Interfacial structure changes between amorphous silicon anode/liquid electrolyte using a highly dense and flat model electrode

Changes in the interfacial structures of the amorphous silicon (a-Si) anode/organic electrolyte interfaces in lithium-ion batteries were investigated using highly dense a-Si films fabricated by cathodic arc plasma deposition as a model electrode. Raman spectroscopy, transmission electron microscopy (TEM), and X-ray reflectivity revealed that the Si films were grown in an amorphous state with an atomically flat surface. The a-Si films exhibited lithium alloying and de-alloying reactions, with a large irreversible capacity during the first cycle. The irreversible capacity was derived from the formation of a solid electrolyte interphase (SEI) along with an incompletely de-alloyed Li-Si phase, as confirmed by ex situ TEM and X-ray photoelectron spectroscopy observations. The discharge and charge capacities of the Si films gradually decreased in the subsequent cycles, despite the fact that no further SEI formation or cracking of the Si layer occurred. Scanning electron microscopy observations combined with energy-dispersive X-ray spectroscopy revealed the miniaturization of the a-Si film in the surface region to generate domains measuring less than a few hundred nanometers. These results suggest that delamination and miniaturization of the a-Si nanodomains from the electrode surface are partly responsible for degradation of the a-Si anode.