Reduced graphene oxide nanosheets as electron sink for MnFe2O4 nanoparticles: A synergistically boosted supercapacitance

Abstract

Spinel ferrite structures have shown promise for energy storage. However, they are insulators and need a conductive substrate for better charge transfer. Here, we utilized a simple hydrothermal technique to in-situ coat a nickel foam with few-layer nanosheets of reduced graphene oxide (rGO) decorated with manganese ferrite (MnFe2O4) nanoparticles. We then studied the supercapacitance/pseudocapacitance properties of the rGO/MnFe2O4 composite. X-ray diffraction patterns, energy-dispersive X-ray maps, and X-ray photoelectron spectra of the composite were investigated to confirm its structural, elemental, and surface chemical composition, respectively. Scanning electron microscopy and transmission electron microscopy images demonstrated the decoration of rGO nanosheets with MnFe2O4 nanoparticles. In a three-electrode setup, the rGO/MnFe2O4 nanocomposite exhibits a specific capacitance per loaded material mass (2446 F/g at 1 A/g) which is higher than the sum of rGO (304 F/g) and MnFe2O4 (1084 F/g) electrodes, suggesting a synergistic effect between rGO and MnFe2O4. The energy density and power density of the rGO/MnFe2O4 electrode were also calculated 58.24 Wh/kg and 260.82 W/kg (at 1 A/g), respectively. We found that the resistance of the rGO/MnFe2O4 electrode (2.53 Ω) is much lower than the MnFe2O4 electrode (6.15 Ω), and the interfacial resistance of the rGO/MnFe2O4 electrode with electrolyte was found low, confirming the rGO role as a conductive substrate for insulating MnFe2O4 nanoparticles. We also showed that surface-related capacitance, rather than pseudocapacitance, is more dominant in the rGO/MnFe2O4 composite electrode than in the separate rGO and MnFe2O4 electrodes. We also demonstrated the practical performance of the rGO/MnFe2O4 electrode in a two-electrode setup. Finally, density functional theory calculations showed the considerable potential drop (16.5 eV) between MnFe2O4 and graphene that leads to a strong built-in electric field from graphene towards MnFe2O4. This indicates the role of graphene as a wide electron sink for MnFe2O4 nanoparticles that results in better charge distribution and storage.