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A new composite solid polymer electrolyte (SPE) PPC-PEO 10 W [5:5]-1%wt LAGP with high conductivity is successfully prepared. The relationships between the conductivities and compositions are systematically characterized. The optimal composite polymer electrolyte presents a maximum conductivity of 8.39 × 10−4 S cm−1 with a 4.5 V electrochemical window and excellent stability with lithium at 60 °C...