Dual robust electrode-electrolyte interfaces enabled by fluorinated electrolyte for high-performance zinc metal batteries

Rechargeable zinc metal batteries (ZMBs) are promising for fabricating low-cost, safe, and high-energy-density storage systems. However, ZMBs typically undergo interfacial side reactions and cathode dissolution during cycling, resulting in the depletion of active materials and performance decay of batteries. Here, we develop a localized high-concentration fluorinated electrolyte featuring a high fluorine/oxygen atomic ratio (388.72%) with beneficial solvation chemistry, fostering the simultaneous formation of a cathode-electrolyte interphase (CEI) enriched with C–F bonds and a ZnF₂-dominant solid-electrolyte interphase (SEI). The constructed robust electrode-electrolyte interfaces (EEIs) contribute to dendrite-free zinc deposition and a highly stable cathode, demonstrating soft-packed Zn||Mn-doped V₂O₅ batteries with an exceptional energy density (91.25 Wh kg⁻¹_{cathode+anode}) and capacity retention (90.5%) over 500 cycles employing a limited zinc supply. The anode-free ZMBs deliver a record power density of 153.9 Wh kg⁻¹_{cathode+anode} with a high capacity retention of 80.2% over 1,500 cycles. This research provides significant insights for interface construction in multivalent ion batteries.