The electrochemical oxidative stability of solvent molecules used for lithium ion battery, ethylene carbonate (EC), propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate in the forms of simple molecule and coordination with anion PF(6)(-), is compared by using density functional theory at the level of B3LYP/6-311++G (d, p) in gas phase. EC is found to be the most stable against oxidation in its simple molecule. However, due to its highest dielectric constant among all the solvent molecules, EC coordinates with PF(6)(-) most strongly and reaches cathode most easily, resulting in its preferential oxidation on cathode. Detailed oxidative decomposition mechanism of EC is investigated using the same level. Radical cation EC(*+) is generated after one electron oxidation reaction of EC and there are five possible pathways for the decomposition of EC(*+) forming CO(2), CO, and various radical cations. The formation of CO is more difficult than CO(2) during the initial decomposition of EC(*+) due to the high activation energy. The radical cations are reduced and terminated by gaining one electron from anode or solvent molecules, forming aldehyde and oligomers of alkyl carbonates including 2-methyl-1,3-dioxolane, 1,3,6-trioxocan-2-one, 1,4,6,9-tetraoxaspiro[4.4]nonane, and 1,4,6,8,11-pentaoxaspiro[4.6]undecan-7-one. The calculation in this paper gives a detailed explanation on the experimental findings that have been reported in literatures and clarifies the mechanism on the oxidative decomposition of EC.

The failure mechanism of graphite/LiNi 0.5 Mn 1.5 O 4 cells cycled at 25 • C and 55 • C have been analyzed by electrochemical methods and ex-situ surface analysis of the electrodes. Graphite /LiNi 0.5 Mn 1.5 O 4 cells cycle well at 25 • C, but have rapid capacity fade upon cycling at 55 • C. Independent electrochemical analysis of anodes and cathodes extracted from cells cycled at 55 • C suggest that both electrodes have significant capacity loss, although the cathode capacity can be recovered with longer charging times. Ex-situ surface analysis of the cathode with SEM reveals that the bulk cathode particles and the cathode laminate are retained while XPS confirms the presence of a cathode electrolyte interface composed of the decomposition products of the electrolyte. Ex-situ analysis of the anode reveals a thick anode solid electrolyte interphase (SEI), anode delamination, and the presence of Mn. The results suggest that both the anode and the cathode contribute to performance loss in graphite/LiNi 0.5 Mn 1.5 O 4 cells.

High energy batteries urgently required to power electric vehicles are restricted by a number of challenges, one of which is the sluggish kinetics of cell reactions under low temperatures. A novel approach is reported to improve the low temperature performance of high energy batteries through rational construction of low impedance anode and cathode interface films. Such films are simultaneously formed on both electrodes via the reduction and oxidation of a salt, lithium difluorobis(oxalato) phosphate. The formation mechanisms of these interface films and their contributions to the improved low temperature performances of high energy batteries are demonstrated using various physical and electrochemical techniques on a graphite/LiNi0.5Co0.2Mn0.3O2 battery using 1 m LiPF6‐ethylene carbonate/ethyl methyl carbonate (1/2, in weight) baseline electrolyte. It is found that the interface impedances, especially the one on the anode, constitute the main obstacle to capacity delivery of high energy batteries at low temperatures, while the salt containing fluorine and oxalate substructures used as additives can effectively suppress them.

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