Nanoscopic Supercapacitance Elucidations of the Graphene-Ionic Interface with Suspended/Supported Graphene in Different Ionic Solutions.

Graphene-based supercapacitors have gained significant attention due to their exceptional energy storage capabilities. Despite numerous research efforts trying to improve the performance, the challenge of experimentally elucidating the nanoscale-interface molecular characteristics still needs to be tackled for device optimizations in commercial applications. To address this, we have conducted a series of experiments using substrate-free graphene field-effect transistors (SF-GFETs) and oxide-supported graphene field-effect transistors (OS-GFETs) to elucidate the graphene-electrolyte interfacial arrangement and corresponding capacitance under different surface potential states and ionic concentration environments. For SF-GFET, we observed that the hysteresis of the Dirac point changes from 0.32 to -0.06 V as the ionic concentration increases. Moreover, it results in the interfacial capacitance changing from 4 to 2 F/g. For OS-GFET, the hysteresis of the Dirac point remains negative (-0.15 to -0.07 V). Furthermore, the corresponding capacitance of OS-GFET decreases (53-16 F/g) as the ionic concentration increases. These suggest that the orderly oriented water structure at the graphene-water interface is gradually replaced by ionic hydration clusters and results in the difference of capacitance. The relationship between Dirac-point hysteresis value and ionic concentration can be modeled by using the first-order Hill equation to obtain the half occupation value (