High‐Work‐Function Semiconducting Artificial Layer for Durable Zinc Metal Anodes

Abstract Rechargeable aqueous zinc‐ion batteries are a promising solution for safe, cost‐effective, and sustainable energy storage. However, their widespread adoption is thwarted by challenges, such as dendrite formation, hydrogen evolution, and corrosion of Zn anode. Herein, a low‐cost and eco‐friendly p‐type high‐work‐function semiconducting artificial layer (HWF‐SAL) is designed on Zn anode, achieving desirable electrochemical performance for durable Zn anode. HWF‐SAL initially forms a Schottky barrier with Zn, which impedes electron transfer to the electrolyte and thereby suppresses hydrogen evolution. Additionally, in situ formation of CuZn alloy during cycling modulates the interfacial electronic nature, effectively curtailing the Schottky barrier and inducing an ohmic contact. This facilitates spontaneous electron accumulation at the Zn/HWF‐SAL interface, thereby guiding dendrite‐free Zn deposition, alleviating Zn corrosion, and improving Zn anode stability. As a result, HWF‐SAL symmetric cells manifest stable Zn plating/stripping reversibility over 3500 h while HWF‐SAL/Cu asymmetric cells exhibit an impressive average Coulombic efficiency (ACE) of 99.70% over 1150 cycles at 0.5 mA cm −2 /0.5 mAh cm −2 . Furthermore, the HWF‐SAL/NVO full cell delivers a high specific capacity of ≈300 mAh g −1 , retaining 82% capacity after 600 cycles, along with an ACE of 99.98%. These findings offer a practical pathway toward high‐performance aqueous Zn‐ion batteries.