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Sample records for alh3 vliyanie dobavok

  1. Doping of AlH3 with alkali metal hydrides for enhanced decomposition kinetics

    NASA Astrophysics Data System (ADS)

    Sandrock, Gary; Reilly, James

    2005-03-01

    Aluminum hydride, AlH3, has inherently high gravimetric and volumetric properties for onboard vehiclular hydrogen storage (10 wt% H2 and 0.148 kg H2/L). Yet it has been widely neglected because of its kinetic limitations for low-temperature H2 desorption and the thermodynamic difficulties associated with recharging. This paper considers a scenario whereby doped AlH3 is decomposed onboard and recharged offboard. In particular, we show that particle size control and doping with small levels of alkali metal hydrides (e.g., LiH) results in accelerated H2 desorption rates nearly high enough to supply fuel-cell and ICE vehicles. The mechanism of enhanced H2 desorption is associated with the formation of alanate windows (e.g., LiAlH4) between the AlH3 particles and the external gas phase. These alanate windows can be doped with Ti to further enhance transparency, even to the point of accomplishing slow decomposition of AlH3 at room temperature. It is highly likely 2010 gravimetric and volumetric vehicular system targets (6 wt% H2 and 0.045 kg/L) can be met with AlH3. But a new, low-cost method of offboard regeneration of spent Al back to AlH3 is yet needed.

  2. Undamped low-energy plasmon in AlH3 at high pressure

    NASA Astrophysics Data System (ADS)

    Gurtubay, I. G.; Rousseau, B.; Bergara, A.

    2010-08-01

    Pressure strongly modifies electronic and optical properties of solids. In this work we report ab initio time-dependent density-functional theory calculations of the dielectric response of the high-pressure metallic phase of aluminum hydride (AlH3) within the random-phase approximation. Besides the conventional free-electronlike plasmon, which is highly damped, low-energy transitions between states near the Fermi level that appear in this metallized phase give rise to a low-energy undamped collective mode. This feature is expected to induce an abrupt edge in the experimentally measured reflectivity just below 1 eV and also affect electronic correlations close to the Fermi energy. Our work shows that AlH3 is basically a hydrogen sublattice weakly perturbed by Al atoms.

  3. Electrical conductivity of aluminum hydride AlH3 at high pressure and temperature

    NASA Astrophysics Data System (ADS)

    Shakhray, Denis; Molodets, Alexander; Fortov, Vladimir; Khrapak, Aleksei

    2009-06-01

    A study of electrophysical and thermodynamic properties of alane AlH3 under multi shock compression has been carried out. The increase in specific electroconductivity of alane at shock compression up to pressure 100 GPa have been measured. High pressures and temperatures were obtained with explosive device, which accelerates the stainless impactor up to 3 km/sec. The impact shock is split into a shock wave reverberating in alane between two stiff metal anvils. The conductivity of shocked alane increases in the range up to 60-75 GPa and is about 30 1/Ohm*cm. In this region the semiconductor regime is true for shocked alane. The conductivity of alane achieves approximately 500 1/Ohm*cm at 80-90 GPa. In this region conductivity is interpreted in frames of the conception of the ``dielectric catastrophe'', taking into consideration significant difference between electronic states of isolated AlH3 molecule and condensed alane.

  4. Metallization of aluminum hydride AlH3 at high multiple-shock pressures

    NASA Astrophysics Data System (ADS)

    Molodets, A. M.; Shakhray, D. V.; Khrapak, A. G.; Fortov, V. E.

    2009-05-01

    A study of electrophysical and thermodynamic properties of alane AlH3 under multishock compression has been carried out. The increase in specific electroconductivity of alane at shock compression up to pressure 100 GPa has been measured. High pressures and temperatures were obtained with an explosive device, which accelerates the stainless impactor up to 3 km/s. A strong shock wave is generated on impact with a holder containing alane. The impact shock is split into a shock wave reverberating in alane between two stiff metal anvils. This compression loads the alane sample by a multishock manner up to pressure 80-90 GPa, heats alane to the temperature of about 1500-2000 K, and lasts 1μs . The conductivity of shocked alane increases in the range up to 60-75 GPa and is about 30(Ωcm)-1 . In this region the semiconductor regime is true for shocked alane. The conductivity of alane achieves approximately 500(Ωcm)-1 at 80-90 GPa. In this region, conductivity is interpreted in frames of the conception of the “dielectric catastrophe,” taking into consideration significant differences between the electronic states of isolated molecule AlH3 and condensed alane.

  5. Watching the dehydrogenation of alane (AlH3) in a TEM

    NASA Astrophysics Data System (ADS)

    Beattie, Shane; Humphries, Terry; Weaver, Louise; McGrady, Sean

    2008-03-01

    Alane (AlH3) is a promising candidate for on-board hydrogen storage applications. Its theoretical gravimetric capacity is 10.1 percent and decomposition is achieved with modest heating (60-200 deg C). We studied the dehydrogenation of alane, insitu, in a TEM. Alane powder was loaded into the TEM and heated at 80 deg C. We were able to `watch' the dehydrogenation of the alane to aluminum. Electron diffraction and dark fiend images are used to show how and where the aluminum crystallites grow. Although crystalline aluminum phases were successfully identified, some of the sample remained amorphous. We will discuss the nature of the amorphous material and present images clearly identifying the nature of the aluminum crystallites.

  6. Elastic, superconducting, and thermodynamic properties of the cubic metallic phase of AlH3 via first-principles calculations

    NASA Astrophysics Data System (ADS)

    Wei, Yong-Kai; Ge, Ni-Na; Ji, Guang-Fu; Chen, Xiang-Rong; Cai, Ling-Cang; Zhou, Su-Qin; Wei, Dong-Qing

    2013-09-01

    The lattice dynamic, elastic, superconducting, and thermodynamic properties of the high-pressure cubic metallic phase AlH3 are studied within density function theory. The calculated elastic modulus and phonon dispersion curves at various pressures indicate that the cubic phase is both mechanically and dynamically stable above 73 GPa. The superconducting transition temperature was calculated using Allen-Dynes modification of the McMillan formula based on the Bardeen-Cooper-Schrieffer theory. It is found that Tc approaches a linear decrease in the low pressure range at the rate dTC/dP ≈-0.22 K/GPa but gradually decreases exponentially at higher pressure, and then it becomes 0 K upon further compression. The calculations indicate that Tc is about 2.042 K at 110 GPa, in agreement with experimental results. The soft phonon modes, especially the lowest acoustic mode, contribute almost 79% to the total electron-phonon coupling parameter sλ for cubic AlH3 at 73 GPa. However, they disappear gradually with increasing pressure, showing a responsibility for the variation of Tc. The thermodynamic properties of cubic AlH3, such as the dependence of thermal expansion coefficient αV on pressure and temperature, the specific heat capacity CP, as well as the electronic specific heat coefficient Cel, were also investigated by the quasi-harmonic approximation theory.

  7. Formation of Al2H7- anions--indirect evidence of volatile AlH3 on sodium alanate using solid-state NMR spectroscopy.

    PubMed

    Felderhoff, Michael; Zibrowius, Bodo

    2011-10-14

    After more than a decade of intense research on NaAlH(4) doped with transition metals as hydrogen storage material, the actual mechanism of the decomposition and rehydrogenation reaction is still unclear. Early on, monomeric AlH(3) was named as a possible transport shuttle for aluminium, but never observed experimentally. Here we report for the first time the trapping of volatile AlH(3) produced during the decomposition of undoped NaAlH(4) by an adduct of sodium alanate and crown ether. The resulting Al(2)H(7)(-) anion was identified by solid-state (27)Al NMR spectroscopy. Based on this indirect evidence of volatile alane, we present a simple description of the processes occurring during the reversible dehydrogenation of NaAlH(4).

