Ultrafast microwave heated form-stable thermal package providing operating temperature for PEO all-solid-state batteries

•A form-stable thermal package and microwave transducing energy system were proposed.•The composite realized leakage-proof, at the cost of minor enthalpy loss of 11.27%.•Ultrafast microwave heating realized by graphene and enhanced microwave absorption with CF.•ASSBs achieved safe and low-power cold-starting in 1 min.