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The reactions of sodium amidoborane (NaNH2BH3) with NiBr2 have been investigated, and the results showed that black precipitate 1 including the NiBNHx composites could be obtained. From the aqueous solution of the precipitate 1, the hydrolysis product Ni-B (2) was isolated and characterized. Both the in situ formed precipitate 1 and the hydrolysis product 2 can catalyze the formation of Na[BH3(NH2BH2)2H]. CoCl2 showed comparable performance with NiBr2. Based on these results, a facile method for the synthesis of Na[BH3(NH2BH2)2H] has been developed. This wo