  8. Reaction kinetics for the solid state synthesis of the AlH3/MgCl2 nano-composite by mechanical milling.

    PubMed

    Duan, C W; Hu, L X; Sun, Y; Zhou, H P; Yu, H

    2015-09-14

    The process of mechanical milling has been proved to be a cost-effective way to synthesize the AlH3/MgCl2 nano-composite by using MgH2 and AlCl3 as reagents. However, so far there is no comprehensive knowledge of the kinetics of this process. In an effort to predict the reaction progress and optimize the milling parameters, the kinetics of the synthesis of the AlH3/MgCl2 nano-composite by mechanical milling of MgH2 and AlCl3 is experimentally investigated in the present work. The reaction progress or the transformation fraction upon milling for different times is evaluated using the isothermal hydrogen desorption test of the as-milled samples at 220 °C, which is much lower than the threshold temperature for the de-hydriding of the reagent MgH2 but enough for the de-hydriding of the as-synthesized nano-sized AlH3. The effects of milling parameters on the reaction kinetics as well as the underlying mechanism are discussed by referring to the mechanical energy input intensity, the vial temperature and the Gibbs free energy change for the reaction. Furthermore, it is found that the Johnson-Mehl-Avrami (JMA) model can well describe the kinetics theoretically. By fitting the experimental data with the JMA expression, the theoretical kinetics expressions, the equation parameters, and the activation energy are obtained.

  9. Ab initio studies on phase transition, thermoelastic, superconducting and thermodynamic properties of the compressed cubic phase of AlH3

    NASA Astrophysics Data System (ADS)

    Wei, Yong-Kai; Ge, Ni-Na; Chen, Xiang-Rong; Ji, Guang-Fu; Cai, Ling-Cang; Gu, Zhuo-Wei

    2014-03-01

    The phase transition, thermoelastic, lattice dynamic, and thermodynamic properties of the cubic metallic phase AlH3 were obtained within the density-function perturbation theory. The calculated elastic modulus and phonon dispersion curves under various pressures at 0 K indicate the cubic phase is both mechanically and dynamically stable above 73 GPa. The superconducting transition temperature Tc was calculated using the Allen-Dynes modification of the McMillan formula based on BCS theory. The calculations show that Tc for the cubic phase AlH3 is 8.5 K (μ*=0.1) at the onset of this phase (73 GPa), while decreases to 5.7 K at 80 GPa and almost disappears at 110 GPa, consisting with experimental phenomenon that there was no superconducting transition observed down to 4 K over a wide pressure range 110-164 GPa. It is found that the soft phonon mode for branch 1, namely, the lowest acoustic mode, plays a crucial role in elevating the total EPC parameter λ of cubic AlH3. And the evolution of Tc with pressure follows the corresponding change of this soft mode, i.e. this mode is responsible for the disappearance of Tc in experiments. Meanwhile, the softening of this lowest acoustic mode originates from the electronic momentum transfer from M to R point. This phenomenon provides an important insight into why drastic changes in the diffraction pattern were observed in the pressure range of 63-73 GPa in Goncharenko's experiments. Specifically, once finite electronic temperature effects are included, we find that dynamical instabilities can be removed in the phonon dispersion for P ≥63 GPa, rendering the metastability of this phase in the range of 63-73 GPa, and Tc (15.4 K) becomes remarkably high under the lowest possible pressure (63 GPa) compared with that of under 73 GPa (8.5 K). Our calculations open the possibility that finite temperature may allow cubic AlH3 to be dynamically stabilized even for pressures below 73 GPa. It is reasonable to deduced that if special techniques, such as rapid decompression, quenching, and annealing, are implemented in experiments, higher Tc can be observed in hydrides or hydrogen-rich compounds under much lower pressure than ever before.

  10. Regeneration of AlH3 studied with Raman and Infrared Spectroscopy

    NASA Astrophysics Data System (ADS)

    Lacina, David; Wegrzyn, J.; Reilly, J. J.; Graetz, Jason

    2010-03-01

    Aluminum hydride compounds are known to exhibit a 10% by weight hydrogen storage capacity that makes them suited for technologies that require hydrogen as a fuel. The current challenge associated with this material is how to regenerate the hydride from the spent fuel and H2 gas. We employ a two-step process to regenerate the hydride compound which first requires the formation of a stable aluminum hydride adduct using a tertiary amine. This is followed by a second step consisting of adduct separation and hydride recovery, involving transamination to create a less stable adduct. We present results which show that alane-amines can be formed by hydrogenation of catalyzed aluminum in a solvent at low pressures using one of several tertiary amines. Raman and infrared spectroscopy was performed on the products of these reactions to better understand the structure of the alane amines that are formed, as well as the hydrogenation reactions that take place. A vibrational analysis of the regeneration products performed with Raman and infrared spectroscopy is presented and will help clarify the molecular and vibrational structures of these alane amine adducts.

  11. Hydrazine bisalane is a potential compound for chemical hydrogen storage. A theoretical study.

    PubMed

    Nguyen, Vinh Son; Swinnen, Saartje; Leszczynski, Jerzy; Nguyen, Minh Tho

    2011-09-14

    Electronic structure calculations suggest that hydrazine bisalane (AlH(3)NH(2)NH(2)AlH(3), alhyzal) is a promising compound for chemical hydrogen storage (CHS). Calculations are carried out using the coupled-cluster theory CCSD(T) with the aug-cc-pVTZ basis set. Potential energy surfaces are constructed to probe the formation of, and hydrogen release from, hydrazine bisalane which is initially formed from the reaction of hydrazine with dialane. Molecular and electronic characteristics of both gauche and trans alhyzal are determined for the first time. The gauche hydrazine bisalane is formed from starting reactants hydrazine + dialane following a movement of an AlH(3) group from AlH(3)AlH(3)NH(2)NH(2) rather than by a direct attachment of a separate AlH(3) group, generated by predissociation of dialane, to AlH(3)NH(2)NH(2). The energy barriers for dehydrogenation processes from gauche and transalhyzal are in the range of 21-28 kcal mol(-1), which are substantially smaller than those of ca. 40 kcal mol(-1) previously determined for the isovalent hydrazine bisborane (bhyzb) system. H(2) release from hydrazine bisalane is thus more favored over that from hydrazine bisborane, making the Al derivative an alternative candidate for CHS.

  12. Formation and bonding of alane clusters on Al(111) surfaces studied by infrared absorption spectroscopy and theoretical modeling.

    PubMed

    Chaudhuri, Santanu; Rangan, Sylvie; Veyan, Jean-Francois; Muckerman, James T; Chabal, Yves J

    2008-08-13

    Alanes are believed to be the mass transport intermediate in many hydrogen storage reactions and thus important for understanding rehydrogenation kinetics for alanates and AlH3. Combining density functional theory (DFT) and surface infrared (IR) spectroscopy, we provide atomistic details about the formation of alanes on the Al(111) surface, a model environment for the rehydrogenation reactions. At low coverage, DFT predicts a 2-fold bridge site adsorption for atomic hydrogen at 1150 cm(-1), which is too weak to be detected by IR but was previously observed in electron energy loss spectroscopy. At higher coverage, steps are the most favorable adsorption sites for atomic H adsorption, and it is likely that the AlH3 molecules form (initially strongly bound to steps) at saturation. With increasing exposures AlH3 is extracted from the step edge and becomes highly mobile on the terraces in a weakly bound state, accounting for step etching observed in previous STM studies. The mobility of these weakly bound AlH3 molecules is the key factor leading to the growth of larger alanes through AlH3 oligomerization. The subsequent decomposition and desorption of alanes is also investigated and compared to previous temperature programmed desorption studies.

  13. Studying aluminum hydride by means of thermal analysis

    NASA Astrophysics Data System (ADS)

    Milekhin, Yu. M.; Koptelov, A. A.; Matveev, A. A.; Baranets, Yu. N.; Bakulin, D. A.

