EC–DMC–DEC solutions comprising LiPF3(CF2CF3)3 (LiFAP), LiPF6 and LiN(SO2CF2CF3)2 (LiBETI) were tested with graphite and LiMn2O4 electrodes. Cyclic voltammetry (CV, fast and slow scan rates), chronopotentiometry, impedance spectroscopy, surface sensitive FTIR and XPS were used for this study. It was found that the new salt LiFAP is a promising candidate for use in rechargeable Li-ion batteries. The thermal behavior of these electrolyte solutions was also studied using accelerating rate calorimetry (ARC). It was found that LiFAP solutions are more stable than LiPF6 solutions while LiBETI solutions have the highest thermal stability.