The phase change material is currently being regarded as an effective cooling media to be applied in the thermal management of lithium batteries-powered vehicles, in which the inorganic hydrate phase change material is desirable and widely investigated due to the high thermal conductivity, latent heat value, and low cost. However, when applied to thermal energy storage applications, supercooling and phase separation are problematic. To effectively circumvent this issue, this work considers utilizing the disodium hydrogen phosphate dodecahydrate as the matrix of the composite phase change material, as the phase transition temperature is suitable for the battery's operating temperature range. Meanwhile, the nucleating agent sodium metasilicate nonahydrate with similar lattice parameters and the thickener carboxymethyl cellulose are used to suppress the supercooling and eliminate the phase separation, respectively. Effects of nucleating agent, surface modified aluminum nitride, and short-cut carbon fiber on the supercooling degree, and thermal conductivity and curing performance in the phase change material are evaluated and discussed in detail to determine the optimal preparation scheme for Na2HPO4·12H2O/modified AlN/CF inorganic composite phase change materials. Experimental results show that the addition of 4 wt% Na2SiO3·9H2O, 4 wt% CMC, 12 wt% modified AlN, and 6 wt% CF reduces the supercooling degree of the composite phase change material to 1.9°C and increases the thermal conductivity to 1.86 W/(m·K). The composite phase change material is found to have a suitable phase change temperature (35°C), high latent heat (249 J/g), excellent shaping effect, and electrical safety performance. In addition, the composite phase change material battery module can effectively control the battery's temperature, with the maximum temperature reduced by 40.9°C at 3C discharge rate and 30°C ambient temperature compared with the natural cooling battery module. The maximum temperature difference of the composite phase change material battery module is shown to be reduced to the minimum value of 0.9°C. Highlights A novel disodium hydrogen phosphate dodecahydrate—modified aluminum nitride—carbon fiber composite phase change material is designed and prepared for battery thermal management systems. The antiwater modification scheme of AlN is proposed and assessed. The effects of AlN before and after modification on the thermal properties of CPCM are compared. The joint use of nucleating agent sodium metasilicate nonahydrate and thermal conductive filler AlN contributes to significantly inhibiting the supercooling of hydrate salt. The addition of CF can effectively increase the thermal conductivity of CPCM and prevent its leakage. CPCM has suitable phase change temperature, high thermal conductivity and latent heat value, excellent electrical safety, and stable curing performance. The battery test bench is constructed and the discharge test of the CPCM battery module is carried out. The results show that the CPCM battery module has excellent cooling performance and temperature uniformity.