The composite NaNH2-NaBH4 (2/1 molar rate) doped with different amount Co-Ni-B catalyst was synthesized via liquid phase ball milling method in the cyclohexane agent. The composition evolution and dehydrogenation performance of the as prepared sample were characterized by means of XRD (X-ray diffraction), FT-IR (Fourier transform infrared spectroscopy) and TG-DTA-MS (Thermogravimetric-differential thermal analysis-mass spectroscopy) measurements, respectively; and the activation energies were calculated by the Achar differential and Coats-Redfern integral method. The composite NaNH2-NaBH4 (2/1) with 5 wt% Co-Ni-B catalyst (the sample C5) generated Na-3(NH2)(2)BH4 successfully after the liquid phase ball milling. Due to the interaction between functional groups of NaNH2-NaBH4 (2/1) with catalyst, Co-Ni-B catalyst not only benefits improving the thermodynamical performance, that is, the initial dehydrogenation temperature is as low as 200 degrees C and the weight percentage of hydrogen is about 5.05 wt% obtained from TG-DTA-MS curves; but also promoting the kinetics property that the activation energy of the major dehydrogenation stage is only 68.2 kJ mol(-1). Furthermore, it is revealed that the kinetics mechanism of the dehydrogenation performance depends on the synthesis methods and adding catalyst. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.