Relaxation of the Adsorbed Material and Shadowing Effects on the Shape and Size of Electrodeposited Dendrites.

Materials with dendritic morphologies exhibit large surface areas that improve the catalytic, optical, and wetting properties but have ambiguous effects in batteries, so modeling their growth may help find the best operation conditions in each case. Kinetic Monte Carlo simulations are used here to study a metal electrodeposition model that represents the interplay between diffusive cation flux in the electrolyte and surface diffusion of adsorbed atoms (adatoms) with electrodes perpendicular to the gradient of the electrolyte concentration and different crystallographic orientations. In FCC lattices, dendrites with a pine tree shape are formed for all orientations, with dominant (111) surfaces and with trunks propagating in [001] and equivalent directions. However, with (110) and (111) substrates, secondary branches do not grow because the inclined primary branches block the cation flux (shadowing effect), so the dendrites may have a leaf-like shape. Some morphologies obtained here resemble those of the silver and gold electrodeposits. The extension to electrodeposition of HCP crystals with (0001) substrates shows the formation of leaf-like dendrites with a hexagonal symmetry. In both lattices, hierarchically organized structures appear for model parameters that warrant large diffusion lengths of adsorbed atoms on flat planes (typically coordination numbers