| Summary: | Currently, silicon and silicon-based composite materials are widely used in microelectronics and solar energy devices. At the same time, silicon in the form of nanoscale fibers and various particles morphology is required for lithium-ion batteries with increased capacity. In this work, we studied the electrolytic production of nanosized silicon from low-fluoride KCl–K<sub>2</sub>SiF<sub>6</sub> and KCl–K<sub>2</sub>SiF<sub>6</sub>–SiO<sub>2</sub> melts. The effect of SiO<sub>2</sub> addition on the morphology and composition of electrolytic silicon deposits was studied under the conditions of potentiostatic electrolysis (cathode overvoltage of 0.1, 0.15, and 0.25 V vs. the potential of a quasi-reference electrode). The obtained silicon deposits were separated from the electrolyte residues, analyzed by scanning electron microscopy and spectral analysis, and then used to fabricate a composite Si/C anode for a lithium-ion battery. The energy characteristics of the manufactured anode half-cells were measured by the galvanostatic cycling method. Cycling revealed better capacity retention and higher coulombic efficiency of the Si/C composite based on silicon synthesized from KCl–K<sub>2</sub>SiF<sub>6</sub>–SiO<sub>2</sub> melt. After 15 cycles at 200 mA·g<sup>−1</sup>, material obtained at 0.15 V overvoltage demonstrates capacity of 850 mAh·g<sup>−1</sup>.
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