Hysteresis effects and roughness suppression efficacy of polyethylenimine additive in Cu electrodeposition in ethaline

Abstract

Deep eutectic solvents (DES) are environmentally-friendly electrolytes that are gaining interest for electrodeposition and energy storage applications. In these applications, metal electrodeposits with smooth, non-dendritic morphology are desired and thus effective strategies for suppressing roughness evolution are critically needed. A commonly employed and rather effective strategy for suppressing roughness evolution in metal electrodeposition is the use of electrolyte additives; however, the availability of such additives in DES electrolytes is limited and so is the understanding of the mechanisms through which additives suppress roughness amplification in DES media. In the present contribution, we demonstrate that polyethylenimine (PEI) is an effective electrolyte additive that suppresses roughness evolution during Cu electrodeposition in ethaline DES. PEI, due to its adsorption–deactivation properties, exhibits a unique hysteresis response during voltammetric studies of Cu electrodeposition – this response is analyzed using a mathematical model incorporating the relevant PEI transport, surface adsorption and deactivation processes. The model provides guidelines for selection of optimal conditions (e.g., PEI concentration) for effective suppression of roughness amplification in Cu electrodeposition.