Theoretical Insight into Oxidative Decomposition of Propylene Carbonate in the Lithium Ion Battery
- 23 March 2009
- journal article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry B
- Vol. 113 (15), 5181-5187
- https://doi.org/10.1021/jp810279h
Abstract
The detailed oxidative decomposition mechanism of propylene carbonate (PC) in the lithium ion battery is investigated using density functional theory (DFT) at the level of B3LYP/6-311++G(d), both in the gas phase and in solvent. The calculated results indicate that PC is initially oxidized on the cathode to a radical cation intermediate, PC•+, and then decomposes through three pathways, generating carbon dioxide CO2 and radical cations. These radical cations prefer to be reduced on the anode or by gaining one electron from PC, forming propanal, acetone, or relevant radicals. The radicals terminate by forming final products, including trans-2-ethyl-4-methyl-1,3-dioxolane, cis-2-ethyl-4-methyl-1,3-dioxolane, and 2,5-dimethyl-1,4-dioxane. Among all the products, acetone is most easily formed. The calculations in this paper give detailed explanations of the experimental findings that have been reported in the literature and clarify the role of intermediate propylene oxide in PC decomposition. Propylene oxide is one of the important intermediates. As propylene oxide is formed, it isomerizes forming a more stabile product, acetone.Keywords
This publication has 31 references indexed in Scilit:
- Solvation Structure of Li+ in Concentrated LiPF6−Propylene Carbonate SolutionsThe Journal of Physical Chemistry B, 2007
- Mass Spectrometry Investigations on Electrolyte Degradation Products for the Development of Nanocomposite Electrodes in Lithium Ion BatteriesAnalytical Chemistry, 2006
- Behaviour of highly crystalline graphites in lithium-ion cells with propylene carbonate containing electrolytesJournal of Power Sources, 2005
- Characterisation of the SEI formed on natural graphite in PC-based electrolytesElectrochimica Acta, 2004
- Associations of Alkyl Carbonates: Intermolecular C−H···O InteractionsThe Journal of Physical Chemistry A, 2001
- Computation of Thermodynamic Oxidation Potentials of Organic Solvents Using Density Functional TheoryJournal of the Electrochemical Society, 2001
- Electron-Spin-Resonance Study of the Reaction of Electrolytic Solutions on the Positive Electrode for Lithium-Ion Secondary BatteriesJournal of the Electrochemical Society, 2001
- Ab Initio and Semiempirical Study of the Effect of Ethereal Solvent on Aggregation of a Lithium EnolateJournal of the American Chemical Society, 1997
- Anodic oxidation of propylene carbonate and ethylene carbonate on graphite electrodesJournal of Power Sources, 1995
- Anodic stability of propylene carbonate electrolytes at potentials above 4V against lithium: An on-line MS andin situ FTIR studyJournal of Applied Electrochemistry, 1991