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.

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Summary The widespread use of lithium‐ion battery (LIB) urgently needs a thermal management system with excellent performance to manage it. Phase change material (PCM) has been adapted for thermal management of LIB because it can absorb a mass of energy without additional power. In this research, the thermal conductivity of PCM is improved, and its cooling effect is detected. The addition of hybrid thermal conductivity filler is beneficial to its uniform dispersion and improvement of aggregation phenomenon on the surface of materials. The results show that the PCM with hybrid filler has better thermal conductivity, which is increased by 264%. In different proportions of composite materials, the composite phase change material with 1% few‐layer graphene and 2% graphite nanoplatelet can play a better cooling effect in LIB module thermal management, and it respectively decreases the maximal temperature of the battery module by 7.17°C, 10.52°C, and 16.33°C at 1C, 2C, and 3C conditions, and the maximal temperature difference does not exceed the safety range of 5°C.

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