Ligand engineering regulation toward Zn ions and Zn substrate for all‐climate Zn metal batteries

The regulation of artificial interphase for advanced Zn anode is an effective solution to achieve superior electrochemical performance for aqueous batteries. However, the deployment of atomically precise architectures and ligand engineering to achieve functionalization‐oriented regulatory screening is lacking, which is hindered by higher requirements for synthetic chemistry and structural chemistry. Herein, we have first performed ligand engineering which selected zinc ion trapping ligands (–CH3) based on the coordination effect, and zinc substrate binding ligands (–N=N‐xC6H5) based on the electrostatic interaction. Correspondingly, octa nuclear Zn(II)‐Siloxane‐PhPz/BiPhPz/TriPhPz Cluster (OZSPC/OZSBPC/OZSTPC) are accurately synthesized, and OZSBPC is verified to serve as the most suitable artificial interphase via balancing the interactions with both Zn2+ and Zn substrate (“Zn‐Zn effect”). Consequently, at –30 °C, the assembled OZSBPC‐Zn symmetric cells run for 3000 h and the assembled full cells with OZSBPC‐Zn anode could be stable for 10,000 cycles. The pouch cells using OZSBPC‐Zn anode deliver a reversible capacity of ~1.2 Ah and the energy density of 41 Wh kgtotal−1 with excellent cycling performance. The successful structural design of OZSBPC explores a novel well‐defined structural design concept as one criterion for artificial interface as well as motivates batteries systems to meet the requirements of industrialization.