Quantification of the Charge Consuming Phenomena under High‐Voltage Hold of Carbon/Carbon Supercapacitors by Coupling Operando and Post‐Mortem Analyses

Abstract Enhancing the operating voltage of supercapacitors (SCs), hence their specific energy, is important. However, long‐term hold at high voltage entails loss of capacitance, increase of resistance and internal pressure. Such detrimental effects could be reduced by obtaining quantitative information on the relative impact of the various mechanisms leading to the worsening of the SCs performance. Now, for a carbon/carbon supercapacitor in aqueous Li2SO4, a self‐consistent approach is used to assign leaking charge during high voltage hold to the charge: 1) distributed throughout the electrochemical cell (steady‐state leakage current measurements), 2) spent at each electrode for gases production (operando electrochemical mass spectrometry (EMS) analysis and pressure records), 3) utilized to oxidize the electrodes surface (from post‐mortem surface functionality determination by temperature programmed desorption (TPD)), and 4) used for other parasitic reactions.