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Its limitations included Zn corrosion and the requirement of management of solids due to the ZnO slurry generated during discharge and the presence of ferri- and ferrocyanide crystals in the positive electrolyte. Cell balance was achieved by directing H2 evolved at the Zn electrode to the positive electrolyte in order to reduce ferricyanide. Mass transfer at the zinc electrodes and its current distribution were studied [272] and the cycling of the battery was simulated [273]. Although the system yielded an energy efficiency of 75% and low-cost sulfonated polystyrene and polysulfone membranes were especially developed [274], the cost of commercial membranes and the difficult management of solids stopped this development. Furthermore, the speciation of ferricyanide in NaOH solutions and its effects on the electrochemistry at nickel-coated electrodes appear to have been ignored at the time. However, due to its relative low cost the Zn-ferricyanide alkaline RFB was commercially re- introduced in 2013 by ViZn Energy Inc. (USA) claiming future development of utility-scale installations [275]. Technological improvements on the Lockheed battery have not been disclosed. Studies on the long-term stability of the photosensitive ferricyanide under closed battery conditions have not been reported. A Zn-Fe RFB with a thermodynamic cell potential of 1.53 V has been developed [276]. This battery differs from the Zn-ferricyanide as its employs an iron chloride in an acetate buffer solution as electrolyte in order to prevent the hydrolysis of Fe3+ ions. An energy efficiency of 71% was reported and the system presented as a lower cost alternative to the Zn-Ce RFB. A similar Zn-Fe RFB comprises Zn electrode reaction in an alkaline electrolyte, the Fe electrode reaction in an acidic chloride reaction and an intermediate ‘middle electrolyte’ [277]. The intermediate flow compartment with NaCl requiring two membranes to separate the electrodes would be difficult to implement in practice, not to mention higher potential losses. Another Zn-Fe cell employing a single acidic chloride solution containing NH4+ ions has also 51PDF Image | hybrid redox flow batteries with zinc negative electrodes
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