Inhibition of Redox Behaviors in Hierarchically Structured Manganese Cobalt Phosphate Supercapacitor Performance by Surface Trivalent Cations

Abstract

The stability and performance of supercapacitor devices are limited by the diffusion-controlled redox process occurring at materials' surfaces. Phosphate-based metal oxides could be effectively used as pseudocapacitors because of their polar nature. However, electrochemical energy storage applications of Mn-Co-based phosphate materials and their related kinetics studies have been rarely reported. In this work, we have reported a morphology-tuned MnxCo3-x(PO4)2·8H2O (MCP) spinel compound synthesized by a one-step hydrothermal method. Detailed physical and chemical insights of the active material coated on the nickel substrate are examined by X-ray diffraction, field-emission scanning electron microscopy, field-emission transmission electron microscopy, and high-resolution X-ray photoelectron spectroscopy analyses. Physiochemical studies reveal that the well-defined redox behavior usually observed in Co2+/Ni2+ surface-terminated compounds is suppressed by reducing the divalent cation density with an increased Co3+ and Mn3+ surface states. A uniform and dense leaflike morphology observed in the MnCo2 phosphate compound with an increased surface area enhances the electrochemical energy storage performance. The high polar nature of P-O bonding formed at the surface leads to a higher rate of polarization and a very low relaxation time, resulting in a perfect square-shaped cyclic voltagram and triangular-shaped galvanostatic charge and discharge curve. We have achieved a highly pseudocapacitive MCP, and it can be used as a vital candidate in supercapacitor energy storage applications.