In view of the growing need for clean energy, supercapacitors (SC), especially those based on activated carbon (AC) and organic electrolyte are attracting great attention for their theoretically infinite life span. However, they still age much faster than expected due to certain mechanisms. Several researches is being conducted to understand these mechanisms, but so far, the chemical reactions at the phase boundary of the activated carbon electrodes and organic electrolyte have been very unclear. Some pathways have not yet been investigated; there is no research on the reactions that can take place between acetonitrile in the vapor phase and the oxides presented on the surface of activated carbons. For this reason, in this study, divided into two parts, the first based on a thermal simulation and the second based on an experimental study, we have systematically described the ageing mechanisms by determining the gas-phase reactions that can occur at the electrode–electrolyte interface. On the one hand, a thermal model of a supercapacitor cell using activated carbon and organic electrolyte technology has been developed. This model allowed us to study the temperature distribution of supercapacitors, and thus to determine the thermodynamic parameters related to the phenomena produced at the electrode–electrolyte interface. On the other hand, a thermo-gravimetric analysis coupled with gas phase infrared spectroscopy on the activated carbons of an aged supercapacitor of the same technology as that used in the simulation was carried out. The results obtained made it possible to identify the chemical groups produced by ageing.