Electrocatalytic activity of Nb-doped hexagonal WO ₃ nanowire-modified graphite felt as a positive electrode for vanadium redox flow batteries

Abstract

We report a facile hydrothermal method to synthesize low-cost, high-catalytic-activity, and stable niobium-doped hexagonal tungsten trioxide nanowires; these were employed as catalysts to improve the electrocatalytic activity of graphite felt (GF) electrodes for use as positive electrodes in an all-vanadium redox flow battery (VRFB).

Abstract

In this paper, we report a facile hydrothermal method to synthesize low-cost, high-catalytic-activity, and stable niobium-doped hexagonal tungsten trioxide nanowires (Nb-doped h-WO ₃ NWs); these NWs were employed as catalysts to improve the electrocatalytic activity of graphite felt (GF) electrodes for use as positive electrodes in an all-vanadium redox flow battery (VRFB). The effect of Nb doping and its composition on the electrochemical performance of GF electrodes for a VRFB was investigated. Cyclic voltammetry and electrochemical impedance spectroscopy results showed that Nb-doped h-WO ₃ NWs with a Nb/W atomic ratio of 0.03 exhibited the highest electrocatalytic activities for VO ²⁺/VO ₂ ⁺ couples among all the tested electrodes. This observation was attributed to the optimal Nb-doping concentration producing moderate defect states, thereby creating structural disorders, such as oxygen vacancies, in WO ₃ and leading to the generation of more active sites for the VO ²⁺/VO ₂ ⁺ redox reaction on the electrode. Moreover, in charge–discharge tests, a VRFB single cell using the Nb-doped h-WO ₃ NW (Nb/W = 0.03) catalyst demonstrated an excellent energy efficiency of 78.10% with a current density of 80 mA cm ⁻². This efficiency is much higher than that demonstrated by VRFB cells with untreated GF (67.12%) and heat-treated GF obtained through the conventional method (72.01%). Furthermore, in the stability test of a VRFB single cell with the Nb-doped h-WO ₃ NW (Nb/W = 0.03) catalyst, almost no decay of the cell was observed even after 30 cycles. This observation indicates the outstanding stability of the cell during the redox reaction of vanadium ions under highly acidic conditions.