Modulation of Si-O Structure in Uniformly Ultrasmall Silicon Oxycarbide for Superior Lifespan of Lithium Metal Anodes.

Abstract

Utilizing nanoseeds guiding homogeneous deposition of lithium is an effective strategy to inhibit disorderly growth of lithium, where silicon oxide has been attracting attention as a transform seed. However, the research on silicon-oxide-based seeds has concentrated more on utilizing their lithiophilicity but less on their Si-O structures, which could result in different failure mechanisms. In this study, various Si-O structures of silicon oxycarbide carbon nanofibers are prepared by adjusting the content of octa(aminopropylsilsesquioxane). According to XANES and experimental observations, the C-rich SiOC has an active Si-O-C structure but generates a larger volume variation during lithiation, while in the O-rich phase, the silica-oxygen tetrahedral structure can contribute to alleviate the volume expansion but has poor electrochemical activity. SiOC, which is dominated by SiO₃C, has a suitable Si-O and silica-oxygen tetrahedral-structure distribution, which balances the electrochemical activity and volume expansion. This allows the host to demonstrate an excellent lifespan over 3740 h with a tiny voltage hysteresis (22 mV) at 2 mA cm^-2, and it retains a favorable capacity of 97 mA h g^-1 after 630 cycles with a high Coulombic efficiency of 99.7% in full cells. This study experiences the influence of various Si-O structures on lithium metal anodes.