Phosphated Electrolyte Enabling Dual Robust Electrode–Electrolyte Interfacial Reconstruction Toward Capable Zn Metal Batteries

Abstract Rechargeable aqueous zinc‐ion batteries (ZIBs) are expected to be the next generation of low‐cost, safe, and high‐energy‐density energy storage systems. However, undesirable electrode/electrolyte interfacial (EEI) side reactions of anode and dissolution of cathode materials during cycling of ZIBs have led to drastic degradation of battery performance. Here, a phosphated electrolyte is developed to facilitate the simultaneous formation of a Zn 3 (PO 4 ) 2 ‐rich solid electrolyte interphase (SEI) and the cathode/electrolyte interface (CEI) as well as improved solvent chemistry. The in situ generated robust EEI induce uniform deposition of zinc and inhibit solvation of the cathode material to achieve a high performance ZIBs. The improved solvent chemistry promises stable cycling at low temperatures with an ultra‐long life of 600 h at −10 °C. Moreover, the pouch cell with phosphated electrolyte exhibits excellent cycling performance with no significant capacity degradation after 150 cycles. In addition, the phosphated electrolyte in anode‐free ZIBs performances a long lifetime of 200 cycles. This study provides a simple and effective strategy for interface construction in ZIBs.