    2015-07-01

    Chemical reactions and physical transformations that occur upon heating aluminum hydride (AlH3, alane), stored for 25 years, in the temperature range of 50-1200°C in an atmosphere of nitrogen, argon, and air are studied by means of thermogravimetric analysis and differential scanning calorimetry. The heat of thermal decomposition and the hydrogen content are determined for the AlH3 samples and are found to be 318 ± 25 J/g and 9.32 ± 0.24 wt %, respectively. It is established that the estimated enthalpy of formation of AlH3 in stoichiometric composition (Δf H ≈ -10.3 kJ/mol) agrees with the literature data. After the release of hydrogen, the mass of the precipitate increases by 0.5 ± 0.3%, relative to the initial mass of the AlH3 samples; the most likely reason for this effect is the adsorption of nitrogen (argon) in the micropores and mesopores that form. Thermal phenomena associated with the crystallization of the amorphous aluminum that forms after hydrogen is released from the alane particles are analyzed. It is established that the aluminum contained in initial AlH3 samples is almost completely transformed into aluminum nitride and oxide (AlN and Al3O3) upon heating to 1200°C in nitrogen and air, respectively.

  14. Low-pressure Structural Modification of Aluminum Hydride

    DTIC Science & Technology

    2011-02-01

    pressure release. 15. SUBJECT TERMS High - pressure , Diamond anvil cell, aluminum hydride 16. SECURITY CLASSIFICATION OF...loaded into the diamond anvil cell using a specialized high - pressure gas loading system (18). The in-situ pressure within the diamond anvil cell was...Visible Absorption Study of AlH3. Journal of Physics: Conference Series 2010, 215, 012047. 18. Jayaraman, A. Diamond Anvil Cell and High -

  15. Solid State NMR Studies of the Aluminum Hydride Phases

    NASA Technical Reports Server (NTRS)

    Hwang, Son-Jong; Bowman, R. C., Jr.; Graetz, Jason; Reilly, J. J.

    2006-01-01

    Several solid state NMR techniques including magic-angle-spinning (MAS) and multiple-quantum (MQ) MAS experiments have been used to characterize various AlH3 samples. MAS-NMR spectra for the 1H and 27Al nuclei have been obtained on a variety of AlH3 samples that include the (beta)- and (gamma)- phases as well as the most stable (alpha)-phase. While the dominant components in these NMR spectra correspond to the aluminum hydride phases, other species were found that include Al metal, molecular hydrogen (H2), as well as peaks that can be assigned to Al-O species in different configurations. The occurrence and concentration of these extraneous components are dependent upon the initial AlH3 phase composition and preparation procedures. Both the (beta)-AlH3 and (gamma)-AlH3 phases were found to generate substantial amounts of Al metal when the materials were stored at room temperature while the (alpha)-phase materials do not exhibit these changes.

  16. Alanes formation on the Al(111) surface

    NASA Astrophysics Data System (ADS)

    Rangan, Sylvie; Veyan, Jean-Francois; Chabal, Yves J.; Chaudhuri, Santanu; Muckerman, James T.

    2008-03-01

    Alane clusters (AlxHy) are believed to be the ubiquitous intermediates in hydrogen storage reactions for a wide variety of alanates (LiAlH4, NaAlH4) currently considered for hydrogen storage. The formation and behavior of alanes at surfaces appear to control and limit the efficiency of hydrogen storage. In particular, hydrogen adsorption on the Al(111) surface leads to the coexistence of several adsorbed species, the concentration of which is affected by the step density, the surface coverage and the temperature. We combine density functional theory (DFT) and surface infra-red (IR) absorption spectroscopy to uncover the mechanisms for alane formation on Al(111) surfaces. At low coverage, DFT predicts a two-fold bridge site adsorption for atomic hydrogen, consistent with previous Electron Energy Loss Spectroscopy measurements. At higher coverage, the formation of small chemisorbed AlH3 occurs at the step edges. With increasing coverage AlH3 is extracted from the step edge and becomes highly mobile on the terraces in a weakly bound state. This mobility is the key factor leading to the growth of larger alanes through AlH3 oligomerization. For these large alanes, previous Thermal Programmed Desorption studies are discussed and compared to the thermal stability observed in IR.

  17. pardInvestigation of the Direct Hydrogenation of Aluminum to Alane in Supercritical Fluids

    NASA Astrophysics Data System (ADS)

    Jensen, Craig; McGrady, Sean; Ayabe, Reyna; Reddy, Ben

    2007-03-01

    Alane, AlH3 has many of the properties that are requisite for materials to be considered viable for onboard hydrogen storage applications. Most notibly, it contains 10.1 wt% hydrogen and undergoes dehydrogenation at appreciable rates at temperatures below 100^oC. However, the very low, >= 6 kJ/mol, enthalpy of dehydrogenation of AlH3 prohibits subsequent re-hydrogenation through standard gas-solid techniques except at very high pressures or very low temperatures. The extremely low solubility of gaseous H2 in conventional organic solvents also vitiates a solution-based approach. Re-hydrogenation of Al using a supercritical fluid potentially offers a workable approach since the fluid can act as a solvent, at the same time remaining completely miscible with permanent gases like hydrogen. Recently, it has been found that mixtures of NaH and Al can be hydrogenated to sodium alanate, NaAlH4 under modest pressures and temperatures in supercritical fluids. We have now extended these studies to the hydrogenation of Al to AlH3. The results of these studies and experimental details will be reported.

  18. Thermodynamic properties of molecular borane phosphines, alane amines, and phosphine alanes and the [BH(4)(-)][PH(4)(+)], [AlH(4)(-)][NH(4)(+)], and [AlH(4)(-)][PH(4)(+)] salts for chemical hydrogen storage systems from ab initio electronic structure theory.

    PubMed

    Grant, Daniel J; Dixon, David A

    2005-11-10

    The heats of formation for the molecules BH(3)PH(3), BH(2)PH(2), HBPH, AlH(3)NH(3), AlH(2)NH(2), HAlNH, AlH(3)PH(3), AlH(2)PH(2), HAlPH, AlH(4)(-), PH(3), PH(4), and PH(4)(+), as well as the diatomics BP, AlN, and AlP, have been calculated by using ab initio molecular orbital theory. The coupled cluster with single and double excitations and perturbative triples method (CCSD(T)) was employed for the total valence electronic energies. Correlation consistent basis sets were used, up through the augmented quadruple-zeta, to extrapolate to the complete basis set limit. Additional d core functions were used for Al and P. Core/valence, scalar relativistic, and spin-orbit corrections were included in an additive fashion to predict the atomization energies. Geometries were calculated at the CCSD(T) level up through at least aug-cc-pVTZ and frequencies were calculated at the CCSD(T)/aug-cc-pVDZ level. The heats of formation of the salts [BH(4)(-)][PH(4)(+)](s), [AlH(4)(-)][NH(4)(+)](s), and [AlH(4)(-)][PH(4)(+)](s) have been estimated by using an empirical expression for the lattice energy and the calculated heats of formation of the two component ions. The calculations show that both AlH(3)NH(3)(g) and [AlH(4)(-)][NH(4)(+)](s) can serve as good hydrogen storage systems that release H(2) in a slightly exothermic process. In addition, AlH(3)PH(3) and the salts [AlH(4)(-)][PH(4)(+)] and [BH(4)(-)][PH(4)(+)] have the potential to serve as H(2) storage systems. The hydride affinity of AlH(3) is calculated to be -70.4 kcal/mol at 298 K. The proton affinity of PH(3) is calculated to be 187.8 kcal/mol at 298 K in excellent agreement with the experimental value of 188 kcal/mol. PH(4) is calculated to be barely stable with respect to loss of a hydrogen to form PH(3).

