Insight is given on the type of ion-pairs that could be formed in EC/DMC by Li-salts LiTDI, LiFSI and LiPF6.

The (de)lithiation process and resulting atomic and nanoscale morphological changes of an a-Si/ c-FeSi 2 /graphite composite negative electrode are investigated within a Li-ion full cell at several current rates (Crates) and after prolonged cycling by simultaneous operando synchrotron wide-angle and small-angle X-ray scattering (WAXS and SAXS). WAXS allows the probing of the local crystalline structure. In particular, the observation of the graphite (de)lithiation process, revealed by the Li x C 6 Bragg reflections, enables access to the respective capacities of both graphite and active silicon. Simultaneously and independently, information on the silicon state of (de)lithiation and nanoscale morphology (1 to 60 nm) is obtained through SAXS. During lithiation, the SAXS intensity in the region corresponding to characteristic distances within the a-Si/c-FeSi 2 domains increases. The combination of the SAXS/WAXS measurements over the course of several charge/ discharge cycles, in pristine and aged electrodes, provides a complete picture of the C-rate-dependent sequential (de)lithiation mechanism of the a-Si/c-FeSi 2 /graphite anode. Our results indicate that, within the composite electrode, the active silicon volume does not increase linearly with lithium insertion and point toward the important role of the electrode morphology to accommodate the nanoscale silicon expansion, an effect that remains beneficial after cell aging and most probably explains the excellent performance of the composite material.