The HEROES-Li project aims to design new "all solid" electrolytes for lithium-ion battery technology by combining the intrinsic properties of polysiloxane materials and ionomers. These new generation of electrolytes will allow more efficient and safer storage of electrical energy. The ionic conduction provided by the ionic Li+ groups carried by the main Sol-Gel phase will be assisted by the non-binding doublets of the oxygen atoms of the SG phase but also by the ionic Li+ groups of the host membrane. These hybrid membranes will be obtained by direct impregnation of the host ionomer membrane without dissolution. The host membrane will thus have a structuring effect on the growth of the SG phase thanks to its well-defined conduction paths. An in-depth multi-scale characterization of the physicochemical properties of the obtained hybrid membranes will be carried out in order to determine the structure/ionic transport/durability relationships.