In situ electrochemical techniques can be used to investigate the intercalation process of lithium into several inserting materials used in rechargeable lithium battery anodes. Alloying materials on the basis of aluminium, with the addition of small portions of a second metal such as nickel or manganese, are especially examined. The chemical diffusion coefficient of lithium was estimated using the potentiostatic transient technique. Chronoamperometry gives information on the diffusion process related to the chemical composition, grain structure and crystallinity of the alloying material. The measurements have been carried out in a 1M LiClO4/propylene carbonate solution at room temperature.