Control of Growth Front Evolution by Bi Additives during ZnAu Electrodeposition.

The performance of many electrochemical energy storage systems can be compromised by the formation of metal dendrites during charging. Additives in the electrolyte represent a useful strategy to mitigate dendrite formation, but understanding the mechanisms involved requires knowledge of the nanoscale effects of additives during electrochemical deposition. Here we quantify the effects of an inorganic additive on the morphology of an evolving electrochemical growth front, using liquid cell electron microscopy to provide the necessary spatial and temporal resolution. We examine deposition of ZnAu on Au in the presence of Bi additive, and show that low concentrations of Bi delay but do not prevent the formation of growth front instabilities. We describe a model in which Bi segregates at the growth front and promotes the surface diffusion and relaxation of Zn, allowing better coverage of the initial Au electrode surface. A more precise knowledge of the mechanism of inorganic additive effects may help in designing electrolyte chemistry for battery and other applications where morphology control is essential.