Abstract
The thermal stability of 1M LiPF 6, LiClO 4, LiN(SO 2CF 2CF 3) 2 (LiBETI) and LiPF 3(CF 2CF 3) 3 (LiFAP) solutions in mixtures of ethylene carbonate, diethyl carbonate and dimethyl carbonate in the temperature range 40–350 °C was studied by ARC and DSC. NMR was used to analyze the reaction products at different reaction stages. The least thermally stable are LiClO 4 solutions. LiPF 3(CF 2CF 3) 3 solutions showed higher thermal stability than LiPF 6 solutions. The highest thermal stability was found for LiN(SO 2CF 2CF 3) 2 solutions. Studies by DSC and pressure measurements during ARC experiments with LiPF 6 and LiFAP solutions detected an endothermic reaction, which occurs before a number of exothermic reactions as the temperature increases. Fluoride ions are formed and react with the alkyl carbonate molecules both as bases and as nucleophiles.
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