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The mixing soft-segment WPU (waterborne polyurethane) polymer electrolytes were synthesized by using PEO (poly(ethylene oxide)) and PDMS (polydimethylsiloxane) as the soft segments. These polymer electrolytes exhibit good thermal and electro-chemical stability. The conductivity of the gel polymer electrolyte is 2.52×10-3 S/cm at 25 ℃ with the LiTFSI/(DMC + EC) content of 130%.