Thin silicon layers containing about 20% carbon and 20% oxygen were deposited on copper substrates by potentiostatic electroreduction from a 1 M SiCl4 1-butyl-1-methyl-pyrrolidinium bis (trifluoromethyl) sulfonylimide [BMP][TFSI] electrolyte. The electrodeposition process was investigated by means of voltammetric techniques, coupled with in-situ microgravimetry (quartz crystal microbalance, QCM). The electrochemical and QCM data suggest a possible contribution of a partial Si4+ to Si2+ reduction and/or a restructuring of the metallic substrate. Considerable impact of side reactions parallel to the deposition process was indicated by QCM measurements performed under potentiostatic and potentiodynamic conditions. The deposition of silicon-based films was confirmed by energy dispersive X-ray analysis (EDX). Analysis of the chemical composition of the deposit and its elemental distribution were achieved by depth profiling X-ray photoelectron spectroscopy (XPS). The electrodeposited silicon containing layers showed stable lithiation and delithiation with capacity values of about 1200 mAhg (1) and 80% capacity retention after 300 cycles in standard EC/DMC electrolytes. In ionic liquid (IL) the material displayed lower capacity of ca. 500 mAhg (1), which can be attributed to the higher viscosity of this electrolyte and deposition of IL decomposition products during lithiation. (C) 2015 Elsevier Ltd. All rights reserved.