  19. Theoretical exploration of hydrogen loss from Al3H9.

    PubMed

    Nold, Christopher P; Head, John D

    2012-05-03

    The Al(3)H(9) and Al(3)H(7) potential energy surfaces were explored using quantum chemistry calculations to investigate the H(2) loss mechanism from Al(3)H(9), which provide new insights into hydrogen production from bulk alane, [AlH(3)](x), a possible energy storage material. We present results of B3LYP/6-311++G(d,p) calculations for the various Al(3)H(9) and Al(3)H(7) optimized local minima and transition state structures along with some reaction pathways for their interconversion. We find the energy for Al(3)H(9) decomposition into Al(2)H(6) and AlH(3) is slightly lower than that for H(2) loss and Al(3)H(7) formation, but the calculations show that H(2) loss from Al(3)H(9) is a lower energy process than for losing hydrogen from either Al(2)H(6) or AlH(3). We found four transition state structures and reaction pathways for Al(3)H(9) → Al(3)H(7) + H(2), where the lowest energy activation barrier is around 25-73 kJ/mol greater than the experimental value for H(2) loss from bulk alane. Intrinsic reaction coordinate calculations show that the H(2) loss pathway involves considerable rearrangement of the H atom positions around a single Al center. Three of the pathways start with the formation of an AlH(3) moiety, which then enables a terminal H on the AlH(3) to get within 1.1 to 1.2 Å of a nearby bridging H atom. The bridging and terminal H atoms eventually combine to form H(2) and leave Al(3)H(9). One implication of these H(2) loss reaction pathways is that, since the H atoms in bulk alanes are all at bridging positions, if a similar H(2) loss mechanism were to apply to bulk alane, then H(2) loss would most likely occur on the bulk alane surface or at a defect site where there should be more terminal H atoms available for reaction with nearby bridging H atoms.

  20. Point-defect-mediated dehydrogenation of alane

    NASA Astrophysics Data System (ADS)

    Ismer, Lars

    2011-03-01

    For the engineering of better hydrogen storage materials a systematic understanding of their hydrogen sorption kinetics is crucial. Theoretical studies on metal hydrides have indicated that in many cases point defects control mass transport and hence hydrogen uptake and release. Manipulating point-defect concentrations thus allows control over hydrogen sorption kinetics, opening up new engineering strategies. However, in some cases the relevance of kinetic limitations due to point defects is still under debate; kinetic inhibition of hydrogen sorption has also been attributed to surface effects, e.g. oxide layers or low recombination rates. We present a systematic analysis of the dehydrogenation kinetics of alane (AlH3), one of the prime candidate materials for hydrogen storage. Using hybrid-density functional calculations we determine the concentrations and mobilities of point defects and their complexes. Kinetic Monte Carlo simulations are used to describe the full dehydrogenation reaction. We show that under dehydrogenation conditions charged hydrogen vacancy defects form in the crystal, which have a strong tendency towards clustering. The vacancy clusters denote local nuclei of Al phase, and the growth of these nuclei eventually drives the AlH3/Al transformation. However, the low concentration of vacancy defects limits the transport of hydrogen across the bulk, and hence acts as the rate-limiting part of the process. The dehydrogenation is therefore essentially inactive at room temperature, explaining why AlH3 is metastable for years, even though it is thermodynamically unstable. Our derived activation energy and dehydrogenation curves are in excellent agreement with the experimental data, providing evidence for the relevance of bulk point-defect kinetics. Work performed in collaboration with A. Janotti and C. G. Van de Walle, and supported by DOE.

  1. Pressure-induced hydrogen-dominant metallic state in aluminum hydride.

    PubMed

    Goncharenko, Igor; Eremets, M I; Hanfland, M; Tse, J S; Amboage, M; Yao, Y; Trojan, I A

    2008-02-01

    Two structural transitions in covalent aluminum hydride AlH3 were characterized at high pressure. A metallic phase stable above 100 GPa is found to have a remarkably simple cubic structure with shortest first-neighbor H-H distances ever measured except in H2 molecule. Although the high-pressure phase is predicted to be superconductive, this was not observed experimentally down to 4 K over the pressure range 120-164 GPa. The results indicate that the superconducting behavior may be more complex than anticipated.

  2. On the existence of MH(n) species with M = Al, Ga and n = 4, 5, 6. Computational study of structures, stabilities and bonding.

    PubMed

    Moc, Jerzy; Bober, Karolina; Panek, Jarosław

    2005-12-01

    Based on second-order perturbation theory (MP2) predictions with large 6-311 + + G(3df, 3pd) basis set we have reviewed the possible structures and stabilities of a series of neutral MH(n)(M = Al, Ga; n = 4, 5, 6) species. For AlH4 and AlH5, our results confirm the previous theoretical findings, which indicate the dihydrogen C(s) complexes (2A') AlH2(H2) and (1A') AlH3(H2), respectively, as the lowest energy isomers. We found, similarly, C(s) (2A') GaH2(H2) and (1A') GaH3(H2) van der Waals complexes as the most stable species of the gallium analogues GaH4 and GaH5. The calculated H2 dissociation energies (D(e)) for AlH2(H2) and AlH3(H2) are of the order 1.8-2.5 kcalmol(-1), whereas this range of values for GaH2(H2) and GaH3(H2) is 1.4-1.8 kcalmol(-1) . Symmetry-adapted perturbation theory (SAPT) was used to analyze the interaction energies of these dihydrogen complexes (for n = 5) to determine why the Ga species show a smaller binding energy than the Al species. The SAPT partitioning of the interaction energy showed significant differences between AlH3(H2) and GaH3(H2), resulting from the much stronger "hydride" character of the aluminum species. The experimental observation of AlH2(H2) and AlH3(H2), and likely GaH3(H2), via low-temperature matrix isolation has been reported recently by Pullumbi et al. and Andrews et al., supporting the theoretical predictions. For n = 6, we found the degenerate C2(2A) and C(s)(2A') MH2(H2)2 "double H2" type van der Waals complexes as the lowest energy species for both M = Al and Ga.

  3. Selected boron, aluminum, and gallium trihalide and trihydride anions

    NASA Astrophysics Data System (ADS)

    Brzeski, Jakub; Czapla, Marcin; Skurski, Piotr; Simons, Jack

    2017-01-01

    Ab initio methods with flexible orbital basis sets are used to examine the electron binding strengths of tri-fluorides, tri-chlorides, and tri-hydrides of B, Al, and Ga. The adiabatic electron affinities are found to increase with increasing atomic number of the central atom. For any given central atom M (M = B, Al, Ga), the adiabatic and vertical electronic stability for MCl3 is larger than that of the corresponding MF3. The tri-hydrides have quite different electron binding strengths than the corresponding tri-halides. BH3 has a very small EA (ca. 0.02 eV) and its anion is planar whereas the tri-halide anions and AlH3- and GaH3- are non-planar. AlH3 and GaH3 have considerably smaller EAs (ca. 0.3 eV) than the Al and Ga tri-halides (0.9-1.8 eV). In all, these anions provide species whose electron binding strengths span a considerable range (0.3-1.8 eV).

  4. Electronic and vibrational properties of γ-AlH3

    NASA Astrophysics Data System (ADS)

    Wang, Yan; Yan, Jia-An; Chou, M. Y.

    2008-01-01

    Aluminum hydride (alane) AlH3 is an important material in hydrogen storage applications. It is known that AlH3 exists in multiply forms of polymorphs, where α-AlH3 is found to be the most stable with a hexagonal structure. Recent experimental studies on γ-AlH3 reported an orthorhombic structure with a unique double-bridge bond between certain Al and H atoms. This was not found in α-AlH3 or other polymorphs. Using density functional theory, we have investigated the energetics, and the structural, electronic, and phonon vibrational properties for the newly reported γ-AlH3 structure. The current calculation concludes that γ-AlH3 is less stable than α-AlH3 by 1.2KJ/mol , with the zero-point energy included. Interesting binding features associated with the unique geometry of γ-AlH3 are discussed from the calculated electronic properties and phonon vibrational modes. The binding of H-s with higher energy Al-p,d orbitals is enhanced within the double-bridge arrangement, giving rise to a higher electronic energy for the system. Distinguishable new features in the vibrational spectrum of γ-AlH3 were attributed to the double-bridge and hexagonal-ring structures.

  5. Towards direct synthesis of alane: A predicted defect-mediated pathway confirmed experimentally

    DOE PAGES

    Wang, Lin -Lin; Herwadkar, Aditi; Reich, Jason M.; ...

