Microstructured Metal Electrodeposition at a Micellar Brush-Decorated Interface

Metal electrodeposition is usually interfered by stochastic ion arrival, local field amplification, and uncontrolled crystal growth, rendering it difficult to translate molecular-level interfacial design into prescribed mesoscale architectures. Here, we report that surface-emanated micellar brush with a forest-like soft architecture can finely modulate the orientation and microstructure of metal electrodeposition. The poly(l-lactic acid)-b-poly(2-vinylpyridine) micellar brush provides a hierarchically open nanoarray platform for continuous accumulation of metal ions through dynamical coordination with the pyridyl-rich corona and sustained deposition of reduced metal at the inter-micellar voids. Unlike conventional homopolymer coatings that mainly lead to flat deposition of Zn, such micellar-brush layer promotes vertically aligned zinc blades through coupled ion funneling and oriented nanoconfinement. The resulting zinc anode reveals a low nucleation overpotential of ∼21 mV, a high Zn²⁺ transference number of 0.79, a rapid rate of ∼24.2 µm h^-1 at 10 mA cm^-2, and a polarization of only 18 mV upon reversible plating/stripping over 3000 h. The full cells integrated by vertically microstructured Zn anode with V₂O₅ cathode retain 89.6% capacity after 1000 cycles at 1 A g^-1. This work establishes a general route to tailored metal microstructures through softly confined electrodeposition across a spatially directing and chemically associating polymer self-assembly interfaces.