A systematic study1 of the solvent/solvent, solvent/anion and solvent/(lithium salt) complexes using DFT and correlated wave function methods demonstrated the deficiencies of projecting oxidation stability and decomposition reactions from isolated solvents and isolated anions to electrolytes due to rapid H-transfer reaction occurring in the electrolyte model clusters. The presence of anions and other solvent molecules was found to lead to the reduced solvent oxidative stability, changed the order of the solvent decomposition reactions, altered decomposition products and influenced the decomposition kinetics for carbonate (EC,DMC,PC), alkyl phosphate (TMP) and ether-based electrolytes with LiPF6, LiBF4, LiB(CN)4, LiTFSI, LiTFSI salts. This presentation will extend upon the previous results and will focus on the connection between the oxidation rate and oxidation potential in order to enable a direct comparison of with the linear sweep voltammetry measurements. The quantum chemistry results indicate that oxidation stability of the model system for the carbonate-based electrolytes is below 5 V vs. Li+/Li even on non-active electrodes. The propagation and termination oxidation induced reactions will be also discussed.References 1. Borodin, O.; Behl, W.; Jow, T. R., Oxidative Stability and Initial Decomposition Reactions of Carbonate, Sulfone, and Alkyl Phosphate-Based Electrolytes. J. Phys. Chem. C 2013,  117, 8661-8682.

Oxidation stability and decomposition reactions of battery electrolytes

247th National Meeting (2014)

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