Provided are novel electrode material composite structures containing high capacity active materials formed into porous base structures. The structures also include shells that encapsulate these porous base structures. During lithiation of the active material, the shell mechanically constrains the porous base structure. The shell allows lithium ions to pass through but prevents electrolyte solvents from interacting with the encapsulated active material. In certain embodiments, the shell contains carbon, while the porous base structure contains silicon. Although silicon tends to swell during lithiation, the porosity of the base structure and/or void spaces inside the shell helps to accommodate this additional volume within the shell without breaking it or substantially increasing the overall size of the composite structure. This allows integration of the composite structures into various types of battery electrodes and cycling high capacity active materials without damaging the electrodes' internal structures and deteriorating cycling characteristics of batteries.