Study of silver electrodeposition in deep eutectic solvents using atomic force microscopy

The electrodeposition of metals in ionic liquids and deep eutectic solvents leads to deposits with significantly different morphologies to those seen with aqueous solutions. The classical methods of fitting amperometric data to nucleation and growth mechanisms do not fit the data well in ionic systems and tend to focus on the short time-scale aspects of nucleation. In the current study, ex-situ AFM was used to model crystallite sizes and distributions by digitising and modelling the images. The deposition of silver from a deep eutectic solvent was chosen as it has been studied by several groups with a variety of techniques. The crystallite size data obtained from AFM and chronoamperometry for long time-scale deposition studies are compared and it is shown that the trends are similar, but there is a discrepancy in the nuclear number density of approximately an order of magnitude. The nuclear number density was found to be consistent with aqueous nucleation studies once differences in concentration and mass transport were accounted for.