Abstract <p>Due to increased lithium capacity silicon and silicon-based materials appear promising for their use in high-power lithium-ion power sources. In the present work a comparative analysis of the electrochemical behavior of electrodeposited thin films, submicron fibers, and needles during their multiple lithiation and delithiation as part of the anode half-cell of a lithium-ion power source has been performed. Silicon samples electrodeposited from molten KCl–K₂SiF₆–SiO₂, KCl–CsCl–K₂SiF₆, and LiCl–KCl–CsCl–K₂SiF₆ electrolytes were taken for comparison. The kinetics of lithiation and delithiation of samples was studied by cyclic voltammetry, and the behavior of silicon samples during multiple lithiation was studied by galvanostatic electrolysis with limitation of the anode potential to 0.05 V relative to the lithium potential. As a result of the studies, it is shown that the silicon samples possess discharge capacity from 20 to 1500 mA h g^–1 depending on the charge and discharge current (from 0.1 to 2 C). At the same time, in the course of multiple lithiation, a gradual decrease in the charging and discharging capacity of all the studied samples was observed as a result of silicon expansion, which leads to the formation of new surfaces for the formation of SEI, and the degradation of electrical contacts both in the volume of the anode mass and between the anode and the substrate.</p>