Coexistence of both edge plane and basal plane in graphite often hinders the understanding of lithium ion diffusion mechanism. In this report, two types of graphene samples were prepared by chemical vapor deposition (CVD): (i) well-defined basal plane graphene grown on Cu foil and (ii) edge plane-enriched graphene layers grown on Ni film. Electrochemical performance of the graphene electrode can be split into two regimes depending on the number of graphene layers: (i) the corrosion-dominant regime and (ii) the lithiation-dominant regime. Li ion diffusion perpendicular to the basal plane of graphene is facilitated by defects, whereas diffusion parallel to the plane is limited by the steric hindrance that originates from aggregated Li ions adsorbed on the abundant defect sites. The critical layer thickness (lc) to effectively prohibit substrate reaction using CVDgrown graphene layers was predicted to be ∼6 layers, independent of defect population. Our density functional theory calculations demonstrate that divacancies and higher order defects have reasonable diffusion barrier heights allowing lithium diffusion through the basal plane but neither monovacancies nor Stone-Wales defect.

a b s t r a c tThe effect of the Si electrode morphology (amorphous hydrogenated silicon thin films -a-Si:H as a model electrode and Si nanowires -SiNWs electrode) on the interphase chemistry was thoroughly investigated by the surface science techniques: X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). XPS analysis shows a strong attenuation and positive shift of the Si 2p peaks after a complete charge/discharge performed in PC-and EC:DMC-based electrolytes for both electrodes (a-Si:H and SiNW), confirming a formation of a passive film (called solid electrolyte interphase -SEI layer). As evidenced from the XPS analysis performed on the model electrode, the thicker SEI layer was formed after cycling in PC-based electrolyte as compared to EC:DMC electrolyte. XPS and ToF-SIMS investigations reveal the presence of organic carbonate species on the outer surface and inorganic salt decomposition species in the inner part of the SEI layer. Significant modification of the surface morphology for the both electrodes and a full surface coverage by the SEI layer was confirmed by the scanning electron microscopy (SEM) analysis.