In this paper we report a novel redox flow battery using a titanium and manganese mixed solution as both positive and negative electrolytes. Ti(IV) ions existing in positive electrolyte suppress the Mn(III) disproportionation reaction, as well as particle growth of Mn dioxides. The energy density of 23.5 kWh m-3 was obtained in a single cell test, which is comparable to that of all-vanadium RF battery. Mn dioxide nanoparticles contribute to excellent flowablity and electro-active performance. In the cycling stability test, the performance is stable over more than 40 cycles. It is considered that the same electrolyte in both half-cells prevent mixing of electro-active species.
The mixed electrolyte of titanium and manganese is one of the promising candidates as low-cost electrolytes for redox flow batteries. In this study, the effect of Ti4+ ion in the positive electrolyte was examined in detail. With an increase of Ti4+ ion concentration, the formation reaction of MnO2 particle was slowed down significantly, which means the stability of Mn3+ ion is enhanced. Moreover, the particle size of MnO2 precipitate became smaller in electrolytes containing certain amount of Ti4+ ion. These MnO2 particles were small enough to be flowed in the electrolyte and to be reduced to Mn2+ ion again. Ti4+ ion also affected the crystal structures of MnO2, limiting to gamma-MnO2 which is assumed to be reactive. In cyclic voltammetry study, the higher Ti4+ ion concentration was, the better reversibility of Mn redox reaction was observed. The ion interaction between Ti4+ and Mn3+ was confirmed by UV-visible spectroscopy.
In this paper we investigate the effect of heat treatment of carbon papers on Ti-Mn redox system. The heat treatment improves the redox reaction kinetics of carbon paper electrode for both positive and negative half-cell. It is considered that the enhanced kinetic performance is attributed to the increased wettability of carbon surface, because a significant increase in the surface area was not observed. In the full-cell evaluation, mass transport loss increased significantly with increasing the state of charge. It is considered that the precipitation of MnO 2 caused decrease of reactants and prevented reactants diffusion. The low kinetics of negative halfcell limited the cell performance. The cell performance has been greatly improved by using a high capacitance carbon felt as negative electrode. A high energy efficiency of 83.2% at current density of 100 mA cm -2 was obtained in a single cell test.
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