O vacancy-rich doped WO3/GF as a novel electrode for an aqueous DHAQ/ K4Fe(CN)6 redox flow battery

Abstract

In this study, a graphite felt (GF) electrode was modified with N and S heteroatoms before being loaded with Ti-doped or Nb-doped WO3 to produce Ti-WO3/GF-N-S and Nb-WO3/GF-N-S electrodes. X-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy were used to analyze the crystal structure, morphology, and elemental state of the modified GF electrodes and investigate the impact of nonmetallic and metallic element doping. The influence of metal doping on the electronic distribution of the oxide was determined using first-principle calculations. The electrochemical properties of the modified GF were studied using cyclic voltammetry, electrochemical impedance spectroscopy, and single-cell tests. The results showed that Ti or Nb doping changed the energy band structure, bond length, and bond angle in the WO3 crystal and formed O vacancies. The chemical properties of Ti and Nb resulted in different numbers of O vacancies for the two doped-WO3.The doping of N and S heteroatoms on the carbon fibres altered the O vacancy concentration of WO3. The synergism between the two doping methods accelerated electron transfer in the anthraquinone redox reaction. In addition, the N-containing functional groups provide lone-pair electrons, which accelerate electron transfer and anthraquinone adsorption. Therefore, compared to the pristine GF, the discharge capacities of the Ti-WO3/GF-N-S and Nb-h-WO3/GF-N-S graphite GF electrodes increased by 58 % and 41 %, respectively, and the Nb-h-WO3/GF-N-S graphite GF electrodes exhibited a good capacity retention rate. This study broadens the practical applications of aqueous anthraquinone redox flow batteries.