The electrochemical reduction of five organic carbonates, EC, PC, DEC, DMC and VC were studied via cyclic voltammetry at a Au electrode. More detailed studies of the chemistry of VC reduction were carried out using IRRAS at a glassy carbon electrode. The measured reduction potentials for EC, DEC and PC were consistent with thermodynamic values calculated using density functional theory (DFT) assuming one-electron reduction to the radical anion. The experimental values for VC and DMC were,

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... r, much more positive than the calculated values, which we attribute to different reaction pathways. The role of VC as an additive in a PCbased electrolyte was investigated. We confirmed stable cycling of a commercial lithium-ion battery carbon anode in a PC-based electrolyte with 5 mol % VC added. A surface layer indicative of preferential reduction of VC in the PC-based electrolyte was observed by IRRAS with both a glassy carbon and composite carbon electrode. The preferential reduction of VC and the SEI layer formation therefrom appears to inhibit PC co-intercalation and subsequent graphite exfoliation.