Cerium: an unlikely replacement of dysprosium in high performance Nd-Fe-B permanent magnets.

Replacement of Dy and substitution of Nd in NdFeB-based permanent magnets by Ce, the most abundant and lowest cost rare earth element, is important because Dy and Nd are costly and critical rare earth elements. The Ce, Co co-doped alloys have excellent high-temperature magnetic properties with an intrinsic coercivity being the highest known for T ≥ 453 K.

Sodium magnesium amidoborane: the first mixed-metal amidoborane.

The first example of a mixed-metal amidoborane Na(2)Mg(NH(2)BH(3))(4) has been successfully synthesized. It forms an ordered arrangement in cation coordinations, i.e., Mg(2+) bonds solely to N(-) and Na(+) coordinates only with BH(3). Compared to ammonia borane and monometallic amidoboranes, Na(2)Mg(NH(2)BH(3))(4) can release 8.4 wt% pure hydrogen with significantly less toxic gases.

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.

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.

Improved hydrogen release from LiB0.33N0.67H2.67 with noble metal additions.

The hydrogen release behavior of the quaternary hydride LiB(0.33)N(0.67)H(2.67) has been successfully improved through the incorporation of small quantities of noble metal. Adding 5 wt % Pd either as Pd metal particles or as PdCl(2) reduced the temperature T(1/2) corresponding to the midpoint of the hydrogen release reaction by DeltaT(1/2) = -43 degrees C and -76 degrees C, respectively. PtCl(2) and Pt nanoparticles supported on a Vulcan carbon substrate proved to be even more effective, with DeltaT(1/2) = -90 degrees C. The amount of NH(3) released during dehydrogenation is reduced compared to that from additive-free material, and, more importantly, at temperatures below 210 degrees C hydrogen is released with no detectable NH(3). In contrast to additive-free LiB(0.33)N(0.67)H(2.67), which melts completely above 190 degrees C and releases hydrogen from the liquid state only above approximately 250 degrees C, hydrogen release from LiB(0.33)N(0.67)H(2.67) + 5 wt % Pt/Vulcan carbon is accompanied by partial melting plus a cascade through a series of solid intermediate phases. Calorimetric measurements indicate that both additive-free and Pt-added LiB(0.33)N(0.67)H(2.67) release hydrogen exothermically, and hence the reverse reaction is thermodynamically unfavorable. By exposing partially dehydrogenated samples to high H(2) pressures at modest temperatures, fractional hydrogen uptake (roughly 15% of the released hydrogen) has been achieved. The mechanism by which noble metals promote hydrogen release is not known, but the behavior is consistent with that expected for a catalyst, including a large effect with small additions and saturation of the effect at low concentration.

Hydrogen release from mixtures of lithium borohydride and lithium amide: a phase diagram study.

We recently reported the synthesis of a new quaternary hydride in the lithium-boron-nitrogen-hydrogen quaternary phase diagram with the approximate composition LiB0.33N0.67H2.67 having a theoretical hydrogen content of 11.9 wt %. This new compound forms by the reaction of appropriate amounts of lithium amide (LiNH2) and lithium borohydride (LiBH4) and releases greater than 10 wt % hydrogen when heated. A small amount of ammonia, 2-3 mol % of the generated gas, is also released. We now report a study of hydrogen and ammonia release from the series of reactant mixtures (LiNH2)x(LiBH4)1-x, where x=0.667 corresponds to the composition LiB0.33N0.67H2.67. We measured hydrogen and ammonia release amounts as a function of composition and found that maximum hydrogen and minimum ammonia release do occur for x=0.667. We also present evidence for an additional new quaternary phase and for two possibly metastable phases in this system.

On the composition and crystal structure of the new quaternary hydride phase Li4BN3H10.

X-ray data on single crystals of the quaternary metal hydride near the composition LiB(0.33)N(0.67)H(2.67), previously identified as "Li3BN2H8", reveal that its true composition is Li4BN3H10. The structure has body-centered-cubic symmetry [space group I2(1)3, cell parameter a = 10.679(1)-10.672(1) Angstroms] and contains an ordered arrangement of BH4- and NH2- anions in the molar ratio 1:3. The borohydride anion has an almost ideal tetrahedral geometry (angleH-B-H approximately 108-114 degrees), while the amide anion has a nearly tetrahedral bond angle (angleH-N-H approximately 106 degrees). Three symmetry-independent Li atom sites are surrounded by BH4- and NH2- anions in various distorted tetrahedral configurations, one by two B and two N atoms, another by four N atoms, and the third by one B and three N atoms. The Li configuration around B is nearly tetrahedral, while that around N resembles a distorted saddlelike configuration, similar to those in LiBH4 and LiNH2, respectively.

Hydrogen desorption exceeding ten weight percent from the new quaternary hydride Li3BN2H8.

Mobile applications of hydrogen power have long demanded new solid hydride materials with large hydrogen storage capacities. We report synthesis of a new quaternary hydride having the approximate composition Li(3)BN(2)H(8) with 11.9 wt % theoretical hydrogen capacity. It forms by reacting LiNH(2) and LiBH(4) powders in a 2:1 molar ratio either by ball milling or by heating the mixed powders above 95 degrees C. This new quaternary hydride melts at approximately 190 degrees C and releases > or =10 wt % hydrogen above approximately 250 degrees C. A small amount of ammonia (2-3 mol % of the generated gas) is released simultaneously. Preliminary calorimetric measurements suggest that hydrogen release is exothermic and, hence, not easily reversible.