Refining the Grain Size of Zinc Electrodeposit by Pb2+ Ion Grinding for Compact and Stable Zinc Anode

Abstract Recently, aqueous zinc‐based batteries (AZBs) have become a promising candidate for energy storage devices due to the high safety of aqueous electrolytes and the appealing features of Zn anodes, for example, low cost and high theoretical capacity. However, the excessive growth of Zn electrodeposits as well as the uneven stacking of large hexagonal Zn crystal units always render loose and irregular electrodeposition or even dendritic growth, which seriously deteriorates the actual performance of AZBs. Herein, to refine the grain size of Zn electrodeposits, a trace of Pb 2+ ions as a novel electrolyte additive is performed to inhibit the growth of Zn grain during the Zn electrodeposition. Owing to the higher adsorption energy of Pb 2+ ions on Zn crystal when compared with Zn 2+ ions, the strongly positively‐charged Pb 2+ ions are tightly absorbed on the typical crystal planes of initially‐formed Zn nuclei, which block the way for the subsequent absorption and electroreduction of Zn 2+ ions. As a result, the Pb 2+ ions‐containing electrolyte refines the grain size of Zn electrodeposits from 7.43–7.87 μm to 0.88–2.26 μm, and affords a high reversibility of Zn plating/stripping behavior with a high Coulombic efficiency of 99.9 % over 1000 cycles.