Zinc deposition and dissolution in methanesulfonic acid onto a carbon composite electrode as the negative electrode reactions in a hybrid redox flow battery

► Use methanesulfonic acid to avoid dendrite formation during a long (>4h) zinc electrodeposition. ► Electrochemical characterization of Zn(II) deposition and its morphology using methanesulfonic acid solutions. ► Use of additives to improve the efficiency of zinc deposition and dissolution as the half cell reaction of a redox flow battery. Electrodeposition and dissolution of zinc in methanesulfonic acid were studied as the negative electrode reactions in a hybrid redox flow battery. Cyclic voltammetry at a rotating disk electrode was used to characterize the electrochemistry and the effect of process conditions on the deposition and dissolution rate of zinc in aqueous methanesulfonic acid. At a sufficiently high current density, the deposition process became a mass transport controlled reaction. The diffusion coefficient of Zn2+ ions was 7.5×10−6cm2s−1. The performance of the zinc negative electrode in a parallel plate flow cell was also studied as a function of Zn2+ ion concentration, methanesulfonic acid concentration, current density, electrolyte flow rate, operating temperature and the addition of electrolytic additives, including potassium sodium tartarate, tetrabutylammonium hydroxide, and indium oxide. The current-, voltage- and energy efficiencies of the zinc-half cell reaction and the morphologies of the zinc deposits are also discussed. The energy efficiency improved from 62% in the absence of additives to 73% upon the addition of 2×10−3moldm−3 of indium oxide as a hydrogen suppressant. In aqueous methanesulfonic acid with or without additives, there was no significant dendrite formation after zinc electrodeposition for 4h at 50mAcm−2.