Manipulating the Zinc Deposition Behavior in Hexagonal Patterns at the Preferential Zn (100) Crystal Plane to Construct Surficial Dendrite‐Free Zinc Metal Anode

Abstract Zinc metal has a severe dendrite issue caused by the uneven Zn plating/stripping during continual cycles, which hinders the practical application of ZIBs. The surficial atomic structure of zinc anode plays a decisive role in solving dendrites and improving the electrochemical performance. According to the density functional theory results, Zn (100) plane possesses a much stronger adsorption energy of zinc atom compared with the (002), thus zinc atom preferentially nucleates on the (100) surface. It subsequently continues to grow vertically on (100). Herein, the zinc anode is designed with hexagonal‐hole patterns (h‐Zn) through a phosphoric acid etching reaction. An abundance of Zn (100) crystal planes are exposed perpendicularly to the anode surface, while the (002) surfaces are at the bottom of these hexagonal holes. Zinc prefers to deposit in hexagonal holes at the (100) surfaces, favoring the restraining of the surficial dendrite growth and accelerating the Zn deposition kinetics. Thus, the symmetric cell using h‐Zn exhibits a long cycling lifespan for over 1200 h and extremely low polarization voltage of ≈80 mV at 5 mA cm –2 and 1 mAh cm –2 . This work provides an insight into the surficial structure design and crystal plane regulation to fabricate brilliant zinc metal anodes.