title: Quantum chemistry study of the oxidation-induced stability and decomposition of propylene carbonate-containing complexes.
abstract: Oxidation-induced decomposition reactions of the representative complexes of propylene carbonate (PC)-based electrolytes were investigated using density functional theory (DFT) and a composite G4MP2 method. The cluster-continuum approach was used, where the oxidized PCn cluster was surrounded by the implicit solvent modeled via a polarized continuum model (PCM). The oxidative stability of the PCn (n = 2, 3, and 4) complexes was found to be around 5.4-5.5 V vs. Li(+)/Li, which is not only lower than the stability of an isolated PC but also lower than the stability of the PC-PF6(-), PC-BF4(-) or PC-ClO4(-) complexes surrounded by the implicit solvent. The oxidation-induced decomposition reactions were studied. The decomposition products of the oxidized PC2 contained CO2, acetone, propanal, propene, and carboxylic acid in agreement with the previous experimental studies.
authors.affiliation: School of Chemistry and Environment, South China Normal University, Guangzhou 510006, China. xingld@scnu.edu.cn liwsh@scnu.edu.cn.
authors.forename: Yating
authors.initials: Y
authors.lastname: Wang
authors.forename: Lidan
authors.initials: L
authors.lastname: Xing
authors.forename: Oleg
authors.initials: O
authors.lastname: Borodin
authors.forename: Wenna
authors.initials: W
authors.lastname: Huang
authors.forename: Mengqing
authors.initials: M
authors.lastname: Xu
authors.forename: Xiaoping
authors.initials: X
authors.lastname: Li
authors.forename: Weishan
authors.initials: W
authors.lastname: Li