In an attempt to develop lithium borohydrides as reversible hydrogen storage materials with high hydrogen storage capacities, the feasibility of reducing the dehydrogenation temperature of the lithium borohydride and moderating rehydrogenation conditions was explored. The lithium borohydride was modified by ball milling with metal oxides and metal chlorides as additives. The modified lithium borohydrides released 9 wt % hydrogen starting from 473 K. The dehydrided modified lithium borohydrides absorbed 7-9 wt % hydrogen at 873 K and 7 MPa. The modification with additives reduced the dehydriding starting temperature from 673 to 473 K and moderated the rehydrogenation conditions from 923 K/15 MPa to 873 K/7 MPa. XRD and SEM analysis revealed the formation of an intermediate compound that might play a key role in changing the reaction path, resulting in the lower dehydriding temperature and reversibility. The reversible hydrogen storage capacity of the oxide-modified lithium borohydrides decreased gradually during hydriding/dehydriding cycling. One of the possible reasons for this effect might be the loss of boron during dehydrogenation, but this can be prevented by changing the dehydriding path using appropriate additives. The additives reduced the dehydriding temperature and improved the reversibility, but they also reduced the hydrogen storage capacity. The best compromise can be reached by selecting appropriate additives, optimizing the additive loading, and using new synthesis processes other than ball milling.

This paper reports the results of the effort to destabilize lithium borohydride for reversible hydrogen storage. Various metals, metal hydrides, and metal chlorides were selected and evaluated as destabilization agents for reducing dehydriding temperatures and improving dehydriding/rehydriding reversibility. The most effective material was LiBH4 + 0.2MgCl2 + 0.1TiCl3 which starts desorbing 5 wt % of hydrogen at 60 degrees C and can be rehydrogenated to 4.5 wt % at 600 degrees C and 70 bar. X-ray diffraction and Raman spectroscopic analysis show the interaction of LiBH4 with additives and the unusual change of B-H stretching.

In an effort to develop reversible metal borohydrides with high hydrogen storage capacities and low dehydriding temperature, doping LiBH4 with various metal halides and hydrides has been conducted. Several metal halides such as TiCl3, TiF3, and ZnF2 effectively reduced the dehydriding temperature through a cation exchange interaction. Some of the halide doped LiBH4 are partially reversible. The LiBH4 + 0.1TiF3 desorbed 3.5 wt % and 8.5 wt % hydrogen at 150 and 450 °C, respectively, with subsequent reabsorption of 6 wt % hydrogen at 500 °C and 70 bar observed. XRD and NMR analysis of the rehydrided samples confirmed the reformation of LiBH4. The existence of the (B12H12)−2 species in dehydrided and rehydrided samples gives insight into the resultant partial reversibility. A number of other halides, MgF2, MgCl2, CaCl2, SrCl2, and FeCl3, did not reduce the dehydriding temperature of LiBH4 significantly. XRD and TGA-RGA analyses indicated that an increasing proportion of halides such as TiCl3, TiF3, and ZnCl2 from 0.1 to 0.5 mol makes lithium borohydrides less stable and volatile. Although the less stable borohydrides such as LiBH4 + 0.5TiCl3, LiBH4 + 0.5TiF3, and LiBH4 + 0.5ZnCl2 release hydrogen at room temperature, they are not reversible due to unrecoverable boron loss caused by diborane emission. In most cases, doping that produced less stable borohydrides also reduced the reversible hydrogen uptake. It was also observed that halide doping changed the melting points and reduced air sensitivity of lithium borohydrides.