Electrochemical and In Situ Spectroscopic Study of the Effect of Prussian Blue as a Mediator in a Solid-State Supercapacitor

In situ X-ray absorption spectroscopy (XAS) along with electrochemical measurements were used to explore the redox activity of Prussian blue (PB) and its contribution to pseudocapacitance in an asymmetrical solid-state supercapacitor (SC). The SC, with a configuration of (activated carbon)/polymer electrolyte membrane/(activated carbon + PB), was fabricated with an embedded KCl saturated Ag/AgCl reference electrode. The potentials of the two electrodes were generally displaced proportionally with increase in the cell voltage. Upon negative polarization from the open circuit voltage (OCV) condition to −3 V, the charge capacity was greater than that upon positive polarization from the OCV condition to +3 V, in agreement with the higher fraction of Fe(III) than that of Fe(II) and the low concentration of K ions in PB. Detailed analysis of cyclic voltammetry data in the range between 0 and −3 V indicates that the battery-like contribution to the charge current was 96% that of the capacitor-like contribution at a scanning rate of 2.5 mV s ⁻¹ but only 15% at 100 mV s ⁻¹ . The in situ XAS characterization results indicate that the majority of Fe was reversibly charged and discharged between Fe(III) and Fe(II) during positive and negative polarizations with minimal changes in local atomic structure.