Achieving electrode smoothing by controlling the nucleation phase of metal deposition through polymer-substrate binding

TL;DR

This study reveals that polymer additives like PEO smooth zinc electrodeposition by promoting nucleation of specific crystal orientations through substrate interactions, supported by in-situ microscopy and DFT simulations.

Contribution

It uncovers a new mechanism where PEO interacts with the substrate to control nucleation, advancing understanding of electrode morphology regulation in batteries.

Findings

PEO promotes nucleation of (002)-oriented Zn platelets.

DFT simulations show PEO modifies interfacial energy at the Zn/Cu interface.

Substrate-polymer interactions are key to electrode smoothing.

Abstract

Polymer additives [like polyethylene oxide (PEO)] are widely used for smooth electrode deposition in aqueous zinc and a number of other battery systems currently investigated for energy storage applications. However, the precise mechanism by which they regulate morphology and suppress dendrite formation remains unclear. In this study, we address this knowledge gap by using in-situ electrochemical atomic force microscopy (EC-AFM) to directly observe the interfacial evolution during Zn electrodeposition and polymer adsorption on copper (Cu) substrates in the presence of varying concentrations of ZnSO4 and PEO. Contrary to previous literature assumptions which emphasize the binding to the growing Zn crystal surfaces or Zn2+ ions, our results demonstrate that PEO smooths Zn films by promoting nucleation of (002)-oriented Zn platelets through interactions with the Cu substrate. Density functional theory (DFT) simulations support this finding by showing that PEO adsorption on Cu modifies the interfacial energy of Zn/Cu/electrolyte interfaces, favoring the stabilization of Zn (002) on the Cu substrate, as well as confines Zn electrodeposition to a narrow near-surface region. These findings elucidate a novel design principle for electrode smoothing, emphasizing the importance of substrate selection paired with polymer additives that exhibit an attractive interaction with the substrate, but minimal interaction with growing crystals, offering a mechanistic perspective for improved battery performance.