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Zn/Br flow batteries are one of the promising technologies for stationary energy storage. Bromine complexing agents have been used to form phase-separated liquid polybromide charging products. However, dynamic and microscopic understanding of the nucleation and growth of the polybromides on the electrode is limited due to the beam-sensitivity and complexity of polybromides and their surrounding electrolytes. In this communication, we report an in operando platform composed of dark field light microscopy and a transparent planar electrochemical cell to dynamically reveal the electrochemical nucleation and formation of polybromides. Using our platform we confirm and reveal the liquid nature, pinning effect (strong interaction with Pt), memory effect (surface residual charge products), self-discharge of the polybromide product, and over-oxidation as a side reaction. We also conclude that the electrochemically formed droplets are mainly MEPBr5 rather than previously reported MEPBr3 with in situ Ra-man spectroscopy. These results provide mechanistic insight into the role of ionic liquid complexing agents and Zn/Br battery design. The in operando visualization platform can also be applied to study other unstable or transient products or intermediates in electrochemical reactions in a non-perturbing manner.
This article was published in the following journal.
Name: Angewandte Chemie (International ed. in English)
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