Silicon nano- and microwires have been obtained by KCl-KF-K2SiF6-SiO2 melt electrolysis in air; this material is suitable as anode component for lithium ion batteries. Optimal conditions of electrolysis were determined. Morphology, phase and chemical composition of silicon deposits were established. Electrochemical behavior of silicon nanowires as anode component was evaluated using solid polymer electrolyte cells.