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Electrolyte additives are the most common strategy to obtain smooth zinc deposits and inhibiting H2 evolution. Additives can produce compact deposits by enabling the complete dissolution of the zinc deposit during discharge, stopping the build/up of material and the depletion of zinc ion in the electrolyte, which lead to electrode overpotentials. Research on electroplating and primary batteries has reported a large number of electrolyte additives, as shown in Table 5. They include organics, acids, polymers and metal ions. Some of these compounds can be incorporated into solid electrodes [241]. Some of the most effective additives in zinc electrodeposition are heavy metals such as mercury, cadmium, lead or oxides of these [233, 240]. These additives can be present in the solution or be alloyed in zinc electrodes in order to supress dendritic growths and inhibit H2 evolution. Nevertheless, environmental and health concerns have imposed restrictions to the use of these metals, resulting in a requirement for non-toxic and cost effective replacements, usually organics. Alternatives to heavy metals include bismuth, calcium, magnesium, indium, tin and tungsten [233, 240], as well as fluorides, phosphates and borates [249]. Calcium is one of the most promising due to the formation of insoluble calcium zincate, Ca(OH)2×2Zn(OH)2×2H2O. By decreasing the migration of zincates from the electrode into the electrolyte, shape problems can be ameliorated [240], since zinc can migrate across the soluble zincates layer. Jain et al. [242] have confirmed these effects of calcium-zincate in a Zn-Ni RFB, noting that the utilization of zinc increased and that 25% w.t. calcium affords better results. The same group have reported that a KOH-KF-K2CO3 electrolyte also suppressed electrode shape change, preventing short-circuiting by dendrite for 575 cycles in Zn-Ni cell [250]. 43PDF Image | hybrid redox flow batteries with zinc negative electrodes
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