Robust Piezoelectric-Derived Bilayer Solid Electrolyte Interphase for Zn Anodes Operating from −60 to 60 °C

Research on the reversibility and long-term cycling stability of zinc-ion batteries (ZIBs) over a wide temperature range remains limited. One major challenge with gel electrolytes is ensuring the interface stability with Zn metal anodes under varying conditions. In this study, we introduce a multicomponent gel electrolyte that effectively addresses the interface stability challenges associated with Zn anodes under high current densities and wide temperature ranges. This advanced electrolyte is synthesized via the polymerization of poly(VDF-TrFE-CTFE) within a polyimide fiber network, which enables hydrogen-free and dendrite-free Zn deposition/stripping over 4350 h at 1 mA cm–2, even over 1500 h from −60 to 60 °C, even sustaining 20 mA cm–2 operation. Fluorine-rich components promote a self-adaptive bilayer solid electrolyte interphase (SEI) comprising an ultrathin amorphous outer layer and an inorganic/organic inner layer (ZnF2–ZnS–ZnO–ZnCO3), synergistically suppressing side reactions and guiding uniform Zn deposition via piezoelectric effects. Consequently, all-solid-state ZIBs paired with an iodine cathode achieve cycling stability: 36,500 cycles at 5 A g–1 (30 °C) and 1500 cycles at −30 °C, setting benchmarks for extreme-condition performance. This work advances interfacial engineering for high-rate, wide-temperature ZIBs through a rational electrolyte design and SEI modulation.