Abstract
A polymer electrolyte is developed by integrating a poly(methyl methacrylate) (PMMA)/eutectic electrolyte (EE) phase into a porous polyethylene (PE) scaffold via a solution-casting strategy. In this rigid–flexible coupled architecture, the PMMA matrix serves as a solid host that coordinates with Li(+) through its polar carbonyl groups, thereby promoting lithium salt dissociation and establishing a stable ion transport network. The incorporated EE, composed of ethylene carbonate and LiTFSI, effectively reduces the glassy rigidity of PMMA and provides continuous pathways for fast ionic conduction. Meanwhile, the porous PE scaffold reinforces mechanical strength and resists lithium dendrite penetration, enabling a thin electrolyte membrane with excellent flexibility. The resulting electrolyte achieves an ionic conductivity of 1.59 × 10(−4) S cm(−1) at 30 °C, a lithium-ion transference number of 0.45, and an electrochemical stability window up to 4.75 V. In Li||LiFePO(4) cells, it delivers stable cycling at 3 C for 1000 cycles with 76.8% capacity retention and a Coulombic efficiency exceeding 99.9%. The monomer-free design eliminates residual reactive species that commonly compromise interfacial stability, offering a reliable pathway toward high-voltage solid-state lithium-metal batteries.