Development of Waste Red-Mud Nanoparticle Decorated Laser-Induced Graphene Flexible Sueprcapacitor

Abstract

Environmental benign, inexpensive, flexible, smart energy storage micro-supercapacitors, with high energy and power densities and long-term cyclic stability are appealing for next generation energy storage devices. Conventionally, highly conducting carbon-based nanomaterials with high-surface areas are extensively used as supercapacitor electrode and the introduction of metal oxides (or conducting polymers) induces pseudocapacitance and can further enhances the specific capacitance and energy density. Red mud (RM), an aluminum industry waste by-product which is a rich source of hematite phase Fe2O3. RM is environmentally hazardous due to its alkalinity and is produced at an annual rate of ~ 110 million tonnes each year, much of which is not well utilized, and left to lie in large lakes; thus, methods of finding value-added applications for RM are well sought after. In this study, we used mechanical milling to produce uniform spherical RM nanoparticles and utilized these in a flexible micro-supercapacitor device. The as-synthesized nanoparticles were decorated over a laser induced porous 3D graphene (LIG) on a polyimide substrate. The composite electrode material was characterized using transmission electron microscopy (TEM), field effect scanning electron microscopy (FESEM), X-ray photo electron spectroscopy (XPS), Raman spectroscopy and cyclic voltammetry (CV). A solid-state ionic liquid based polymer gel electrolyte was produced using a mixture of ionic liquids {[EMI][TFSI] and [EMIM][BF4]} and a PVDF polymer. Inkjet printing technique was employed to produce the silver current collector and the as fabricated inter-digitated micro-supercapacitor device (Figure 1a) exhibited an areal capacitance of 203 mF cm-2 with a higher potential window of 2.7 V, high energy density of 0.018 mW h/cm2 at 0.66 mW/ cm2 power density. RM decoration increased the energy density of the device by 3.7 fold compared with pristine LIG device (Figure 1b). Rapid lateral ion flow in the planar architecture, presence of metal oxides (mostly hematite), higher electrochemically active surface area, better charge transfer kinetics were shown to yield improvements in the energy-density and the electrochemical performance of the device. An in-depth electrochemical study also revealed that the charge storage mechanism was governed by diffusion driven pseudocapacitance. The device exhibited good robustness and could resist bending and flexing and the prototype device exhibited to power a white-light LED (Figure 1c). Overall, this work demonstrates that RM may be used as a low-cost pseudocapacitive element in supercapacitor electrodes and aid in reducing the environmental impact of the aluminium production cycle by recycling this abundant waste product. Figure 1