    2016-08-18

    Here, alane (AlH3) is a unique energetic material that has not found a broad practical use for over 70 years because it is difficult to synthesize directly from its elements. Using density functional theory, we examine the defect-mediated formation of alane monomers on Al(111) in a two-step process: (1) dissociative adsorption of H2 and (2) alane formation, which are both endothermic on a clean surface. Only with Ti dopant to facilitate H2 dissociation and vacancies to provide Al adatoms, both processes become exothermic. In agreement, in situ scanning tunneling microscopy showed that during H2 exposure, alane monomers and clusters formmore » primarily in the vicinity of Al vacancies and Ti atoms. Moreover, ball milling of the Al samples with Ti (providing necessary defects) showed a 10 % conversion of Al into AlH3 or closely related species at 344 bar H2, indicating that the predicted pathway may lead to the direct synthesis of alane from elements at pressures much lower than the 104 bar expected from bulk thermodynamics.« less

  6. Aluminium Diphosphamethanides: Hidden Frustrated Lewis Pairs.

    PubMed

    Styra, Steffen; Radius, Michael; Moos, Eric; Bihlmeier, Angela; Breher, Frank

    2016-07-04

    The synthesis and characterisation of two aluminium diphosphamethanide complexes, [Al(tBu)2 {κ(2) P,P'-Mes*PCHPMes*}] (3) and [Al(C6 F5 )2 {κ(2) P,P'-Mes*PCHPMes*}] (4), and the silylated analogue, Mes*PCHP(SiMe3 )Mes* (5), are reported. The aluminium complexes feature four-membered PCPAl core structures consisting of diphosphaallyl ligands. The silylated phosphine 5 was found to be a valuable precursor for the synthesis of 4 as it cleanly reacts with the diaryl aluminium chloride [(C6 F5 )2 AlCl]2 . The aluminium complex 3 reacts with molecular dihydrogen at room temperature under formation of the acyclic σ(2) λ(3) ,σ(3) λ(3) -diphosphine Mes*PCHP(H)Mes* and the corresponding dialkyl aluminium hydride [tBu2 AlH]3 . Thus, 3 belongs to the family of so-called hidden frustrated Lewis pairs.

  7. Synthesis of square-planar aluminum(III) complexes.

    PubMed

    Thompson, Emily J; Myers, Thomas W; Berben, Louise A

    2014-12-15

    The synthesis of two four-coordinate and square planar (SP) complexes of aluminum(III) is presented. Reaction of a phenyl-substituted bis(imino)pyridine ligand that is reduced by two electrons, Na2((Ph)I2P(2-)), with AlCl3 afforded five-coordinate [((Ph)I2P(2-))Al(THF)Cl] (1). Square-planar [((Ph)I2P(2-))AlCl] (2) was obtained by performing the same reaction in diethyl ether followed by lyphilization of 2 from benzene. The four-coordinate geometry index for 2, τ4, is 0.22, where 0 would be a perfectly square-planar molecule. The analogous aluminum hydride complex, [((Ph)I2P(2-))AlH] (3), is also square-planar, and was characterized crystallographically and has τ4=0.13. Both 2 and 3 are Lewis acidic and bind 2,6-lutidine.

  8. DFT and CCSD(T) study of the AH3- (A = Al, Ga) isomerization, [Ga2(μ-H)(μ-H2)]- and [Ga2(μ-H3)]- unprecedented hydrido-bimetallic structures

    NASA Astrophysics Data System (ADS)

    Guermoune, Abdeladim; Jarid, Abdellah

    2007-03-01

    Total potential energy surfaces (PES) are scanned in order to study the isomerization of the AH3- (A = Al, Ga) anions. AlH3- PES is characterized by six minima and seven transition structures which are connectable with themselves. Indeed of these 12 same extrema, the GaH3- PES has three other minima and four TSs. These structures exhibit an activated H 2 molecule in one or both Ga atoms coordination sphere where the Ga atom seems imply its metallic character via its occupied d-orbital. We have also localized two unusual structures: a minimum having M 2(μ-H)(μ-H 2)-like structure and a transition with M 2(μ-H 3)-like arrangement where the H 3 entity is coordinated to both Ga atoms. The connectivity of all these extrema brings to the fore an eventual fluxional behaviour of these compounds.

  9. Calculation of the 13C NMR shieldings of the C0 2 complexes of aluminosilicates

    NASA Astrophysics Data System (ADS)

    Tossell, J. A.

    1995-04-01

    13C NMR shieldings have been calculated using the random-phase-approximation, localized-orbital local-origins version of ab initio coupled Hartree-Fuck perturbation theory for CO 2 and and for several complexes formed by the reaction of CO 2 with molecular models for aluminosilicate glasses, H 3TOT'H3 3-n, T,T' = Si,Al. Two isomeric forms of the CO 2-aluminosilicate complexes have been considered: (1) "CO 2-like" complexes, in which the CO 2 group is bound through carbon to a bridging oxygen and (2) "CO 3-like" complexes, in which two oxygens of a central CO 3 group form bridging bonds to the two TH 3 groups. The CO 2-like isomer of CO 2-H 3SiOSiH 3 is quite weakly bonded and its 13C isotropic NMR shielding is almost identical to that in free CO 2. As Si is progressively replaced by Al in the - H terminated aluminosilicate model, the CO 2-like isomers show increasing distortion from the free CO 2 geometry and their 13C NMR shieldings decrease uniformly. The calculated 13C shielding value for H 3AlO(CO 2)AlH 3-2 is only about 6 ppm larger than that calculated for point charge stabilized CO 3-2. However, for a geometry of H 3SiO(CO 2) AlH 3-1, in which the bridging oxygen to C bond length has been artificially increased to that found in the - OH terminated cluster (OH) 3SiO(CO 2)Al(OH) 3-1, the calculated 13C shielding is almost identical to that for free CO 2. The CO 3-like isomers of the CO 2-aluminosili-cate complexes show carbonate like geometries and 13C NMR shieldings about 4-9 ppm larger than those of carbonate for all T,T' pairs. For the Si,Si tetrahedral atom pair the CO 2-like isomer is more stable energetically, while for the Si,Al and Al,Al cases the CO 3-like isomer is more stable. Addition of Na + ions to the CO 3-2 or H 3AlO(CO 2)AlH 3-2 complexes reduces the 13C NMR shieldings by about 10 ppm. Complexation with either Na + or CO 2 also reduces the 29Si NMR shieldings of the aluminosilicate models, while the changes in 27Al shielding with Na + or CO 2 complexation are much smaller. Complexation with CO 2 greatly increases the electric field gradient at the bridging oxygen of H 3AlOAlH 3-2, raising it to a value similar to that found for SiOSi linkages. Comparison of these results with the experimental 13C NMR spectra support the formation of CO 2-like complexes at SiOSi bridges in albite glasses and CO 3-like complexes at SiOAl and AlOAl bridges in albite and nepheline glasses. Changes in the calculated shieldings as Na + ions are added to the complexes suggest that some of the observed complexes may be similar in their CO 2-aluminosilicate interactions, but different with respect to the positions of the charge-compensating Na + ions.

  10. Hydrogen in aluminum: First-principles calculations of structure and thermodynamics

    NASA Astrophysics Data System (ADS)

    Wolverton, C.; Ozoliņš, V.; Asta, M.

