Electrosynthesis of Metal–Organic Framework Interlayer to Realize Highly Stable and Kinetics‐Enhanced Zn Metal Anode

Abstract To facilitate the practical application of aqueous Zn metal batteries, numerous artificial interlayers are designed to mitigate rampant parasitic reactions and uncontrollable dendrite growth on the Zn metal anode. Traditionally, these interlayers are prepared through the doctor blade method. However, the introduced insulting binder generally compromises their interfacial performance. In this study, the metal–organic framework (MOF) interlayer is fabricated on the Zn metal anode by a facile and binder‐free electrosynthesis technique. The electrosynthetic Co‐ZIF‐8 interlayer enables the Zn metal anode to sustain cycles of 1280 h with a low voltage hysteresis. Moreover, the full cells coupled with MnO₂ and NH₄V₄O₁₀ cathodes exhibit exceptional cycling performance, maintaining 89% and 72% of their initial capacity after numerous cycles, respectively. Based on SEM measurements and density functional theory calculations, the densely packed morphology, unimpeded Zn²⁺ ions transport channels, and affinity of the imidazole ring and Co node within the ZIF‐8 structure to Zn atom are demonstrated to inhibit parasitic reactions, promote Zn²⁺ ions transport, and realize uniform Zn deposition. The proposed electrosynthesis method for constructing the MOF interlayer provides a straightforward and reliable approach to developing a highly stable Zn metal anode.