Da Zhang, Ziyang Song, Yumin Chen, Pingxuan Liu, Rong Gu, Ling Miao, Yaokang Lv, Yinsheng Wang, Lihua Gan, Mingxian Liu
Abstract Compared with (100) and (101) planes, Zn (0002) plane with the lowest nucleation energy is optimal for practical rechargeable zinc metal batteries (ZMBs), but precise crystallographic regulation of Zn (0002) plane orientation to significantly reduce intergranular strain accumulation for lasting ZMBs remain challenges. Herein, we develop an Al‐0.1wt%Si substrate with ultralow lattice mismatch (0.51%) to eliminate hierarchical twins and enable flat Zn nucleation for sustainable epitaxial stacking. Negligible lattice spacing deviation (0.2320 versus 0.2308 nm) between Al‐0.1wt%Si (111) and grown‐Zn (0002) plane achieves near‐zero strain in electrodeposited layer (0.22 versus 7.29 MPa of pure Zn foil). Al‐0.1wt%Si‐Zn (ASZ) anode exhibits a pronounced (0002)‐textured Zn orientation with a high Kearns factor (0.85 versus 0.29 of Zn foil), enabling dendrite‐suppressive planar growth. Consequently, ASZ||Cu cells demonstrate 99.83% Coulombic efficiency, while ASZ||ASZ cells operate stably for 8000 h at 5 mA cm −2 . Besides, ASZ||MnO 2 coin cells retain 73.97% capacity after 1500 cycles at 1 A g −1 , and pouch cells (2.8 Ah) operate over 1000 cycles at 1 A g −1 . This work opens a new window for designing lattice‐matched, strain‐free zinc anodes for advanced ZMBs.