New results for two types of nano-size silicon, prepared via thermal vapour deposition either with or without a graphite substrate are presented. Their superior reversible charge capacity and cycle life as negative electrode material for lithium-ion batteries have already been shown in previous work. Here the lithiation reaction of the materials is investigated more closely via different electrochemical in situ techniques: Raman spectroscopy, dilatometry and differential electrochemical mass spectrometry (DEMS). The Si/graphite compound material shows relatively high kinetics upon discharge. The moderate relative volume change and low gas evolution of the nano silicon based electrode, both being important points for a possible future use in real batteries, are discussed with respect to a standard graphite electrode.