The results on the study of functional layers of a solid-state thin-film lithium-ion batteries are presented. Thin-films of lithium cobaltite (positive electrode), silicon nanocomposite (negative electrode) and lithium phosphorus-oxynitride (solid electrolyte) were studied by the methods of electron microscopy, energy dispersive analysis and X-ray phase analysis. Technological modes have been determined which make it possible to obtain functional layers with a large-block and columnar structure providing the full depth of electrodes lithiation-delithiation and high ionic conductivity of the solid electrolyte.