High-temperature electrochemistry of calcium

Electrolytically produced calcium is one of the most demanded materials in obtaining pure materials. At the same time, the existing technologies and devices for the electrolytic production of calcium were developed in the last century, and at present there are practically no works aimed at optimizing them. However, increasing the capacity and efficiency of existing devices for the production of calcium is in demand. To analyze possible ways to improve calcium production, a comprehensive understanding of the processes occurring at the electrodes and in the electrolyte during electrolytic production of calcium is required.This review briefly outlines the main points concerning the electrolytic production of calcium: from a brief history of the development of methods for the electrolytic production of calcium and established ideas about its physicochemical processes to information about new developments using the electrolysis of CaCl2-based melts. Review content: brief history of process development; base electrolyte for calcium production, including preparation of CaCl2 and influence of additions on it physicochemical properties; data on calcium solubility in CaCl2; information about alternative electrolytes for calcium production; short description of electrode processes in the CaCl2-based melts; proposed technologies and devices for the electrolytic production of calcium. keywords: calcium, calcium chloride, ion-electron liquid, Cu–Ca alloy, molten salt, calcium solubility, electrode processes, inert anode, electrolysis, current efficiency, electrolyzer DOI: https://doi.org/10.15826/elmattech.2022.1.00

Electroreduction of silicon from the NaI–KI–K2SiF6 melt for lithium-ion power sources

Silicon and silicon-based materials are increasingly used in microelectronics, metallurgy and power generation. To date the active study aimed at the development of silicon materials to be used in devices for solar energy conversion, accumulation and storage is underway. In addition, silicon is a promising anode material for lithium-ion fuel cells. In the present paper a possibility of silicon electroreduction from the NaI–KI–K2SiF6 melt in the argon atmosphere is studied. With this aim in view the electrolysis of the NaI–KI–K2SiF6 melt with glassy carbon cathode was performed under galvanostatic and potentiostatic regimes at the temperatures ranging from 650 to 750 °С. The morphology, phase and elemental analyses of the obtained silicon deposits were performed after their separation from the electrolytes by the ICP, SEM-EDX, XRD and Raman spectroscopy methods. Fiber and thread-like silicon samples of 60 to 320 nm in dimeter with admixtures concentrations (mainly oxygen) from 1.2 to 4.6 wt.% were experimentally synthesized. The obtained samples were tested as possible Si/C composite anodes for lithium-ion power sources. The discharge capacity of such power sources after 30 cycles of lithiation-delithiation ranged from 440 to 565 mAh·g–1 and the coloumbic efficiency ranged from 89 to 91%

Silicon Electrodeposition for Microelectronics and Distributed Energy: A Mini-Review

Due to its prevalence in nature and its particular properties, silicon is one of the most popular materials in various industries. Currently, metallurgical silicon is obtained by carbothermal reduction of quartz, which is then subjected to hydrochlorination and multiple chlorination in order to obtain solar silicon. This mini-review provides a brief analysis of alternative methods for obtaining silicon by electrolysis of molten salts. The review covers factors determining the choice of composition of molten salts, typical silicon precipitates obtained by electrolysis of molten salts, assessment of the possibility of using electrolytic silicon in microelectronics, representative test results for the use of electrolytic silicon in the composition of lithium-ion current sources, and representative test results for the use of electrolytic silicon for solar energy conversion. This paper concludes by noting the tasks that need to be solved for the practical implementation of methods for the electrolytic production of silicon, for the development of new devices and materials for energy distribution and microelectronic application

Efficiency of Electrochemical Methods of Purification and Control over the Oxide Concentration in Halide Melts: PbCl₂

