Dynamic Bridging Ligand‐Induced Regulated Coordination Chemistry for Highly Reversible Zn‐Metal Anodes

Abstract The lifespan of aqueous Zn‐ion batteries (AZIBs) is significantly affected by the Zn anode interfacial hydrogen evolution and uncontrolled dendrite growth. Although the development of versatile organic molecule additives presents a promising solution to mitigate these issues, the limited coordinated capability and uncontrolled electrochemical consumption during cycling remain challenging. Herein, a molecular dynamic bridging strategy is proposed by incorporating tris(2‐pyridylmethyl)amine (TPA) into the electrolyte, enabling a highly reversible Zn anode. The TPA additive, featuring four‐nitrogen‐atom coordinated sites, acts as a molecular bridge that dynamically strengthens coordination with Zn 2+ and concurrently attracts more OTf − within the interface. This TPA‐regulated interfacial modulation promotes Zn 2+ transport and subsequent OTf − decomposition, forming a robust and inorganic‐rich solid electrolyte interphase, thereby significantly reducing side reactions and facilitating reversible Zn deposition. Consequently, the Zn anode with TPA electrolyte demonstrates an extended lifespan of over 4000 h in the symmetric cells and an impressive 99.84% Coulombic efficiency. Furthermore, Zn||PANI full cell runs over 4000 cycles with 81.9% capacity retention at 3 A g −1 . This work highlights the potential of a multi‐coordination molecular dynamic bridging strategy to innovatively guide the design of advanced high‐performance electrolyte additives for AZIBs.