Enabling one-step regeneration of LiBH4 with self-sustaining hydrogen in its spent fuel—one pathway to storing renewable hydrogen

LiBH4 (LB in short) with a hydrogen capacity as high as 18.5 wt% and a low molecular weight (21.78 g mol−1) is among the most promising candidates for the hydrogen-based economy. However, current major technologies in (re)generation of LB rely heavily on energy-intensive processes, which greatly prohibits practical scaling-up of applications. Here we report a sustainable and effective approach to (re)generate LB via converting renewable H+ in crystalline water into H-, achieving a desirable yield of ∼50%. This one-step synthesis method relies on the reaction between spent fuels, specifically LiBO2·xH2O, and Mg-based alloys to form LB under ambient atmosphere. Notably, our approach surpasses the efficiency of other conventional method, such as LiH-B-H2 and MgH2-LiBO2 systems, which not only bypasses the energy-intensive dehydration procedure of LiBO2·xH2O (∼470 ℃) but also eliminates the use of costly hydrides or high-pressure H2. Our findings indicate that Mg participated in the regeneration process prior to Al in Mg-Al alloys and [BH4]- is gradually evolved from other intermediate species [BHx(OH)4-x]- (x = 0, 1, 2, 3). By combining hydrogen release and efficient storage of hydrogen-rich substrate in a closed materials cycle, this study may shed light on a promising step toward application of renewable hydrogen in a fuel cell-based hydrogen economy.