Phosphorous‐Doping Strategy Enabled “Concrete‐Slab”‐Like Zn Layer for Highly Stable 3D Composite Anode

Abstract Zinc electroplating/stripping is a promising electrochemical reaction for aqueous battery anodes, offering advantages such as high safety, low cost, and fast reaction kinetics. However, the growth of zinc dendrites is a major obstacle impeding its commercialization. To address these challenges, a phosphorus‐doping strategy is proposed for preparing a high Zn‐affinity C 3 N 4 coupled carbon nanotube 3D framework (PCN‐S). The addition of P facilitates the efficient crystallization of Zn that leads to the formation of a “concrete‐slab”‐like zinc layer on the PCN‐S surface. Moreover, the unique “release effect” possessed by the P‐doped 3D framework contributes to more stable cycling at high current. Such structural characteristics result in significantly enhanced stability of Zn metal deposition and extend the cycle life of full cells. The Zn@PCN‐S//Zn@PCN‐S symmetric cell exhibits an impressive long‐term cycle time exceeding 1500 h (1 mA cm ‒2 ). Consequently, aqueous rechargeable zinc‐metal batteries constructed with the 3D Zn@PCN‐S anode can achieve a specific energy of approximately ≈340 mAh g ‒1 and cycling for over 600 h. This work introduces a promising option for next‐generation energy storage technologies.