Understanding enhanced charge storage of phosphorus-functionalized graphene in aqueous acidic electrolytes

The mechanisms behind enhanced charge storage of P-functionalized carbons are unraveled for the first time using non-porous graphene oxide treated with phosphoric acid and annealed at either 400 or 800 °C. The electrochemical study in 1M H 2 SO 4 reveals that phosphorus groups boost charge storage and electrochemical stability, with more effect for the higher annealing temperature. Annealing at 800 °C also leads to the material withstanding 60,000 charge-discharge cycles with no capacitance loss at 1.5V. The improvement in the electrochemical performance is shown to be mainly governed by the change in surface chemistry comprehensively studied with NMR, FTIR and XPS characterization techniques. The collective analysis of electrochemical response and surface chemistry demonstrates that enhanced charge synstorage by phosphorus-functionalized graphene materials is made possible due to the followingergistic mechanisms: i) non-Faradaic charging; ii) nascent hydrogen storage in the interlayer; iii) benzoquinone-to-hydroquinone redox processes; iv) phosphate-to-phosphonate like transformation. From the practical perspective, the stored charge can be boosted due to the higher capacitance upon prior electrochemical activation in the vicinity of oxygen evolution potential and the wider usable electrochemical window enabled by phosphorus-related groups.