In-situ electrochemical and operando Raman techniques to investigate the effect of porosity in different carbon electrodes in organic electrolyte supercapacitors

•It was observed an ionic insertion in graphite by XRD and raman techniques.•Cell voltage is a function of the carbon material`s porosity.•Energy density depends on electrode porosity. The analyzes of micro-, meso‑ and macro-porous carbon electrodes in a symmetrical supercapacitor filled with a 1.0 M TEABF4 EC-DMC electrolyte were reported in this work. The activated carbon (AC), multi-walled carbon nanotubes, and graphite materials were studied. The results indicate AC is the best electrode material for the application with high specific capacitance and energy. The Raman operando analyzes of AC show that the D- and G- bands shift their positions and intensities. The cause of this phenomenon is the electrostatic ionic adsorption inside very narrow pores, affecting the vibrational mode and the work function of the material, resulting in the shift of the Fermi level of the material. For mesoporous carbon, this phenomenon is much less pronounced. In principle, graphite has enough specific capacitance for competitive application. However, its overall surface area is reduced. Graphite's Raman operando analyzes revealed the BF4−insertion into graphene layers. The G-band splits while the in-situ electrochemical data support a capacitance with three orders of magnitude higher than expected for a purely electrostatic adsorption process on graphite. Overall, this fundamental study evidences that in-situ electrochemistry and Raman spectroscopy combined could offer important information on the energy storage process for supercapacitors.