Fabrication and hydrogen sorption behaviour of nanoparticulate MgH2 incorporated in a porous carbon host.

Nanoparticles of MgH2 incorporated in a mesoporous carbon aerogel demonstrated accelerated hydrogen exchange kinetics but no thermodynamic change in the equilibrium hydrogen pressure. Aerogels contained pores from <2 to approximately 30 nm in diameter with a peak at 13 nm in the pore size distribution. Nanoscale MgH2 was fabricated by depositing wetting layers of nickel or copper on the aerogel surface, melting Mg into the aerogel, and hydrogenating the Mg to MgH2. Aerogels with metal wetting layers incorporated 9-16 wt% MgH2, while a metal free aerogel incorporated only 3.6 wt% MgH2. The improved hydrogen sorption kinetics are due to both the aerogel limiting the maximum MgH(2) particle diameter and a catalytic effect from the Ni and Cu wetting layers. At 250 degrees C, MgH2 filled Ni decorated and Cu decorated carbon aerogels released H(2) at 25 wt% h(-1) and 5.5 wt% h(-1), respectively, while a MgH(2) filled aerogel without catalyst desorbed only 2.2 wt% h(-1) (all wt% h(-1) values are with respect to MgH2 mass). At the same temperature, MgH2 ball milled with synthetic graphite desorbed only 0.12 wt% h(-1), which demonstrated the advantage of incorporating nanoparticles in a porous host.

Kinetic limitations of the Mg(2)Si system for reversible hydrogen storage.

Despite the promising thermodynamics and storage capacities of many destabilized metal hydride hydrogen storage material systems, they are often kinetically limited from achieving practical and reversible behavior. Such is the case with the Mg2Si system. We investigated the kinetic mechanisms responsible for limiting the reversibility of the MgH2+Si system using thin films as a controlled research platform. We observed that the reaction MgH2 + 1/2Mg2Si + H2 is limited by the mass transport of Mg and Si into separate phases. Hydrogen readily diffuses through the Mg2Si material and nucleating MgH2 phase growth does not result in reaction completion. By depositing and characterizing multilayer films of Mg2Si and Mg with varying Mg2Si layer thicknesses, we conclude that the hydrogenation reaction consumes no more than 1 nm of Mg2Si, making this system impractical for reversible hydrogen storage.

The kinetic enhancement of hydrogen cycling in NaAlH(4) by melt infusion into nanoporous carbon aerogel.

Enhanced kinetic performance and reversibility have been achieved with uncatalyzed NaAlH4 by incorporation into nanoporous carbon aerogel. Aerogel with a pore size distribution peaked at 13 nm and a pore volume of 0.8 cm(3) g(-1) was filled with NaAlH4 to 94% capacity by melt infusion at 189 degrees C under 183 bar H(2) gas overpressure. Dehydrogenation to NaH + Al with reasonable kinetics was accomplished at 150 degrees C, well below the NaAlH4 melting temperature (183 degrees C), compared to hydrogen release above 230 degrees C for bulk uncatalyzed NaAlH4. Uncatalyzed bulk samples did not rehydrogenate under laboratory conditions, whereas NaAlH4 in a carbon aerogel host was readily rehydrogenated at approximately 160 degrees C and 100 bar H(2) to approximately 85% of its initial capacity. Ball-milled NaAlH4 catalyzed with 4 mol% TiCl3 showed somewhat better kinetics compared to the infused aerogel; nevertheless, the large kinetic enhancement obtained by incorporation into carbon aerogel, even in the absence of a catalyst, demonstrates the substantial benefit of confining the NaAlH4 to nanoscale dimensions.

The synthesis and hydrogen storage properties of a MgH(2) incorporated carbon aerogel scaffold.

A new approach to the incorporation of MgH2 in the nanometer-sized pores of a carbon aerogel scaffold was developed, by infiltrating the aerogel with a solution of dibutylmagnesium (MgBu2) precursor, and then hydrogenating the incorporated MgBu2 to MgH2. The resulting impregnated material showed broad x-ray diffraction peaks of MgH2. The incorporated MgH2 was not visible using a transmission electron microscope, which indicated that the incorporated hydride was nanosized and confined in the nanoporous structure of the aerogel. The loading of MgH2 was determined as 15-17 wt%, of which 75% is reversible over ten cycles. Incorporated MgH2 had >5 times faster dehydrogenation kinetics than ball-milled activated MgH2, which may be attributed to the particle size of the former being smaller than that of the latter. Cycling tests of the incorporated MgH(2) showed that the dehydrogenation kinetics are unchanged over four cycles. Our results demonstrate that confinement of metal hydride materials in a nanoporous scaffold is an efficient way to avoid aggregation and improve cycling kinetics for hydrogen storage materials.

Size effects on the hydrogen storage properties of nanoscaffolded Li3BN2H8.

The use of Li3BN2H8 complex hydride as a practical hydrogen storage material is limited by its high desorption temperature and poor reversibility. While certain catalysts have been shown to decrease the dehydrogenation temperature, no significant improvement in reversibility has been reported thus far. In this study, we demonstrated that tuning the particle size to the nanometer scale by infiltration into nanoporous carbon scaffolds leads to dramatic improvements in the reversibility of Li3BN2H8. Possible changes in the dehydrogenation path were also observed in the nanoscaffolded hydride.