LAUSR

The tendency of zinc (Zn) anodes to form uncontrolled Zn electrodeposits and the occurrence of side‐reactions at Zn‐electrolyte interfaces are a fundamental barrier hampering broad applications of aqueous rechargeable Zn‐based batteries. Herein, a ferroelectric domain‐mediated strategy is proposed to manipulate the Zn plating behavior and achieve controllable Zn growth orientation by coating Zn foil with a ferroelectric tetragonal KTN (t‐KTN) layer. The ferroelectric domain of t‐KTN single crystals exhibits periodic distribution of upward and downward polarizations, corresponding to alternating positively and negatively charged surfaces. The charged ferroelectric surfaces can manipulate the transfer kinetics of Zn ions and the concentration distribution of anions via the interplay between ferroelectric dipoles and adsorbed ions. With the synergistic effect of the ferroelectric polarization and domain configurations, the well‐aligned interlamellar arrays composed of electrodeposited Zn are formed in the initial deposition process, which enable selective deposition within interlamellar arrays and eliminate the dendrite growth during the following plating process. As a result, the t‐KTN layer‐modified Zn anode enables reversible Zn plating/stripping with low voltage hysteresis for over 1200 h at 1 mA cm−2 in symmetric cells, and the assembled full cell exhibits a significantly enhanced cycling stability of over 5500 cycles at 5 A g−1.