Changfeng Lin, Baoquan Liu, Si Wen Tang, Yanzeng Ge, Haizhen Jiang, Daoxiong Wu, Jing Li, Hui Zhang, Zhuoliang Jiang, Tianyu Qiu, Xinlong Tian, Jinlin Yang
ABSTRACT Modulating the crystallography of Zn metal to promote the growth of the low‐surface‐energy Zn (002) plane has been recognized as an effective strategy for enhancing Zn reversibility. However, the lattice mismatch between the substrate and Zn metal has hampered the epitaxial electrodeposition process. Herein, a class of 2D materials with a six‐membered‐ring (SMR) structure is presented as a low‐lattice‐mismatch substrate to induce Zn (002) heteroepitaxial deposition. Using hydrogenated borophene as a model system, it is demonstrated that the unique SMR structure selectively locks the lattice orientation of the Zn deposits, enabling the close‐packed crystallographic growth of (002)‐textured Zn metal. Meanwhile, the orderly open channels and strong zincophilicity of borophene promote Zn 2+ migration and homogenize the Zn 2+ flux to achieve uniform Zn deposition. These combined advantages of borophene enable the Zn||Zn pouch cell to exhibit a cumulative capacity of 4625 mAh cm −2 . Additionally, the Zn||V 2 O 3 pouch cell operates stably over 200 cycles with a low negative/positive capacity ratio of 2.1. Furthermore, a series of 2D SMR materials is demonstrated to act as an interfacial lattice locking layer through both theoretical and experimental verification. This study provides new insights into the design of heteroepitaxial substrates for highly reversible Zn deposition.