Reduction Mechanisms of Ethylene Carbonate on Si Anodes of Lithium-Ion Batteries: Effects of Degree of Lithiation and Nature of Exposed Surface

Ab initio molecular dynamics simulations are used to identify mechanisms of reduction of ethylene carbonate on Si surfaces at various degrees of lithiation, where the low-coordinated surface Si atoms are saturated with O, OH, or H functional groups. The lowest Si content surfaces are represented by quasi-amorphous LiSi4 and LiSi2; intermediate lithiation is given by LiSi crystalline facets, and the highest Li content is studied through Li13Si4 surfaces. It is found that ethylene carbonate (EC) reduction mechanisms depend significantly on the degree of lithiation of the surface. On LiSi surfaces EC is reduced according to two different two-electron mechanisms (one simultaneous and one sequential), which are independent of specific surface functionalization or nature of exposed facets. On the less lithiated surfaces, the simultaneous two-electron reduction is found more frequently. In that mechanism, the EC reduction is initiated by the formation of a C-Si bond that allows adsorption of the intact molecule to the surface and is followed by electron transfer and ring-opening. Strongly lithiated Li13Si4 surfaces are found to be highly reactive. Reduction of adsorbed EC molecules occurs via a four-electron mechanism yielding as reduction products CO(2-) and O(C2H4)O(2-). Direct transfer of two electrons to EC molecules in liquid phase is also possible, resulting in the presence of O(C2H4)OCO(2-) anions in the liquid phase.