The effect of vinylene carbonate (VC) as electrolyte additive on the formation mechanisms of passivation films covering both electrodes in lithium-ion batteries was investigated by X-ray photoelectron spectroscopy (XPS). LiConormalO2 /graphite coin cells using a LiPnormalF6 /ethylene carbonate:diethyl carbonate:dimethyl carbonate liquid electrolyte with or without VC were charged at 20 and 60°C . The identification of VC-derived products formed at the surface of the electrodes was carried out by a dual experimental/theoretical approach. From a classical XPS core peak analysis completed by a detailed interpretation and simulation of valence spectra supported by ab initio calculations, and through direct synthesis of the VC polymer, we could evidence the formation of the radical poly(VC) at the electrode/electrolyte interfaces. We showed that the radical polymerization is the main reaction mechanism of VC contributing to the formation of the passivation layers at the surface of both electrodes.

The stereo-electronic control over bisadditions of conjugated polymers to fullerene (C 60 ) is explored in the formation of alternating copolymers. The chemistry, resulting configuration, and properties of poly(3-hexylthiophene)-alt-C 60 copolymers prepared by either classic pyrrolidine ring formation or an atom transfer radical addition are compared. Both routes result in controlled additions of polymers to C 60 . Extensive macromolecular modeling through PM6 methods indicate that there is no conjugation between P3HT and C 60 in the systems studied. This along with 2D-NMR, AFM, and photovoltaic characterizations of the materials indicate the importance of the structure of the modified C 60 and the nature of the linking group between C 60 and P3HT segments in determining the morphology of the copolymers in the solid state.