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The kinetics of the electrode processes in the alkaline Zn-air system were described and analysed in detail by Bockris et al. [167]. Since the parasitic H2 evolution occurs at a significant rate, suitable additives are needed in order to suppress this reaction and to control zinc deposition. Several strategies have been studied, for instance, by employing common electrolyte additives in the zinc electroplating industry, which are typically mixtures of polyvinyl alcohols (PVAs), polyamines (PAs) and quaternary ammonium ions [168]. The effect of these organic additives with a brightener (N-benzyl-3-carboxylpyridinium chloride, 3NCP) on zinc morphology have been investigated [169]. The synergetic effect of all three additives caused the deposition to occur at more negative potentials, decrease in the crystal size and changes in crystal growth orientation. Work done on inorganic additives such as lead ions and tungstate ions has shown that concentrations of 1 x 0-4 mol dm-3 and 0.6 mol dm-3, respectively for either additive gave more compact deposits with energy efficiencies of ca. 60% [170]. A subsequent study by the same group also showed that lead and quaternary ammonium salts such as tetrabutylammonium ions give compact morphology [171]. The role of organic additives has also been examined in Hull cells, in both acidic and alkaline zinc plating baths. In comparison to carbonyl compounds, thiosemicarbazides and their derivatives, furfuraldehydethiosemicarbazone (FrTSCN) were found to be effective additives, displaying good throwing power, corrosion mitigation, current efficiency of ca. 99% and glossy deposits [172]. Lee et al. [18] considered the ability of organic acids to hinder the rate of deposition and suppress H2 evolution. Citric acid was concluded to be most effective at inhibiting dendrite formation but least effective at suppressing H2 evolution. A short communication [173] showed that the addition of a surfactant, 2% sodium dodecyl benzene sulfonate, to a dilute KOH electrolyte formed a passivation layer thereby increasing the utilisation of the negative electrode. 31PDF Image | hybrid redox flow batteries with zinc negative electrodes
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