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several industrial electrochemical processes [23]. The Ce(IV)/Ce(III) redox couple is quasi- reversible, as demonstrated by the voltammetric studies by Vijayabarathi et al. [147] and Devadoss et al. [148]. More recently, studies for cerium-based RFBs have shown that both oxidation and reduction reactions have suitable kinetics for RFBs [149-151], although at least one slow reaction step can hinder charge transfer due to the re-organization of the methanesulfonate ligands during the electrode reaction [123]. The high solubility of cerium species in methanesulfonic acid enable their use in aqueous electrochemistry [120], although it declines above acid concentrations above 4 mol dm–3. The concentration of Ce(IV) methanesulfonate can reach up to 1.0 mol dm–3, setting a limit for the volumetric energy density of the Zn-Ce RFB. In sulfuric acid, the kinetics of cerium methanesulfonate redox processes are irreversible and their maximum solubility is 0.125 mol dm–3 [122], making this supporting electrolyte unsuitable for RFB applications. Xie et al. [149] have reported that that both Ce(IV) and Ce(III) ions are soluble up to 333 K. At higher temperatures, Ce(IV) methansulfonate precipitates from the electrolyte when the concentration of Ce(IV) ions is ca. 0.6 mol dm–3. Several electrode materials have been reported for the positive half-cell reaction and the effect of charge-discharge regimes in the Zn-Ce RFB [152]. Although carbon felt electrodes yielded the highest cell potential at a current density of 50 mA cm–2, its low stability meant that Pt/Ti mesh was more suited to use in an RFB. Xie et al. [149] also performed experiments in a Zn- Ce flow cell using a 3 mm thick carbon felt as positive electrode allowed to obtain a charge efficiency of 86% and an energy efficiency of 75% under a regime of one hour charges and discharges at a constant current density of 30 mA cm–2. On the other hand, in a laboratory divided flow cell with a Pt/Ti mesh electrode the conversion of Ce(III) to Ce(IV) was possible at a current efficiency of more than 75% [152]. In the same study, the concentration of 24PDF Image | hybrid redox flow batteries with zinc negative electrodes
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