Operando Monitoring of Local pH Value Changes at the Carbon Electrode Surface in Neutral Sulfate-Based Aqueous Electrochemical Capacitors

[Image: see text] The operando monitoring of pH during the charging and discharging of an electrochemical capacitor in an aqueous neutral salt solution is presented. Proper knowledge of transient and limiting pH values allows for a better understanding of the phenomena that take place during capacitor operation. It also enables the proper assignment of the reaction potentials responsible for water decomposition. It is shown that the pH inside the capacitor is strongly potential-dependent and different for individual electrodes; therefore, the values of the evolution potentials of hydrogen and oxygen cannot be precisely calculated based only on the initial pH of the electrolyte. The operando measurements indicate that the pH at the positive electrode reaches 4, while at the negative electrode, it is 8.5, which in theory could shift the theoretical operating voltage well beyond 1.23 V. On the other hand, high voltage cannot be easily maintained since the electrolyte of both electrode vicinities is subjected to mixing. Operando gas monitoring measurements show that the evolution of electrolysis byproducts occurs even below the theoretical decomposition voltage. These reactions are important in maintaining a voltage-advantaged pH difference within the cell. At the same time, the electrochemical quartz crystal microbalance (EQCM) measurements indicated that the ions governing the pH (OH(–)) that initially accumulated in the vicinity of the positive electrode enter the carbon porosity, losing their pH-governing abilities. pH fluctuations in the cell are important and play a vital role in the description of its performance during the cyclability at a given voltage. This is especially noticeable in cell floating at 1.3 V, where the pH difference between electrodes is the highest (6 units). The increase of the electrode separation distance acts similarly to the introduction of a semipermeable membrane toward the increase of the capacitor cycle life. During floating at 1.6 V, where the pH difference is not as high anymore (4 units), the influence of separation in terms of electrode stability, although present, is less notable.