A Simple and Expeditious Route to Phosphate-Functionalized, Water-Processable Graphene for Capacitive Energy Storage

Phosphate-functionalized carbon-based nanomaterials have attracted significant attention in recent years owing to their outstanding behavior in electrochemical energy-storage devices. In this work, we report a simple approach to obtain phosphate-functionalized graphene (PFG) via anodic exfoliation of graphite at room temperature with a high yield. The graphene nanosheets were obtained via anodic exfoliation of graphite foil using aqueous solutions of H3PO4 or Na3PO4 in the dual role of phosphate sources and electrolytes, and the underlying exfoliation/functionalization mechanisms are proposed. The effect of electrolyte concentration was studied, as low concentrations do not lead to a favorable graphite exfoliation and high concentrations produce fast graphite expansion but poor layer-by-layer delamination. The optimal concentrations are 0.25 M H3PO4 and 0.05 M Na3PO4, which also exhibited the highest phosphorus contents of 2.2 and 1.4 at. %, respectively. Furthermore, when PFG-acid at 0.25 M and PFG-salt at 0.05 M were tested as an electrode material for capacitive energy storage in a three-electrode cell, they achieved a competitive performance of ∼375 F/g (540 F/cm3) and 356 F/g (500 F/cm3), respectively. Finally, devices made up of symmetric electrode cells obtained using PFG-acid at 0.25 M possess energy and power densities up to 17.6 Wh·kg–1 (25.3 Wh·L–1) and 10,200 W/kg; meanwhile, PFG-salt at 0.05 M achieved values of 14.9 Wh·kg–1 (21.3 Wh·L–1) and 9400 W/kg, with 98 and 99% of capacitance retention after 10,000 cycles, respectively. The methodology proposed here also promotes a circular-synthesis process to successfully achieve a more sustainable and greener energy-storage device.