Enhanced ionic conductivity and interface stability of hybrid solid-state polymer electrolyte for rechargeable lithium metal batteries

Compared to conventional organic liquid electrolyte, solid-state polymer electrolytes are extensively considered as an alternative candidate for next generation high-energy batteries because of their high safety, non-leakage and electrochemical stability with the metallic lithium (Li) anode. However, solid-state polymer electrolytes generally show low ionic conductivity and high interfacial impedance to electrodes. Here we report a hybrid solid-state electrolyte, presenting an ultra-high ionic conductivity of 3.27 mS cm⁻¹ at room temperature, a wide electrochemical stability window of 4.9 V, and non-flammability. This electrolyte consists of a polymer blend matrix (polyethylene oxide and poly (vinylidene fluoride-co-hexafluoropropylene)), Li⁺ conductive ceramic filler (Li_1.5Al_0.5Ge_1.5(PO₄)₃) and a solvate ionic liquid (LiFSI in tetra ethylene glycol dimethyl ether, 1:1 in molar ratio) as plasticizer. The introduction of the solvate ionic liquid to the solid-state electrolyte not only improves its ionic conductivity but also remarkably enhances the stability of the interface with Li anode. When applied in Li metal batteries, a Li|Li symmetric cell can operate stably over 800 h with a minimal polarization of 25 mV and a full Li|LiFePO₄ cell delivers a high specific capacity of 158 mAh g⁻¹ after 100 cycles at room temperature.