Low Strain Mediated Zn (0002) Plane Epitaxial Plating for Highly Stable Zinc Metal Batteries

Abstract Optimizing the crystalline orientation to achieve stable Zn (0002) plane growth is pursued for highly reversible zinc metal batteries (ZMBs). However, the lattice strain of Zn substrate hinders stable Zn 2+ plating/stripping and sustainable epitaxial growth of Zn (0002) texture. Herein, we present a low‐strain strategy to mediate nucleated‐Zn grains for stabilizing Zn 2+ electrodeposition/stripping process and guiding sustainable Zn 2+ growth along (0002) surfaces. Fluorinated anthracene triptycene polymer (FATP) photopolymerized on Zn exhibits nanocrystalline structure with highly ordered nanochannels (1.5 nm), enabling oriented nucleation and sustainable epitaxial stacking of Zn (0002) plane due to low nucleation energy (0.2 vs. 1.1 e − Å −3 of pure Zn) and low grain strain (−0.2 to 0.4 vs. −0.9 to 0.9 MPa). Besides, the ordered porous FATP nanofilm refines electroplating Zn grains (9.4 vs. 26.7 µm), alleviating strain accumulation (3.7 vs. 28.2 MPa) and lattice distortion. Consequently, FATP‐Zn||Cu cell achieves a high average Coulombic efficiency of 99.6% over 6000 cycles, while FATP‐Zn||FATP‐Zn cell shows stable plating/stripping after 5000 h. Notably, FATP‐Zn||MnO 2 pouch cell (2.77 Ah) demonstrates stable operation over 1000 cycles. This work presents a new approach to designing Zn anodes with refined nucleated‐Zn grains and sustainable Zn (0002) plane stacking for advanced ZMBs.