Theoretical Insight into Oxidative Decomposition of Propylene Carbonate in the Lithium Ion Battery

详细信息    查看全文

• 作者：Lidan Xing ; Chaoyang Wang ; Weishan Li ; Mengqing Xu ; Xuliang Meng ; Shaofei Zhao
• 刊名：Journal of Physical Chemistry B
• 出版年：2009
• 出版时间：April 16, 2009
• 年：2009
• 卷：113
• 期：15
• 页码：5181-5187
• 全文大小：296K
• 年卷期：v.113,no.15(April 16, 2009)
• ISSN：1520-5207

文摘

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.