Crystallography-Dependent Plating/Stripping Kinetics and Interfacial Morphologies in Zn Metal Anodes.

Crystallographic orientation governs Zn deposition, dissolution, and cycling stability, but its influence on interfacial charge-transfer kinetics remains difficult to quantify. Here, scanning electrochemical cell microscopy coupled with fast scan cyclic voltammetry (FSCV) is used to resolve Zn plating and stripping on single-crystal (002), (100), and (101) surfaces. Meniscus-confined measurements reveal facet-dependent branch-specific apparent zero-current potentials and apparent exchange current densities, j0, with the kinetic ordering j0(100) > j0(101) > j0(002) for both plating and stripping. This ordering is reproduced across independently prepared electrodes and retained over different scan rates and aqueous electrolytes. Beyond charge transfer, Zn removal and regrowth are strongly crystallographically encoded: dissolution footprints preserve the symmetry of the parent facets, while potentiostatically deposited Zn adopts substrate-dependent growth geometries. These coupled kinetic and morphological differences translate directly to battery performance. Despite its slower apparent kinetics, the close-packed, low-energy (002) facet exhibits the longest cycling life in Zn/Zn symmetric cells and substantially improved capacity retention in both polyaniline/Zn and Na0.33V2O5/Zn full cells, whereas the faster (100) and (101) interfaces fail earlier. These findings establish a facet-dependent kinetics-stability trade-off and show that durable Zn anodes require coordinated control of charge transfer, dissolution topology, and crystallographic reconstruction.