Adsorption of Ultrathin Ethylene Carbonate Films on Pristine and Lithiated Graphite and Their Interaction with Li.

Abstract

Aiming at a better understanding of the solid-electrolyte interphase formation in Li-ion batteries, we have investigated the interaction of ultrathin films of ethylene carbonate (EC), which is a key solvent of battery electrolytes, with pristine and lithiated highly oriented pyrolytic graphite (HOPG) and with postdeposited Li. Employing X-ray and ultraviolet photoelectron spectroscopy as well as Fourier transform infrared spectroscopy under ultrahigh-vacuum conditions, in combination with density functional theory (DFT)-based calculations, we find that EC adsorbs molecularly intact on pristine HOPG in the entire temperature range between 80 K and desorption at 200 K. Features in the ultraviolet photoelectron spectra could be related to the molecular orbitals of EC obtained from DFT calculations, and a similar adsorption/desorption behavior is obtained also on lithiated HOPG. In contrast, stepwise postdeposition of ∼0.5 and one monolayer of Li0 on a preadsorbed EC adlayer leads not only to stabilization of Li+/Liδ+ at the surface, possibly as adsorbed Li+(EC) n species, but also to EC decomposition, forming products such as Li2CO3, ROCO2Li (CH2OCO2Li)2, and Li2O. Consequences on the electronic surface properties and on the stabilization of the resulting adlayer are discussed. Upon annealing up to room temperature, some residual Li-containing decomposition products remain on the surface, which is considered as the initial stage of the solid|electrolyte interphase formation at the electrode|electrolyte interface.