ZINC-BROMIDE RFB

1. Hybrid Battery with metallic electrodes.

2. The most well-known zinc–halogen RFB system is the zinc–bromine flow battery (ZBB) system,
which is another system other than VRBs to be demonstrated at large scales (50–500 kWh).30
ZBBs utilize the reaction between zinc and bromine and have a high theoretical potential of
1.85 V. The development of ZBBs, however, is hindered by the highly corrosive and toxic nature
of bromine, as well as the evolution of zinc dendrite and hydrogen gas. To replace the corrosive
bromine, a zinc–polyiodide RFB system has recently been developed.
3. Advantages: good energy density, high cell voltage, high degree of reversibility, and abundant
low cost reactants.
4. Disadvantages: high cost electrodes, material corrosion, the formation of dendrites during zinc
deposition on charge, high self-discharge rates, unsatisfactory energy efficiency, and relatively
low cycle life (400-600 cycles).
5. The electrochemical reactions that are assumed to occur are, at the bromine electrode
−¿⇋ Br 2 ¿

2 Br −¿+2 e ¿

and at the zinc electrode

−¿⇋ Zn¿

Zn−¿+2 e ¿
6. The net is reaction is as follows with E=1.84V
−¿ ¿

Zn+ Br 2 ⇋ Zn2+¿+2 Br ¿
7. During charge, the reduction of bromine at the zinc electrode is an undesired side reaction
which competes with zinc deposition. During discharging process, zinc and bromide ions are
generated at the respective electrodes.
8. In the bulk aqueous electrolyte solution, complexing of Br- and Br2 to form tri-bromide ions
(Br3-) occurs according to:
−¿ ¿

Br2 + Br−¿⇋ Br 3 ¿

9. In addition, zinc ions can react with bromide in the electrolyte to form several different zinc-
bromine complexes
+¿ ¿ −¿ ¿ 2−¿¿
−¿⇋ ZnBr ¿ −¿ ⇋ZnBr 2 ¿ −¿⇋ZnBr 3 ¿ −¿⇋ ZnBr 4

Zn2+¿+Br Zn2+¿+2 Br Zn2+¿+3 Br

¿

Zn2+¿+4 Br
¿ ¿ ¿ ¿

10. Electrochemical reactions are assumed to follow the Butler Volmer type rate expression.
11. The kinetics of the zinc electrode and the porous bromine electrode are assumed to obey the
linear form of the Butler-Volmer equation for flat plate electrodes.
12. The electrode potentials are calculated using Ohm's law for the electrodes given the ionic
resistivity of the electrode material and the porosity of the porous positive electrode.
13. Ohm's law for the separator is used to relate the solution potential on either border of the
separator to the current density in the separator.