Self-organized periodic pattern dynamics of porous copper electrodeposition at the industrial large current

Abstract

The formation of porous structure during metal electrodeposition not only provide new ideas for preparing advanced metal materials, but also determines the product defects in industrial electrodeposition processes. However, as for new evidence of ordered sub-structure formation within porous metal even during scalable templateless electrodeposition, existing thermodynamic reasons or exogenous-templates mechanism are under extensively controversial. Herein, we have discovered periodic self-organization behavior of porous copper at the initial stage of industrial large-current electrodeposition. Different from widely-recognized bubble-templated mechanism, the length of periodicity for Cu deposits is orders of magnitude smaller than any possible bubble template, according to in-situ observation. Coloration-tracking and in-situ electrochemical analysis experiments have been designed, to reveal the existence of a micelle-type complex intermediate and its activator effects. A self-organization mechanism has been proposed based on ordered dynamic pattern of micelle-type complex intermediate, rather than intermediate of small ions, which determines the porous structure since the very initial layer. Our findings suggest the important contribution from intrinsic self-organization dynamics of intermediate to the formation of porous metal materials with high activity or surface area in industrial scale.