Influence of vanadium doping on the supercapacitance performance of hexagonal birnessite

Abstract

Nanostructured birnessite, promising candidate for supercapacitor electrode materials, shows greatly improved discharge capacity and cyclic stability with vanadium doping. The influence of vanadium doping on the physicochemical properties and supercapacitance performance of birnessite-type manganese oxides is investigated. Crystal structures, micromorphologies, bond lengths and chemical compositions of vanadium doped birnessites are characterized by XRD, SEM, XPS, TGA, and titration. The electrochemical properties are analyzed using galvanostatic charge–discharge test, cyclic voltammetry, and electrochemical impedance spectroscopy. The results exhibit that V/Mn molar ratio can reach 0.16:1 when Mn(IV) and K+ are partially substituted by V(V) in birnessite. The thickness of disk-shaped crystal, bond length of Mn–O1 and manganese average oxidation state decreases first and then increases with an increase in V/Mn molar ratio in synthesis system. Charge-transfer resistance decreases after doping vanadium, and increases with an increase in the content of vanadium in birnessite. Diffusion resistance increases first and then decreases due to the change of particle size and pore size distribution. The highest specific capacitance of 245 F g−1 is obtained with excellent cyclic stability for doped birnessite with V/Mn molar ratio of 0.14:1. Our study indicates that vanadium remarkably affects micromorphology, substructure, and electrochemical properties of manganese dioxides.