Highly Stable Aqueous/Organic Hybrid Zinc-Ion Batteries Based on a Synergistic Cathode/Anode Interface Engineering

Zn-ion batteries (ZIBs) are developing rapidly due to their advantages of safety, moderate energy density, and abundant Zn-metal reserves. However, the dendritic growth and side reactions at the Zn-based anode and the dissolution of metallic elements at transition metal-based cathodes destabilize the electrode/electrolyte interface, which ultimately reduces the electrochemical performance of ZIBs. Herein, an aqueous/organic hybrid electrolyte that endows synergistic cathode/anode interfacial layers is proposed. On the anode, the ZnF₂/Zn₃(PO₄)₂-rich film induces the Zn nucleation, enabling a dendrite-free and corrosion-free electrode morphology. On the cathode, in contrast to Zn deposition anomalously on the cathode surface due to underpotential deposition during cycling in the unmodified electrolyte, the obtained interfacial film using the hybrid electrolyte inhibits the dissolution of metallic elements and avoids Zn deposition on the transition metal-based cathode. As a result, a pouch cell with a metallic Zn anode and a LiMn₂O₄ cathode (depth of discharge: 40%) based on the modified electrolyte maintains a capacity of 92 mAh g^-1 after 235 cycles with a stable and clean cathode/anode interface. This research presents insight into the construction of a stable cathode/anode interface for long-cycling ZIBs.