Spontaneous Construction of Nucleophilic Carbonyl‐Containing Interphase toward Ultrastable Zinc‐Metal Anodes

Abstract Multifunctional interfacial engineering on the Zn anode to conquer dendrite growth, hydrogen evolution, and the sluggish kinetics associated with Zn deposition is highly desirable for boosting the commercialization of aqueous zinc‐ion batteries. Herein, a spontaneous construction of carbonyl‐containing layer on a Zn anode (Zn@ZCO) is rationally designed as an ion redistributor and functional protective interphase. It has strong zincphilicity and dendrite suppression ability due to the significant interaction of the highly electronegative and highly nucleophilic carbonyl oxygen, favoring ion transport and homogenizing Zn deposition effectively. On the other side, the hydrogen bond formed by the proton acceptor of oxygen atom in ZCO regulates the Zn‐ion desolvation process at the interfaces, thus bounding water activity and then mitigating water‐induced parasitic reactions. Consequently, the Zn@ZCO anode exhibits an extended cycling lifespan of 5000 h (>208 days) with a dendrite‐free surface and negligible by‐products. More encouragingly, the effectiveness is also convincing in NH 4 V 4 O 10 ‐based full‐cells with excellent rate performance and cyclic stability. The stabilized Zn anode enabled by the strategy of spontaneous construction of functional solid electrolyte interphase brings forward a facile and instructive approach toward high‐performance zinc‐storage systems.