The risk of thermal runaway is, for Li-ion batteries, a critical issue for large-scale applications. This results in manufacturers and researchers placing great emphasis on minimizing the heat generation and thereby mitigating safety-related risks through the search for suitable materials or additives. To this end, an in-depth stepwise investigation has been undertaken to provide a better understanding of the exothermic processes that take place at the negative electrode/electrolyte interface as well as an increased visibility of the role of the state-of-the-art electrode binders, additives and lithium salt by means of the classical DSC technique. A reliable experimental set up helped quantify the beneficial or harmful contribution of binder polymers to the exothermic behavior of the CMC/SBR containing graphite electrode film in contact with 1 M LiPF6 in EC:DMC:EMC (1:1:1 v/v/v) electrolyte. Further, the role of the VC, FEC and VEC electrolyte additives (2 wt%) in reinforcing the protective SEI layer towards thermally induced electrolyte reduction is discussed in the light of infrared spectroscopy and transmission electron microscopy analyzes results. Moreover, after a preliminary corrosion study of LiPF6/LiFSI mixtures, we showed that the 0.66/0.33 M composition can be used in commercial NMC-based LiBs with a positive effect on the thermal runaway.