    2004-04-01

    Despite decades of study, several key aspects of the Al-H system remain the subject of considerable debate. In an effort to elucidate some of these unknowns, we perform a systematic study of this system using first-principles density-functional calculations. We show that generalized gradient approximation (GGA) calculations provide an accurate picture of energetics, phase stability and structure, diffusion, and defect binding in the Al-H system. A series of calculations for hydrides in the M-H systems (M=Al, Ba, Ca, K, Mg, La, Li, Na, Ni, Pd, Sc, Sr, Ti, V, and Y) also shows that the GGA calculations are a quantitatively accurate predictor of hydride formation energies. For Al-H, we find: (i) In agreement with experiment, the observed metastable hydride, AlH3 is found to have a small, negative formation enthalpy at ambient conditions, but a strongly positive formation free energy. (ii) Linear response calculations of AlH3 yield vibrational frequencies, phonon densities of states (DOS), and heat capacities in excellent agreement with experimental measurements, and suggest the need for a reinterpretation of measured phonon DOS. (iii) Atomic relaxation and anharmonic vibrational effects both play an important role in the tetrahedral versus octahedral interstitial site preference of H in Al. (iv) The calculated heat of solution of H in the preferred tetrahedral site is large and positive (+0.71 eV), consistent with experimental solubility data and with Al as an endothermic hydrogen absorber. (v) Interstitial H interacts strongly with Al vacancies (□), with a calculated H-□ binding energy of 0.33 eV. (vi) In the absence of vacancies, the calculated migration energy of H between the tetrahedral and octahedral interstitial sites is 0.18 eV, but for H migrating away from an Al vacancy, the migration energy increases to 0.54 eV. Vacancy trapping of H can therefore provide an explanation for observed disparate H migration barriers.

  11. Dihydrogen bonding vs metal-σ interaction in complexes between H2 and metal hydride.

    PubMed

    Alkorta, Ibon; Elguero, Jose; Solimannejad, Mohammad; Grabowski, Sławomir J

    2011-01-20

    The complexes formed by hydrogen with metal hydrides (LiH, NaH, BeH(2), MgH(2), BH(3), AlH(3), Li(2)H(2), Na(2)H(2), Be(2)H(4), and Mg(2)H(4)) have been theoretically studied at the MP2/aug-cc-pVTZ, MP2/aug-cc-pVQZ and CCSD(T)/aug-cc-pVTZ//CCSD/aug-cc-pVTZ levels of theory. The hydrogen molecule can act as a Lewis acid or base. In the first case, a dihydrogen bonded complex is obtained and in the second an interaction between the σ-bond of the hydrogen molecule and an empty orbital of the metal atoms is found. Quantum theory of atoms in molecules and natural bond orbitals methods have been applied to analyze the intermolecular interactions. Additionally, the cooperativity effects are analyzed for selected complexes with two H(2) molecules where both kinds of interactions exist simultaneously.

  12. Synthesis and Hydrogen Desorption Properties of Aluminum Hydrides.

    PubMed

    Jeong, Wanseop; Lee, Sang-Hwa; Kim, Jaeyong

    2016-03-01

    Aluminum hydride (AlH3 or alane) is known to store maximum 10.1 wt.% of hydrogen at relatively low temperature (< 100 degrees C), which partially fulfills the U.S. department of energy requirements for gravimetric loading capacity. However, its detailed mechanisms of appearing of different phases, structural stability, and dynamics of hydrogen desorption are still not clear. To understand the desorption properties of hydrogen in alane, thermodynamically stable α-AlH3 was synthesized by employing an ethereal reaction method. The dependence of pathways on phase formation and the properties of hydrogen evolution were investigated, and the results were compared with the ones for γ-AlH3. It was found that γ-AlH3 requires 10 degrees C higher than that of γ-AlH3 to form, and its decomposition rate demonstrated enhanced endothermic stabilities. For desorption, all hydrogen atoms of alane evolved under an isothermal condition at 138 degrees C in less than 1 hour, and the sample completely transformed to pure aluminum. Our results show that the total amount of desorbed hydrogen from α-AlH3 exceeded 9.05 wt.%, with a possibility of further increase. Easy synthesis, thermal stability, and a large amount of hydrogen desorption of alane fulfill the requirements for light-weight hydrogen storage materials once the pathway of hydrogen cycling is provided.

  13. Aluminum compounds in calcium chloride extracts from podzolic soil and their possible sources

    NASA Astrophysics Data System (ADS)

    Tolpeshta, I. I.; Sokolova, T. A.

    2008-06-01

    Aluminum concentrations in organoaluminum complexes, mineral polymers, Al(H2O){6/3+}, Al(OH)(H2O){5/2+}, Al(OH)2(H2O){4/+}, AlH3SiO{4/2+}, and Al(OH)3(H2O){3/0} extracted with 0.001 M CaCl2 from the main genetic horizons of a podzolic soil on two-layered deposits were determined experimentally and calculated from thermodynamic equations. It was found that aluminum bound in organic complexes was predominant in extracts from the AE horizon, and mineral polymer aluminum compounds prevailed in extracts from the E and IIBD horizons. In the AE horizon, organoaluminum compounds were a major source of aluminum, which passed into solution predominantly by exchange reactions. In the E horizon, aluminum hydroxide interlayers in soil chlorites were the main source of aluminum, which passed into solution by dissolution reactions. In extracts from the IIBD horizon, aluminum was solubilized by the dissolution of aluminosilicates inherited from the parent rock.

  14. Ultrafast bulk diffusion of AlHx in high-entropy dehydrogenation intermediates of NaAlH4 [Highly mobile AlHx species and the dehydogenation kinetics of NaAlH4

    DOE PAGES

    Zhang, Feng; Wood, Brandon C.; Wang, Yan; ...

    2014-07-21

    Using first-principles molecular dynamics (FPMD) and total-energy calculations, we demonstrate low-barrier bulk diffusion of Al-bearing species in γ-NaAlH4, a recently proposed high-entropy polymorph of NaAlH4. For charged AlH4– and neutral AlH3 vacancies, the computed barriers for diffusion are <0.1 eV, and we directly observe the predicted diffusive pathways in FPMD simulations at picosecond time scales. In contrast, such diffusion in the α phase is inaccessible to FPMD, consistent with much higher barriers. The transport behavior of γ-NaAlH4, in addition to key dynamical and structural signatures, is consistent with experimental observations of high-mobility species, strongly supporting the idea that an intermediatemore » transition from the α phase to a high-entropy polymorph facilitates the hydrogen-releasing decomposition of NaAlH4. Lastly, our results provide an answer to longstanding questions regarding the responsible agent for the experimentally observed efficient Al transport during dehydrogenation and suggest that mass transport and phase transformation kinetics are coupled. Implications for understanding the (de)hydrogenation of undoped and catalyzed NaAlH4 are discussed.« less

  15. Multiscale modelling of Interaction of Alane Clusters on Al(111) surface: A Reactive Force Field and Infrared Absorption Spectroscopy Approach

    NASA Astrophysics Data System (ADS)

    Ojwang, Julius; van Duin, Adri; Goddard, William, III; van Santen, Rutger

    2010-10-01

    Alanes are believed to be the ubiquitous facilitators of mass transport of aluminum atoms during the thermal decomposition of NaAlH4. Alanes also take part on decomposition of AlH3, another important material for hydrogen storage. We have used interplay of theoretical simulations (reactive force field and density functional theory) and experiments (IR reflection absorption spectroscopy) to address the issue of the role of alanes as facilitators of mass transport of aluminum atoms. We have obtained valuable details on the mechanism of formation and agglomeration of alanes on Al(111) surface. Our simulations show that, on the Al(111) surface, alanes oligomerize into larger alanes. The identification of these string like intermediates as a precursor to the bulk hydride phase allows us to explain the loss of resolution in surface IR experiments with increasing hydrogen coverage on single crystal Al(111) surface. This is in excellent agreement with the experimental works of Go et al. (E. Go, K. Thuermer, J.E. Reutt-Robey, Surf. Sci.,437:377(1999)).

  16. Density Functional Theory Based Kinetic Monte Carlo Approach for Understanding Atomistic Mechanisms for Reversible Hydrogen Storage in Metal Hydrides: Application to Alane Formation on Ti Doped Al Surfaces

    NASA Astrophysics Data System (ADS)

    Karim, A.; Muckerman, J.; Sutter, P.; Muller, E.

