Study of Interfacial Reaction Mechanism of Silicon Anodes with Different Surfaces by Using the In Situ Spectroscopy Technique

The interfacial reaction of a silicon anode is very complex, which is closely related with the electrolyte components and surface elements' chemical status of the Si anode. It is crucial to elucidate the formation mechanism of the solid electrolyte interphase (SEI) on the silicon anode, which promotes the development of a stable SEI. However, the interface reaction mechanism on the silicon surface is closely related to the surface components. This work systematically investigates the interfacial reaction mechanism on silicon materials with three representative coatings of graphene, TiO₂, and SiO₂ by ex situ X-ray photoelectron spectroscopy (XPS) and dynamic analysis in operando attenuated total reflection-Fourier transform infrared (ATR-FTIR), in situ revealing the different ring-opening mechanisms of fluoro-ethylene carbonate (FEC) and ethylene carbonate (EC) on different silicon surfaces with varying electrical conductivities. Due to the different ring-opening mechanisms, the final decomposition product of FEC on the graphene/electrolyte interface is stable LiF, while on the oxide (native SiO₂ or emerging TiO₂) interface, it forms an unstable solid lithium compound ^•CH₂CHFOCO₂Li. This study demonstrates that the formation mechanism of the SEI on silicon-based electrodes is related to the electron conductivity of surface elements, providing a theoretical basis for further optimization of silicon-based composite materials.