The purification of molten salts from admixtures as well as the effective control of admixture concentration has attracted researchers’ interests. In the present paper, the possibility of the electrochemical purification of PbCl2 from PbO and the effective control over the oxide ions concentration in molten PbCl2 is studied at the temperature of 520 °C. The PbCl2 melt with the initial addition of 0.5 wt% of PbO was used as a molten salt sample. The method of potentiostatic electrolysis was used to remove the oxide additions from the melt; the linear and square-wave voltammetry dependencies were recorded, and the melt samples were taken for analysis. Based both on the results of the electrochemical measurements and the analysis of oxygen concentration in the electrolyte, we built linear empirical dependencies of the anode peak current of the oxidation of oxygen-containing electroactive anions on the PbO concentration in the studied melt. We demonstrated that the obtained dependencies may be used for direct electrochemical nondestructive in-situ control over the concentration of PbO dissolved in the PbCl2 melt containing up to 0.5 wt% of PbO. The deep electrochemical purification of the chloride PbCl2 melt from molten oxide (up to 0.044 wt% PbO or to 0.007 wt% of oxygen) was achieved by the potentiostatic electrolysis

Electrodeposition of Silicon Fibers from KI–KF–KCl–K₂SiF₆ Melt and Their Electrochemical Performance during Lithiation/Delithiation

The possibility of using Si-based anodes in lithium-ion batteries is actively investigated due to the increased lithium capacity of silicon. The paper reports the preparation of submicron silicon fibers on glassy carbon in the KI–KF–KCl–K2SiF6 melt at 720 °C. For this purpose, the parameters of silicon electrodeposition in the form of fibers were determined using cyclic voltammetry, and experimental samples of ordered silicon fibers with an average diameter from 0.1 to 0.3 μm were obtained under galvanostatic electrolysis conditions. Using the obtained silicon fibers, anode half-cells of a lithium-ion battery were fabricated, and its electrochemical performance under multiple lithiations and delithiations was studied. By means of voltametric studies, it is observed that charging and discharging the anode based on the obtained silicon fibers occurs at potentials from 0.2 to 0.05 V and from 0.2 to 0.5 V, respectively. A change in discharge capacity from 520 to 200 mAh g−1 during the first 50 charge/discharge cycles at a charge current of 0.1 C and a Coulombic efficiency of 98–100% was shown. The possibility of charging silicon-based anode samples at charging currents up to 2 C was also noted; the discharge capacity ranged from 25 to 250 mAh g−1

IN-SITU MONITORING ALUMINA DURING ALUMINIUM ELECTROLYTIC PRODUCTION

Alumina content in electrolysis cells for aluminum production is one of the most important and poorly controlled parameters. In order to check the current value of alumina content as well as the dissolution of alumina in industrial electrolytes (NaF-AlF3-CaF2-Al2O3), a novel electrochemical sensor was proposed. It was comprised of a carbon working electrode and a counter electrode interacting with aluminum. The sensor was easy to manufacture, and it allowed reducing the measurement error associated with back reactions at the working electrode. The novel approach was considered on an example of dissolving the alumina in the NaF-AlF3-(5 wt%)CaF2 melt ([NaF]/[AlF3] = 2.1 mol/mol) containing alumina (Al2O3) in amount of 0.69-4.51 wt% at 995 °C in conditions of natural and forced convection. It was found that the alumina solubility in the studied melt was 4.51 wt%. Depending on the initial content of alumina in the melt and convection conditions, its dissolution rate varied up to 0.36 mol/s·m3

Synthesis of C/SiC Mixtures for Composite Anodes of Lithium-Ion Power Sources

Nowadays, research aimed at the development of materials with increased energy density for lithium-ion batteries are carried out all over the world. Composite anode materials based on Si and C ultrafine particles are considered promising due to their high capacity. In this work, a new approach for carbothermal synthesis of C/SiC composite mixtures with SiC particles of fibrous morphology with a fiber diameter of 0.1–2.0 μm is proposed. The synthesis was carried out on natural raw materials (quartz and graphite) without the use of complex equipment and an argon atmosphere. Using the proposed method, C/SiC mixture as well as pure SiC were synthesized and used to manufacture anode half-cells of lithium-ion batteries. The potential use of the resulting mixtures as anode material for lithium-ion battery was shown. Energy characteristics of the mixtures were determined. After 100 cycles, pure SiC reached a discharge capacity of 180 and 138 mAh g−1 at a current of C/20 and C, respectively, and for the mixtures of (wt%) 29.5C–70.5 SiC and 50Si–14.5C–35.5SiC discharge capacity of 328 and 400 mAh g−1 at a current of C/2 were achieved. The Coulombic efficiency of the samples during cycling was over 99%