The results of measuring the charge-discharge characteristics of solid-state thin-film lithium-ion batteries with a nanocomposite anode based on the a-Si(Al) solid solution are presented. The charging characteristics of batteries have a feature in the form of a step on the gentle branch of the U(t) curve. It has been suggested and substantiated that the appearance of the step is related to the gradual compensation and change of the a-Si(Al) hole conductivity to electronic one as the lithium concentration increases. As a result, the a-Si(Al)|Ti ohmic contact becomes rectifying, and the electrons participating in the Faraday process have to overcome the Schottky barrier. The potential growth required to maintain the galvanostatic charge regime manifests itself as a step on the charge curve. Keywords: thin film solid-state lithium-ion battery, amorphous silicon, solid solution, sp3 hybridization, lithiation, Schottky barrier.