Synergistic Modulation of Mass Transfer and Parasitic Reactions of Zn Metal Anode via Bioinspired Artificial Protection Layer

Abstract Rechargeable aqueous zinc–ion batteries are regarded as promising energy storage devices due to their attractive economic benefits and extraordinary electrochemical performance. However, the sluggish Zn²⁺ mass transfer behavior and water‐induced parasitic reactions that occurred on the anode–electrode interface inevitably restrain their applications. Herein, inspired by the selective permeability and superior stability of plasma membrane, a thin UiO‐66 metal‐organic framework layer with smart aperture size is ex‐situ decorated onto the Zn anode. Experimental characterizations in conjunction with theoretical calculations demonstrate that this bio‐inspired layer promotes the de‐solvation process of hydrated Zn²⁺ and reduces the effective contact between the anode and H₂O molecules, thereby boosting Zn²⁺ deposition kinetics and restraining interfacial parasitic reactions. Hence, the Zn||Zn cells could sustain a long lifespan of 1680 h and the Zn||Cu cells yielded a stable coulombic efficiency of over 99.3% throughout 600 cycles under the assistance of the bio‐inspired layer. Moreover, pairing with δ‐MnO₂ cathode, the full cells also demonstrate prominent cycling stability and rate performance. From the bio‐inspired design philosophy, this work provides a novel insight into the development of aqueous batteries.