    2008-03-01

    We describe a density functional kinetic Monte Carlo approach enabling us to study and simulate the steady-state situation of dissociative adsorption of hydrogen along with diffusion and reaction of Al and H atoms leading towards the formation of alane species on Ti-doped Al surfaces. In the first step, density functional theory is used in conjunction with the nudged elastic band/drag method to obtain the energetics of the relevant atomistic processes of Al and H diffusion and their reactions on Al surfaces with different concentration of dopant Ti atoms. Subsequently, the kinetic Monte Carlo method is employed, which accounts for the spatial distribution, fluctuations, and evolution of chemical species at Ti-doped Al surfaces under steady-state conditions. This DFT-based KMC approach provides an insight into the kinetics of alanes at technologically relevant pressure and temperature conditions. Our computed production rates of AlH3 on Al surfaces are in agreement with experimental data. We also obtained temperature programmed desorption spectra of different alane species, which is agreeing well with experiments.

  17. Solution processed aluminum paper for flexible electronics.

    PubMed

    Lee, Hye Moon; Lee, Ha Beom; Jung, Dae Soo; Yun, Jung-Yeul; Ko, Seung Hwan; Park, Seung Bin

    2012-09-11

    As an alternative to vacuum deposition, preparation of highly conductive papers with aluminum (Al) features is successfully achieved by the solution process consisting of Al precursor ink (AlH(3){O(C(4)H(9))(2)}) and low temperature stamping process performed at 110 °C without any serious hydroxylation and oxidation problems. Al features formed on several kinds of paper substrates (calendar, magazine, and inkjet printing paper substrates) are less than ~60 nm thick, and their electrical conductivities were found to be as good as thermally evaporated Al film or even better (≤2 Ω/□). Strong adhesion of Al features to paper substrates and their excellent flexibility are also experimentally confirmed by TEM observation and mechanical tests, such as tape and bending tests. The solution processed Al features on paper substrates show different electrical and mechanical performance depending on the paper type, and inkjet printing paper is found to be the best substrate with high and stable electrical and mechanical properties. The Al conductive papers produced by the solution process may be applicable in disposal paper electronics.

  18. Thermochemistry of Alane Complexes for Hydrogen Storage: A Theoretical and Experimental Investigation

    PubMed Central

    2011-01-01

    Knowledge of the relative stabilities of alane (AlH3) complexes with electron donors is essential for identifying hydrogen storage materials for vehicular applications that can be regenerated by off-board methods; however, almost no thermodynamic data are available to make this assessment. To fill this gap, we employed the G4(MP2) method to determine heats of formation, entropies, and Gibbs free energies of formation for 38 alane complexes with NH3−nRn (R = Me, Et; n = 0−3), pyridine, pyrazine, triethylenediamine (TEDA), quinuclidine, OH2−nRn (R = Me, Et; n = 0−2), dioxane, and tetrahydrofuran (THF). Monomer, bis, and selected dimer complex geometries were considered. Using these data, we computed the thermodynamics of the key formation and dehydrogenation reactions that would occur during hydrogen delivery and alane regeneration, from which trends in complex stability were identified. These predictions were tested by synthesizing six amine−alane complexes involving trimethylamine, triethylamine, dimethylethylamine, TEDA, quinuclidine, and hexamine and obtaining upper limits of ΔG° for their formation from metallic aluminum. Combining these computational and experimental results, we establish a criterion for complex stability relevant to hydrogen storage that can be used to assess potential ligands prior to attempting synthesis of the alane complex. On the basis of this, we conclude that only a subset of the tertiary amine complexes considered and none of the ether complexes can be successfully formed by direct reaction with aluminum and regenerated in an alane-based hydrogen storage system. PMID:22962624

  19. Thermochemistry of Alane Complexes for Hydrogen Storage: A Theoretical and Experimental Investigation.

    PubMed

    Wong, Bryan M; Lacina, David; Nielsen, Ida M B; Graetz, Jason; Allendorf, Mark D

    2011-04-21

    Knowledge of the relative stabilities of alane (AlH(3)) complexes with electron donors is essential for identifying hydrogen storage materials for vehicular applications that can be regenerated by off-board methods; however, almost no thermodynamic data are available to make this assessment. To fill this gap, we employed the G4(MP2) method to determine heats of formation, entropies, and Gibbs free energies of formation for 38 alane complexes with NH(3-n)R(n) (R = Me, Et; n = 0-3), pyridine, pyrazine, triethylenediamine (TEDA), quinuclidine, OH(2-n)R(n) (R = Me, Et; n = 0-2), dioxane, and tetrahydrofuran (THF). Monomer, bis, and selected dimer complex geometries were considered. Using these data, we computed the thermodynamics of the key formation and dehydrogenation reactions that would occur during hydrogen delivery and alane regeneration, from which trends in complex stability were identified. These predictions were tested by synthesizing six amine-alane complexes involving trimethylamine, triethylamine, dimethylethylamine, TEDA, quinuclidine, and hexamine and obtaining upper limits of ΔG° for their formation from metallic aluminum. Combining these computational and experimental results, we establish a criterion for complex stability relevant to hydrogen storage that can be used to assess potential ligands prior to attempting synthesis of the alane complex. On the basis of this, we conclude that only a subset of the tertiary amine complexes considered and none of the ether complexes can be successfully formed by direct reaction with aluminum and regenerated in an alane-based hydrogen storage system.

  20. Structural Characterization of Metal Hydrides for Energy Applications

    NASA Astrophysics Data System (ADS)

    George, Lyci

    Hydrogen can be an unlimited source of clean energy for future because of its very high energy density compared to the conventional fuels like gasoline. An efficient and safer way of storing hydrogen is in metals and alloys as hydrides. Light metal hydrides, alanates and borohydrides have very good hydrogen storage capacity, but high operation temperatures hinder their application. Improvement of thermodynamic properties of these hydrides is important for their commercial use as a source of energy. Application of pressure on materials can have influence on their properties favoring hydrogen storage. Hydrogen desorption in many complex hydrides occurs above the transition temperature. Therefore, it is important to study the physical properties of the hydride compounds at ambient and high pressure and/or high temperature conditions, which can assist in the design of suitable storage materials with desired thermodynamic properties. The high pressure-temperature phase diagram, thermal expansion and compressibility have only been evaluated for a limited number of hydrides so far. This situation serves as a main motivation for studying such properties of a number of technologically important hydrides. Focus of this dissertation was on X-ray diffraction and Raman spectroscopy studies of Mg2FeH6, Ca(BH4) 2, Mg(BH4)2, NaBH4, NaAlH4, LiAlH4, LiNH2BH3 and mixture of MgH 2 with AlH3 or Si, at different conditions of pressure and temperature, to obtain their bulk modulus and thermal expansion coefficient. These data are potential source of information regarding inter-atomic forces and also serve as a basis for developing theoretical models. Some high pressure phases were identified for the complex hydrides in this study which may have better hydrogen storage properties than the ambient phase. The results showed that the highly compressible B-H or Al-H bonds and the associated bond disordering under pressure is responsible for phase transitions observed in brorohydrides or alanates. Complex hydrides exhibited very high compressibility suggesting possibility to destabilize them with pressure. With high capacity and favorable thermodynamics, complex hydrides are suitable for reversible storage. Further studies are required to overcome the kinetic barriers in complex hydrides by catalytic addition. A comparative study of the hydride properties with that of the constituting metal, and their inter relationships were carried out with many interesting features.

