understanding the effects of these elements on the physicochemical properties of the molten salt electrolyte, this work lays a solid foundation for further research in the field.

Study of Lithium-Silicon Anode Materials for Thermal Batteries

Thermal batteries are constructed from a molten salt electrolyte which is solid at room temperature, a FeS2 positive electrode and a lithium-silicon negative electrode. The typical operating temperature of the battery is between 350 to 500°C. Thermal batteries use an inorganic salt as the electrolyte such as binary or ternary alkali halide eutectics. For example, LiCl-KCl and LiF-LiCl-LiBr. At a composition of 44.8 LiCl and 55.2 KCl wt%, the melting point is around 353°C for LiCl-KCl. Molten salts have a very high electrical conductivity, so thermal batteries have a higher power density than room temperature batteries. In this work, LiCl-KCl eutectic was used for electrochemical testing. The performance of an electrode can be studied in single-cell discharge tests where a discharge profile is obtained. The tests were carried out in a cell testing rig inside an argon glovebox. The cells were made from pellets which were placed in a Swagelok casing. The cells were made from 0.15g of FeS2 mixed with 0.05g LiCl-KCl as the positive electrode, 0.2g of LiCl-KCl with 35% wt MgO as the electrolyte and 0.2g of Li13Si4 as the negative electrode. Lithium silicides were made using solid state synthesis in a tube furnace. The electrochemical tests show that the Li13Si4 is a better negative electrode material than Li7Si3 (Figure 1). In addition, powder neutron diffraction was used to probe the lithium silicides with increasing temperature. The high-temperature behaviour of Li13Si4 and Li7Si3 was studied in March 2020 by the JTSI group at the ISIS neutron source, Rutherford Appleton Laboratory, UK. The data gives information on structural changes in Li13Si4 and Li7Si3. The results indicate that Li13Si4 and Li7Si3 remain remarkably stable at 500°C. There are no phase transitions in the materials from room temperature to 500°C and the materials remain crystalline. These findings give a clearer understanding of thermal battery discharge processes. Figure 1