Tailoring the surface chemistry of zeolite templated carbon by electrochemical methods

One option to optimize carbon materials for supercapacitor applications is the generation of surface functional groups that contribute to the pseudocapacitance without losing the designed physical properties. This requires suitable functionalization techniques able to selectively introduce a given amount of electroactive oxygen groups. In this work, the influence of the chemical and electrochemical oxidation methods, on the chemical and physical properties of a zeolite templated carbon (ZTC), as a model carbon material, have been studied and compared. Although both oxidation methods generally produce a loss of the original ZTC physical properties with increasing amount of oxidation, the electrochemical method shows much better controllability and, unlike chemical treatments, enables the generation of a large number of oxygen groups (O = 11000- 3300 μmol/g), with a higher proportion of active functionalities, while retaining a high surface area (ranging between 1900-3500 m2/g), a high microporosity and an ordered 3-D structure.

The contribution of sulfate ions and protons to the specific capacitance of microporous carbon monoliths

The monoliths studied in this work show large specific surface areas (up to 1600 m2 g-1), high densities (up to 1.17 g cm-3) and high electrical conductivities (up to 9.5 S cm-1). They are microporous carbons with pore sizes up to 1.3 nm but most of them below 0.75 nm. They also show oxygen functionalities. The electrochemical behavior of the monoliths is studied in three-electrode cells with aqueous H2SO4 solution as electrolyte. This work deals with the contribution of the sulfate ions and protons to the specific capacitance of carbon monoliths having different surface areas and different contents of oxygen groups. Protons contribute with a pseudocapacitance (up to 152 F g-1) in addition to the double layer capacitance. Sulfate ions contribute with a double layer capacitance only. At the double layer, the capacitance of the sulfate ions (up to 291 F g-1) is slightly higher than that of protons (up to 251 F g-1); both capacitances increase as the surface area increases. The preference of protons to be electroadsorbed at the double layer and the broader voltage window of these ions account for their higher contribution (70 %) to the double layer capacitance.

Design of Activated Carbon/Activated Carbon Asymmetric Capacitors

Supercapacitors are energy storage devices that offer a high power density and a low energy density in comparison with batteries. Their limited energy density can be overcome by using asymmetric configuration in mass electrodes, where each electrode works within their maximum available potential window, rendering the maximum voltage output of the system. Such asymmetric capacitors are optimized using the capacitance and the potential stability limits of the electrodes, with the reliability of the design largely depending on the accuracy and the approach taken for the electrochemical characterization. Therefore, the performance could be lower than expected and even the system could break down, if a well thought out procedure is not followed. In this work, a procedure for the development of asymmetric supercapacitors based on activated carbons is detailed. Three activated carbon materials with different textural properties and surface chemistry have been systematically characterized in neutral aqueous electrolyte. The asymmetric configuration of the masses of both electrodes in the supercapacitor has allowed to cover a higher potential window, resulting in an increase of the energy density of the three devices studied when compared with the symmetric systems, and an improved cycle life.