Electrospinning Fiber Membrane‐Derived Gel Polymer Electrolytes with High Mechanical Strength and Low Swelling Effect for High‐Safety Lithium Metal Batteries

Abstract The practical application of lithium metal batteries (LMBs) is hindered by the issues of flammable electrolytes, lithium dendrites and the resulting thermal runaway. Designing flame‐retardant electrolytes with high performance is a valid strategy to break the current dilemma. In this work, the flame retardant of triphenyl phosphate (TPP) is elaborately encapsulated into the polymer shell of polyacrylonitrile (PAN) and polyvinylidene fluoride‐hexafluoropropylene (PVDF‐HFP) to realize the controllable release of TPP during the soaking process. The resulting TPP@PAN/PVDF‐HFP fiber membrane holds high thermal stability, high mechanical strength, and low swelling rate, which is essential for the preparation of flame‐retardant gel polymer electrolyte (GPE). As demonstrated, the TPP@PAN/PVDF‐HFP GPE can deliver high Li⁺ transference number of 0.877, low interfacial activation energy barrier of 26.6 kJ mol⁻¹ and heterogeneous SEI composition of Li₃PO₄/Li₂CO₃/LiF. The corresponding Li||Li cells achieve stable voltage polarization over 1000 h, and the Li||Cu cells display high plating/stripping CE of 99.1%. Meanwhile, the optimized Li||LiFePO₄ batteries exhibit high reversible capacity of 158 mAh g⁻¹ after 200 cycles at 0.5 C, and present outstanding fire resistance through the thermal runaway and puncture test. This study will open window for the design of high‐safety electrolytes to promote the practical application of LMBs.