Few layered graphene powders were prepared via electrochemical exfoliation of graphite in a deep eutectic solvent (DES) and with aqueous electrolytes to function as electrode catalysts on commercially sourced carbon papers (CPs) for the positive electrolyte of the all-vanadium redox flow battery (VRFB). Both graphene powders were decorated on the CP by means of a horizontal binder-free electrophoretic deposition (EPD) technique (using dimethylformamide as the colloidal solvent). The cyclic voltammetry and electrochemical impedance spectroscopy evaluations of the \({\text{VO}}^{{{2} + }} /{\text{VO}}_{2}^{ + }\) redox couple showed that the graphene prepared electrochemically in an aqueous media provided better performances. Similarly, an attempt was made to electrochemically etch a titanium-based MAX phase to Ti3C2TX-MXene using a DES prepared from choline chloride and methane sulfonic acid. However, the aluminum from the MAX phase could not be etched. Instead, MXene prepared via chemical etching with HCl and LiF was of high quality and could be dispersed easily in water to prepare a colloidal suspension for EPD. After a binder free EPD on the CP substrate, the electrochemical results for MXene modified CP were not as good as that of the graphene modified CP owing to insufficient deposition of the former in the non-optimal EPD process. Moreover, 1,2‑dihydrobenzoquinone‑3,5‑disulfonic acid (BQDS), a high‑solubility, organic quinone redox alternative dissolved at 10 mM in 1 M sulfuric acid was tested for comparative assessments of cyclic voltammetry. While BQDS was primarily examined in organic flow batteries, its inclusion here offers an insight into the electrode behavior beyond traditional \({\text{VO}}^{{{2} + }} /{\text{VO}}_{2}^{ + }\) systems.