Silicon electrodeposition from the KF-KCl-K₂SiF₆ and KF-KCl-KI-K₂SiF₆ melts

Silicon and silicon-based materials find extensive applications in metallurgy, microelectronics, and other emerging industries. The field of use of synthesized silicon varies based on its morphology and purity. This study employs voltammetry, galvanostatic electrolysis, and scanning electron microscopy to examine the impact of KI surfactant (in mol %) to 66.5KF–33.3KCl–0.23K₂SiF₆ melt at 750°C on the electrowinning kinetics of silicon ions and the morphology of silicon deposits formed on a glassy carbon electrode. The findings demonstrate that the addition of potassium iodide to the KF–KCl–K₂SiF₆ melt at a concentration of 2 mol % induces changes in interfacial tension at the boundary between the glassy carbon, melt, and atmosphere. Consequently, the wetting of the glassy carbon with the melt decreases, leading to a reduction in the actual working surface area and, consequently, a decrease in cathode current while maintaining current density. Taking into account this effect and employing an algebraic estimation of the influence of the melt meniscus shape, it is postulated that the addition of KI does not significantly affect the kinetics of the cathode process. Nevertheless, the impact of KI addition on the morphology of electrodeposited silicon is mentioned. During the electrolysis of the KF–KCl–K₂SiF₆ melt, fibrous silicon deposits with arbitrary shapes are formed on the glassy carbon electrode, whereas the addition of 2 and 4 mol % of potassium iodide to the melt leads to the agglomeration and smoothing of silicon deposits under the same electrolysis conditions (cathode current density: 0.02 A/cm², electrolysis duration: 2 h). The obtained results indicate the potential to manipulate the morphology of electrodeposited silicon for specific applications in various fields.

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