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The Zn-Cl2 RFB received consideration in the 70s and 80s following its development by Gulf & Western Industries [50]. Research also took place in Japan by Furukawa Electric Co. [66]. Since the management of gaseous Cl2 generated at the positive electrodes would have been difficult, this technology was based on the storage of Cl2 in the form of hydrate in a refrigerated system [74]. The electrode kinetics and mass transport properties of graphite positive electrodes were studied [266] and porous graphite electrodes were simulated [267]. The battery was limited by the mass transport overpotential at the zinc planar electrodes [24] and by the self-discharge corrosion of the zinc deposits [268]. Porous zinc electrodes made by replaceable rods were proposed to ease mass transport [269], while the morphology and stability of zinc was improved by the addition of Pb2+ [270] and Bi3+ [271] ions into the electrolyte. The Gulf project was considered successful after testing 10 kW h modules as part of a 100 kW h energy storage facility [50]. At a current density of 30 mA cm–2, the system showed an energy efficiency of 68%. The 80 kW h Furukawa project reported a similar overall efficiency of 65% [66] but the complexity of the system has discouraged further development. Another early RFB based on abundant inexpensive reagents is the Zn-ferricyanide system introduced by Lockheed [29]. The unit cell gives a potential of 1.61 V and relies on graphite bipolar electrodes coated with cadmium on the negative side and nickel on the positive side. Alternatively, nickel-coated carbon felt could be used as the positive electrode. Zinc deposition at the negative electrode is coupled to the ferrocyanide/ferricyanide redox couple at the positive electrode: Fe(CN)63– + e– ⇄ Fe(CN)64– (12) 50PDF Image | hybrid redox flow batteries with zinc negative electrodes
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