The thermal safety problem of lithium-ion batteries (LIB) in use requires an excellent thermal management system to preserve it. In the paper, an expansion flame-retardant composed of APP and CFA and kaolinite is used to enhance the flame-retardant property of phase change materials (PCM). The performances of PCM and their property in the thermal management of LIB were studied. The results indicate that the kaolinite can improve the long-term thermostability of PCM. The addition of flame retardant can make the flame-retardant property of PCM reach V0 level. The synergistic action of expansion flame-retardant and kaolinite can increase the residual carbon and enhance the thermal reliability of flame-retardant PCM (RPCM). The RPCM has an obvious cooling effect on the surface temperature of the battery. The RPCM can reduce the maximum temperature of the cell to 37.4 °C at 3 C, which is 12 °C lower than pure PA. The peak temperature of the battery pack at 3 C is also reduced to 50.28 °C by the flame-retardant PCM, and the temperature difference is kept within 5 °C.