As an anode material for liquid lithium-ion batteries, film structures consisting of several identical modules [Co(x)/a-Si(100)/Cu(70)], where the value of x varied from 2 to 10 nm, have been studied. It is shown that relatively thick cobalt layers are effective diffusion barriers for silicon and copper atoms, as well as lithium ions. This leads to a decrease in the capacitive properties of the studied films. Thin cobalt layers (less than 3 nm) with a network structure, on the contrary, contribute to an increase in the capacitive properties of anode films. This is due to a more uniform distribution in their volume of drift channels of lithium ions, which are formed at the initial stage of electrode cycling.