A modified self-extinguishing time (SET) device which enhances the reproducibility of the results is presented. Pentafluoro(phenoxy)cyclotriphosphazene (FPPN) is investigated as flame retardant electrolyte additive for lithium ion batteries (LIBs) in terms of thermal stability and electrochemical performance. SET measurements and adiabatic reaction calorimetry are applied to determine the flammability and the reactivity of a standard LIB electrolyte containing 5% FPPN. The results reveal that the additive-containing electrolyte is nonflammable for 10 s whereas the commercially available reference electrolyte inflames instantaneously after 1 s of ignition. The onset temperature of the safety enhanced electrolyte is delayed by ≈ 21 °C. Compatibility tests in half cells show that the electrolyte is reductively stable while the cyclic voltammogram indicates oxidative decomposition during the first cycle. Cycling experiments in full cells show improved cycling performance and rate capability, which can be attributed to cathode passivation during the first cycle. Post-mortem analysis of the electrolyte by gas chromatography-mass spectrometry confirms the presence of the additive in high amounts after 501 cycles which ensures enhanced safety of the electrolyte. The investigations present FPPN as stable electrolyte additive that improves the intrinsic safety of the electrolyte and its cycling performance at the same time.