Kinetic analysis of silicon–lithium alloying reaction in silicon single crystal using soft X-ray absorption spectroscopy

Abstract

Silicon has been considered to be one of the most promising anode active materials for next-generation lithium-ion batteries due to its large theoretical capacity (4200 mA h g⁻¹, Li₂₂Si₅). However, silicon anodes suffer from degradation due to large volume expansion and contraction. To control the ideal particle morphology, an experimental method is required to analyze anisotropic diffusion and surface reaction phenomena. This study investigates the anisotropy of the silicon–lithium alloying reaction using electrochemical measurements and Si K-edge X-ray absorption spectroscopy on silicon single crystals. During the electrochemical reduction process in lithium-ion battery systems, the continuous formation of solid electrolyte interphase (SEI) films prevents the achievement of steady-state conditions. Instead, the physical contact between silicon single crystals and lithium metals can prevent the effect of SEI formation. The apparent diffusion coefficient and the surface reaction coefficient are determined from the progress of the alloying reaction analyzed by X-ray absorption spectroscopy. While the apparent diffusion coefficients show no clear anisotropy, the apparent surface reaction coefficient of Si (100) is more significant than that of Si (111). This finding indicates that the surface reaction of silicon governs the anisotropy of practical lithium alloying reaction for silicon anodes.