Tungsten oxide nanostructures for all-vanadium redox flow battery: Enhancing the V(II)/(VIII) reaction and inhibiting H₂ evolution

Vanadium redox flow batteries (VRFBs) offer remarkable performance capabilities for renewable energy power plants. However, the kinetics of the VRFBs' redox reactions are slow and the efficiency is low due to parasitic reactions such as the hydrogen evolution reaction (HER). In this work, to overcome these limitations, the effect of modifying the carbon cloth electrode with tungsten oxide nanowires, nanoflakes, and nanospheres prepared was elucidated for the negative half-cell reaction V(II)/V(III). The physical and chemical properties of those nanostructures were characterized using FESEM, XPS, XRD, FTIR, and contact angle measurements. The effect of the catalyst loading and structure, pH and composition of the synthesis solution, and the presence of binder on catalytic activity was evaluated using CV and EIS. The results showed that the effective loading of all three structures is -2 mg/cm(2), with all of the structures showing a significant enhancement of the V(II)/(VIII) reaction kinetics in comparison to the untreated carbon cloth and greater stability than the thermally treated carbon cloth. The tungsten oxide nanostructures prepared at pH 2 showed the best catalytic activity, with the suppression of hydrogen evolution reaction (HER) being inversely proportional to the number of defects. Tungsten oxide nanoflakes prepared at pH 2 using water as a solvent exhibited the optimum balance between promoting the V(II)/(VIII) reaction kinetics and suppressing the HER. The performance evaluation in a two-electrodes setup of all-vanadium RFB revealed that the WNFs structure have the highest charge/discharge capacity and energy efficiency at a relatively high current density of 60 mA/cm(2) due to its improved kinetics.