Hierarchical three-dimensional mesoporous MnO2 nanostructures for high performance aqueous asymmetric supercapacitors†
We describe a new facile chemical route for the synthesis of hierarchical mesoporous α-MnO2 and the development of an aqueous asymmetric supercapacitor. The hierarchical α-MnO2 is synthesized by the thermodynamically favorable redox reaction between metallic Zn and MnO4− in mild acidic solutions without any template. Zn and the in situ generated nascent hydrogen efficiently reduce MnO4− to MnO2. The growth mechanism is studied with time-dependent electron microscopic measurements. The α-MnO2 has a three-dimensional (3D) flower-like mesoporous hierarchical structure with an average size of 500 nm and a large surface area (206 m2 g−1) with a pore size of 48.34 Å and a pore volume of 0.543 cm3 g−1. It has significantly high electronic conductivity with respect to traditional/commercial MnO2. A specific capacitance as high as 322 F g−1 at a current density of 1 A g−1 with excellent cycling stability (90% after 8000 cycles) is achieved. An aqueous asymmetric supercapacitor (ASC) is developed by pairing α-MnO2 and reduced graphene oxide-based electrodes. An ASC could deliver a specific capacitance of 63.5 F g−1 at 2 A g−1 with a potential window of 0–2 V. The ASC retains 100% initial specific capacitance even after 3000 continuous charge–discharge cycles. It has an energy density of 35.28 W h kg−1 at a power density of 2.0 kW kg−1 and could retain 27.78 W h kg−1 at a power density of 16.67 kW kg−1. The three-dimensional mesoporous structure favors the facilitated transport of the electrolyte across the electrode. The post-mortem XRD analysis shows that the MnO2 nanostructure retains its initial α phase even after 3000 charge–discharge cycles, though a partial disintegration of the hierarchical structure was observed.