With view on the further energy increase at cell level, so-called “lithium storage metals”, in particular silicon (Si) arise a lot of interest as possible next generation negative electrode materials due to their high theoretical specific capacity of 3,579 mAh g-1 corresponding to crystalline Li15Si4, high abundance and low costs. However, Si still suffers from severe drawbacks hindering its commercial breakthrough so far, which are most likely related to the large volume changes (up to 300%) during lithiation/de-lithiation, thus, leading to a disconnection of the active Si particles from the electronically conductive network. Moreover, in contrast to graphite anodes, where the electrolyte reduction and corresponding solid electrolyte interphase (SEI) formation is mainly limited to the initial cycles, the SEI formation for Si-based anodes is a dynamic process of breaking off and reforming, due to the constant structural changes during cycling. This leads to a huge irreversible capacity as well as high active lithium losses and a continuous increase in interfacial resistance upon charge/discharge cycling, which results in rapid capacity fading and short cycle life.