Observing Nonpreferential Absorption of Linear and Cyclic Carbonate on the Silicon Electrode

Silicon is reported to be a promising anode material due to its high storage capacity and excellent energy conversion rate. Molecular-level insight into the interaction between silicon electrodes and electrolyte solutions is essential for understanding the formation of a stable solid electrolyte interphase (SEI), but it is yet to be explored. In this study, we apply femtosecond sum frequency generation vibrational spectroscopy to investigate the initial adsorption of various pure and mixed electrolyte molecules on the silicon anode surface by monitoring the SFG signals from the carbonyl group of electrolyte molecules. When the silicon comes in contact with a pure carbonate solution, the linear carbonates of diethyl carbonate and ethyl methyl carbonate adopt two conformations with opposite C=O orientations on the silicon interface while the cyclic carbonates of ethylene carbonate and propylene carbonate almost adopt one conformation with C=O bonds pointing toward the silicon electrode. When the silicon comes in contact with the mixed linear and cyclic carbonate solutions, the total SFG intensity from the mixed solutions is approximately 2 similar to 5 times weaker than those of pure cyclic carbonates. The C=O bonds of cyclic carbonates point toward the silicon electrode, while the C=O bonds of linear carbonates face toward the bulk solution at the silicon/mixed solution interface. No preferential absorption behaviors of the linear and cyclic carbonate electrolytes on the silicon electrode are observed. Such findings may help to understand the mechanism by which the SEI formed on the silicon anode is unstable.

Automated summary

Silicon is a promising anode material with high storage capacity and excellent energy conversion rate. Understanding the interaction between silicon electrodes and electrolyte solutions at a molecular level is crucial for stable solid electrolyte interphase formation, but this has not been explored yet. In this study, femtosecond sum frequency generation vibrational spectroscopy was used to investigate the initial adsorption of various electrolyte molecules on the silicon anode surface. The findings provide insights into the instability of the solid electrolyte interphase formed on the silicon anode.