Nitrogen-doped graphene with high nitrogen level via a one-step hydrothermal reaction of graphene oxide with urea for superior capacitive energy storage

Abstract

Nitrogen-doped graphene nanosheets (NGS) with the nitrogen level as high as 10.13 atom% were synthesized via a simple hydrothermal reaction of graphene oxide (GO) and urea. N-doping and reduction of GO were achieved simultaneously under the hydrothermal reaction. In the fabrication, the nitrogen-enriched urea plays a pivotal role in forming the NGS with a high nitrogen level. During the hydrothermal process, the N-dopant of urea could release NH₃ in a sustained manner, accompanied by the released NH₃ reacting with the oxygen functional groups of the GO and then the nitrogen atoms doped into graphene skeleton, leading to the formation of NGS. The nitrogen level and species could be conveniently controlled by easily tuning the experimental parameters, including the mass ratio between urea and GO and the hydrothermal temperature. Remarkably, in 6 M KOH electrolyte, the synthesized NGS with both high nitrogen (10.13 atom%) and large surface area (593 m² g⁻¹) exhibits excellent capacitive behaviors (326 F g⁻¹, 0.2 A g⁻¹), superior cycling stability (maintaining initial capacity even) and coulombic efficiency (99.58%) after 2000 cycles. The energy density of 25.02 Wh kg⁻¹ could be achieved at power density of 7980 W kg⁻¹ by a two-electrode symmetric capacitor test. A series of experiments results demonstrated that not only the N-content but also the N-type are very significant for the capacitive behaviors. In more detail, the pyridinic-N and pyrrolic-N play mainly roles for improving pseudo-capacitance by the redox reaction, while quaternary-N could enhance the conductivity of the materials which is favorable to the transport of electrons during the charge/discharge process. Hence, the approach in this work could provide a new way for preparing NGS materials which could be used as advanced electrodes in high performance supercapacitors.