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In-situ formation of ultrafine MgNi3B2 and TiB2 nanoparticles: Heterogeneous nucleating and grain coarsening retardant agents for magnesium borate in Li–Mg–B–H reactive hydride composite.
- Source :
-
International Journal of Hydrogen Energy . Oct2019, Vol. 44 Issue 50, p27529-27541. 13p. - Publication Year :
- 2019
-
Abstract
- Li–Mg–B–H reactive hydride composite (RHC) has attracted extensive attention over the past decades for its extremely high hydrogen storage capacity (11.5 wt%). But the sluggish desorption kinetics for the second step dehydrogenation reaction need to be further improved. Herein, short rod-like TMTiO 3 (TM = Co, Ni) bimetallic oxides, which contain two kinds of transition metal elements, were synthesized and introduced into Li–Mg–B–H RHC for the first time. The NiTiO 3 exhibits excellent catalytic effect on the hydrogen desorption kinetic performance of Li–Mg–B–H RHC, and the incubation period for the second step dehydrogenation reaction is eliminated completely by reducing the apparent activation energy for the generation of MgB 2 from 296 kJ/mol to 269 kJ/mol. The NiTiO 3 doped Li–Mg–B–H RHC can desorb about 9.0 wt% H 2 without obvious attenuation of kinetic performance in five cycles. Mechanism analyses reveal that the in-situ generated nano-sized MgNi 3 B 2 and TiB 2 species (∼5 nm) both meet the critical value (< 10%) of the edge-to-edge matching model (5.77% for MgNi 3 B 2 and 2.22% for TiB 2), which play a significant role in supporting the nucleation of MgB 2. Meanwhile, the extremely fine MgNi 3 B 2 and TiB 2 heterogeneous nucleation sites can inhibit the excessive growth for a single crystal nucleus of MgB 2. The heterogeneous nucleation and grain refinement mechanisms caused by the novel bimetallic oxide could provide alternative insights into designing an in-situ generated nano-sized catalytic hydrogen storage system with enhanced kinetics and cyclic stability for hydrogen-fueled applications. Image 1 • Short rod-like NiTiO 3 eliminates the incubation period of dehydrogenation. • In-situ generated MgNi 3 B 2 and TiB 2 nano-species support the nucleation of MgB 2. • Fine MgNi 3 B 2 and TiB 2 nucleation sites cause the grain refinement of MgB 2. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 03603199
- Volume :
- 44
- Issue :
- 50
- Database :
- Academic Search Index
- Journal :
- International Journal of Hydrogen Energy
- Publication Type :
- Academic Journal
- Accession number :
- 139008755
- Full Text :
- https://doi.org/10.1016/j.ijhydene.2019.08.222