Lithium-ion batteries (LIBs) are employed when high energy and power density are required. However, under electrical, mechanical, or thermal abuse conditions a thermal runaway can occur resulting in an uncontrollable increase in pressure and temperature that can lead to fire and/or explosion, and projection of fragments. In this work, the behavior of LIBs under thermal abuse conditions is analyzed. To this purpose, tests on NCA 18,650 cells are performed in a cone calorimeter by changing the radiative heat flux of the conical heater and the State of Charge (SoC) of the cells from full charge to deep discharge. The dependence of SoC and radiative heat flux on the thermal runaway onset is clearly revealed. In particular, a deep discharge determines an earlier thermal runaway of the cell with respect to those at 50% and 100% of SoC when exposed to high radiative heat flux (50 kW/m2). This is due to a mechanism such as an electrical abuse. Cell components before and after tests are investigated using Differential Scanning Calorimetry (DSC), Scanning Electron Microscopy—Energy Dispersive X-ray Spectroscopy (SEM-EDS) and X-ray Diffraction (XRD) to determine the structural, morphological, and compositional changes. It results that the first reaction (423–443 K) that occurs at the anode involves the decomposition of the electrolyte. This reaction justifies the observed earlier venting and thermal runaway of fully charged cells with respect to half-charged ones due to a greater availability of lithium which allows a faster kinetics of the reaction. In the cathode residues, metallic nickel and NO are found, given by decomposition of metal oxide by the rock-salt phase cathode.