Solid-state NMR Study of Ion Adsorption and Charge Storage in Graphene Film Supercapacitor Electrodes

Graphene film has been demonstrated as promising active materials for electric double layer capacitors (EDLCs), mainly due to its excellent mechanical flexibility and freestanding morphology. In this work, the distribution and variation pattern of electrolyte ions in graphene-film based EDLC electrodes are investigated with a ¹¹B magic-angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopy. For neutral graphene films soaked with different amounts of electrolytes (1 M TEABF₄/ACN), weakly and strongly adsorbed anions are identified based on the resonances at different ¹¹B chemical shifts. Unlike other porous carbonaceous materials, the strongly adsorbed anions are found as the major electrolyte anions components in graphene films. Further measurements on the ion population upon charging are carried out with applying different charging voltages on the graphene films. Results indicate that the charging process of graphene-film based EDLCs can be divided into two distinct charge storage stages (i.e., ejection of co-ions and adsorption of counter-ions) for different voltages. The as-obtained results will be useful for the design and fabrication of high performance graphene-film based EDLCs.