Fluoroethylene Carbonate as a Directing Agent in Amorphous Silicon Anodes: Electrolyte Interface Structure Probed by Sum Frequency Vibrational Spectroscopy and Ab Initio Molecular Dynamics.

Fluorinated compounds are added to carbonate-based electrolyte solutions in an effort to create a stable solid electrolyte interphase (SEI). The SEI mitigates detrimental electrolyte redox reactions taking place on the anode's surface upon applying a potential in order to charge (discharge) the lithium (Li) ion battery. The need for a stable SEI is dire when the anode material is silicon as silicon cracks due to its expansion and contraction upon lithiation and delithiation (charge-discharge) cycles, consequently limiting the cyclability of a silicon-based battery. Here we show the molecular structures for ethylene carbonate (EC): fluoroethylene carbonate (FEC) solutions on silicon surfaces by sum frequency generation (SFG) vibrational spectroscopy, which yields vibrational spectra of molecules at interfaces and by ab initio molecular dynamics (AIMD) simulations at open circuit potential. Our AIMD simulations and SFG spectra indicate that both EC and FEC adsorb to the amorphous silicon (a-Si) through their carbonyl group (C═O) oxygen atom with no further desorption. We show that FEC additives induce the reorientation of EC molecules to create an ordered, up-right orientation of the electrolytes on the Si surface. We suggest that this might be helpful for Li diffusion under applied potential. Furthermore, FEC becomes the dominant species at the a-Si surface as the FEC concentration increases above 20 wt %. Our finding at open circuit potential can now initiate additive design to not only act as a sacrificial compound but also to produce a better suited SEI for the use of silicon anodes in the Li-ion vehicular industry.