In this work novel approaches to fabricate silicon-based electrodes are shown. Starting from silicon nano-particles it is possible to create nano-structured porous thin films. Both the synthesis of the Si nano-particles and the electrode assembly are performed via aerosol routes. This guarantees a very good control on the particle size and the particle size distribution, on the purity of the product and on the morphology and texture of the deposited layers. Particles are produced via Laser assisted Chemical Vapor Pyrolysis whereas electrode thin layers are deposited via Electro Spray method. The range of particle sizes can be tailored according to the selected application. Here, particles of a mean size of about 10 nm have been synthesized. Since Si is well known to forms highly lithiated intermetallic compounds [1], it is regarded as one of the most promising material for energy storage [2], especially looking at high energy density applications, such as hybrid/electric vehicle traction. In this work its promising performance are presented. The role of the additives in the composite formulation is also taken into account for a more clear understanding of the capacity fading mechanism of such electrodes.