Non‐Epitaxial Electrodeposition of Overall 99% (002) Plane Achieves Extreme and Direct Utilization of 95% Zn Anode and By‐Product as Cathode

Zn anode protection in Zn‐ion batteries (ZIBs) face great challenges of high Zn utilization rate (i.e., depth of discharge, DOD) and high current density due to the large difficulty in obtaining an extreme overall RTC (relative texture coefficient) of Zn (002) plane. Through the potent interaction of Mn(III)aq and H+ with distinct Zn crystal planes under an electric field, large‐size Zn foils with a breakthrough (002) plane RTC of 99% (i.e., close to Zn single crystal) are electrodeposited on texture‐less substrates, which is also applicable from recycled Zn. The ultra‐high (002) plane RTC remarkably enhances cyclic performance of the Zn anode (70% DOD @ 45.5 mA cm‐2), and the DOD is even up to 95% (@ 28.1 mA cm‐2) with an electrolyte additive of polyaniline. Furthermore, MnO2, the by‐product of electrodeposition, is directly used as cathode of both coin cell and pouch battery, surpassing the cyclic performance exhibited by the majority of Zn||MnO2 batteries in previous instances. These results demonstrate the great potential of our strategy for high‐performance, low‐cost and large‐scale ZIBs.