Cathodic plasma-induced syntheses of graphene nanosheet/MnO2/WO3 architectures and their use in supercapacitors

In this study, we synthesized new 0.01-2 mu m graphene nanosheet/MnO2WO3(G/MnO2/WO3) architectures through an electrochemically induced cathodic plasma process in a single batch at a lower temperature (70 degrees C) and for a shorter time (2 h) than those required for the syntheses of similar structures when using a hydrothermal method. We first obtained 0.01-1 mu m leaf-like graphene (G) nanosheets, then 0.1-0.3 mu m long and approximately 10 nm diameter petiole-like MnO2 nanowires on the G nanosheets, and finally 0.20-2.0 mu m petal-like WO3 on MnO2/G - thereby forming the G/MnO2/WO3 architectures - as evidenced using scanning electron microscopy and transmission electron microscopy. We deciphered the step-wise reaction mechanism behind the formation of the G/MnO2/WO3 architectures during the plasma process. The high surface area of 291 m(2) g(-1) in the G/MnO2/WO3 architecture was contributed mainly by the G nanosheets, providing a suitable surface area for diffusion of the charge carriers during the charging and discharging process. As a result, an electrode incorporating the G/MnO2/WO3 architectures exhibited an excellent specific capacitance of 620 F g(-1) - 45 and 200% higher than those of G/MnO2 (421 F g(-1)) and G (189 F g(-1)) electrodes, respectively - at a current density of 0.5 A g(-1). Moreover, the G/MnO2/WO3-incorporated electrode exhibited good electrochemical cycling stability, with 90% capacitance retention over 5000 cycles at 1 A g(-1). Such new G/MnO2/WO3 heterojunction structures, not only provide high-performance electrode applications, but also suggest a potential approach toward fabricating other heterojunction structures having high surface areas for energy storage applications. (C) 2020 Elsevier Ltd. All rights reserved.