  1. Surface investigations of the atomic layer growth mechanism in aluminum nitride thin film deposition using dimethylethylamine alane and ammonia

    NASA Astrophysics Data System (ADS)

    Kuo, Jason Se-Yung

    Aluminum Nitride (AlN), a wide-bandgap semiconductor, has been shown to be an extremely versatile material in semiconductor applications. Our previous efforts in formulating a Metalorganic Chemical Vapor Deposition (MOCVD) processing strategy to deposit AN using Dimethylethylamine Alane (DMEAA; AlH3:N(CH3)2CH2CH3) and ammonia resulted in high quality film growth at low temperatures (˜600 K). Understanding the surface reactions involved is a key step in successfully optimizing a MOCVD process. In this research, we investigated the surface interactions between DMEAA and ammonia leading to the Atomic Layer Growth (ALG) mode on a Si(100) surface using a combination of surface analysis techniques, including Secondary-Ion Mass Spectrometry (SIMS), Temperature-Programmed SIMS (TPSIMS), X-ray Photoelectron Spectroscopy (XPS), and Temperature-Programmed Desorption (TPD). The exposure of Si(100) to DMEAA at 310 K resulted in self-limiting adsorption of molecular DMEAA and Dimethylethylamine (DMEA). Based on the stoichiometric information from XPS, the molecularly adsorbed DMEA most likely originated from the exposure of a mixed DMEAA-DMEA gas phase rather than a dissociative adsorption process. The DMEAA molecule is susceptible to thermal decomposition, as the aminealane adduct configuration was no longer observed above 490 K. This can impose an upper temperature limit in developing a processing strategy. The chemical interaction between ammonia and DMEAA resulted in a displacement of DMEA by ammonia. A new surface intermediate (AlHND2) was detected with both SIMS and XPS. This displacement mechanism was rationalized using Hard-Soft-Acid-Base (HSAB) theory. We were able to observe, in a step-by-step fashion, the atomic layer growth process by monitoring the C:N ratios using XPS. The resulting AlN film contained substantial hydrogen but the hydrogen content may be removed thermally. Atomic layer growth mechanism provides an effective means to grow high quality thin films by specific chemical interactions. Employing this approach, we have shown that the carbon contamination from the organic ligands may be controlled stringently.

  2. Understanding atomistic phenomenon for hydrogen storage in complex metal hydrides

    NASA Astrophysics Data System (ADS)

    Chopra, Irinder Singh

    The storage of hydrogen into metals in the form of complex metal hydrides is one of the most promising methods. However, the incorporation and release of hydrogen requires very high temperatures. The discovery that the addition of Ti compounds lowers NaAlH4 decomposition barriers closer to ambient conditions, has re-ignited the field, and it is believed that surface processes are responsible for H2 dissociation and mass transport required to form the hydrogenated materials. Such surface reactions mechanisms are however difficult to study with typical spectroscopic and imaging surface science tools. Alanes lack contrast under electron microscopes and can modify the Scanning Tunneling Microscopy (STM) tips. Infrared spectroscopy would be a sensitive probe to investigate the adsorption of hydrogen providing, but has so far failed to detect chemisorbed hydrogen on Ti-doped Al surfaces due to the weak Al-H dynamic dipole moment. Thus despite extensive investigations, the fundamental mechanisms of the role of Ti and alane formation have remained elusive. In this study combining surface infrared (IR) spectroscopy and density functional theory (DFT), we provide atomistic details about the role of Ti as a catalyst for hydrogen uptake and alane formation and evolution on single crystal Al(111) and Al(100) surfaces. We are able to detect H indirectly by using CO as a probe molecule of the weak Al-H species. We demonstrate that aluminum doped with very small amounts of titanium (in a specific configuration) can activate molecular hydrogen at temperatures as low as 90K. Once dissociated, hydrogen spills over from these catalytic sites on to the Al surface and protects the surface from further reactions. We also show that, on Ti-doped Al surfaces, the diffusion dynamics are severely altered by Ti doping (Atomic hydrogen and AlH3 are trapped at the Ti sites) as indicated by a marked decrease of higher alane concentrations, which is deleterious for hydrogen storage for which mass transport is required. These results provide an understanding of the reaction mechanisms for hydrogen storage in the alanates (NaAlH4) that can help in identifying and realizing other complex metal hydrides for an effective hydrogen based economy.

  3. Metal hydride and pyrophoric fuel additives for dicyclopentadiene based hybrid propellants

    NASA Astrophysics Data System (ADS)

    Shark, Steven C.

    The purpose of this study is to investigate the use of reactive energetic fuel additives that have the potential to increase the combustion performance of hybrid rocket propellants in terms of solid fuel regression rate and combustion efficiency. Additives that can augment the combustion flame zone in a hybrid rocket motor by means of increased energy feedback to the fuel grain surface are of great interest. Metal hydrides have large volumetric hydrogen densities, which gives these materials high performance potential as fuel additives in terms of specifc impulse. The excess hydrogen and corresponding base metal may also cause an increase in the hybrid rocket solid fuel regression rate. Pyrophoric additives also have potential to increase the solid fuel regression rate by reacting more readily near the burning fuel surface providing rapid energy feedback. An experimental performance evaluation of metal hydride fuel additives for hybrid rocket motor propulsion systems is examined in this study. Hypergolic ignition droplet tests and an accelerated aging study revealed the protection capabilities of Dicyclopentadiene (DCPD) as a fuel binder, and the ability for unaided ignition. Static hybrid rocket motor experiments were conducted using DCPD as the fuel. Sodium borohydride (NabH4) and aluminum hydride (AlH3) were examined as fuel additives. Ninety percent rocket grade hydrogen peroxide (RGHP) was used as the oxidizer. In this study, the sensitivity of solid fuel regression rate and characteristic velocity (C*) efficiency to total fuel grain port mass flux and particle loading is examined. These results were compared to HTPB combustion performance as a baseline. Chamber pressure histories revealed steady motor operation in most tests, with reduced ignition delays when using NabH4 as a fuel additive. The addition of NabH4 and AlH3 produced up to a 47% and 85% increase in regression rate over neat DCPD, respectively. For all test conditions examined C* efficiency ranges between 80% and 90%. The regression rate and C* efficiency mass flux dependence indicate a shift towards a more diffusion controlled system with metal hydride particle addition. Although these types of energetic particles have potential as high performing fuel additives, they can be in low supply and expensive. An opposed flow burner was investigated as a means to screen and characterize hybrid rocket fuels prior to full scale rocket motor testing. Although this type of configuration has been investigated in the past, no comparison has been made to hybrid rocket motor operation in terms of mass flux. Polymeric fuels and low melt temperature fuels with and without additives were investigated via an opposed flow burner. The effects of laminar and turbulent flow regimes on the convective heat transfer in the opposed flow system was depicted in the regression rate trends of these fuels. Regression rate trends similar to hybrid rocket motor operation were depicted, including the entrainment mechanism for paran fuel. However, there was a shift in overall magnitude of these results. A decrease in regression rate occurred for HTPB loaded with passivated nano-aluminum, due to low resonance time in the reaction zone. Previous results have shown that pyrophoric additives can cause an increase in regression rate in the opposed flow burner configuration. It is proposed that the opposed burner is useful as a screening and characterization tool for some propellant combinations. Gaseous oxygen (GOX) was investigated as an oxidizer for similar fuels evaluated with RGHP. Specifically, combustion performance sensitivity to mass flux and MH particle size was investigated. Similar results to the RGHP experiments were observed for the regression rate tends of HTPB, DPCD, and NabH 4 addition. Kinetically limited regression rate dependence on mass flux was observed at the higher mass flux levels. No major increase in C* efficiency was observed for MH addition. The C* efficiency varied with equivalence ratio by approximately 10 percentage points, which was not observed in the RGHP experiments. A 10 percentage point decrease in C* efficiency was observed with increasing mass flux in the system. This was most likely due to poorly mixed fuel and oxidizer in center of the combustion chamber at the higher mass flux levels. Detailed measurements of the hybrid rocket combustion zone is useful for understanding the mechanisms governing performance, but can be difficult to obtain. Traditional slab burner configurations have proven useful but are operationally limited in pressure and mass flux ranges. A new optical cylindrical combustor (OCC) design is presented that allows surface and flame zone imaging and tracking during hybrid rocket motor operation at appreciable mass flux and pressure levels, > 100 kg/s/m2 and > 0.69 MPa. The flame height and regression rate sensitivity to mass flux and chamber pressure was examined for the same fuels examined in the GOX hybrid rocket motor, with the addition of DCPD fuel loaded with Al and unpassivated mechanically activated Al-PTFE. The regression rate trends were on the same order of magnitude of traditional hybrid rocket motor results. A flame height decrease was observed for increased mass flux. The flame height increased with NabH 4 addition, which is most likely a function of increased blowing at the surface. There was no appreciable flame height sensitivity to NabH4 particle size. There was no relative change in flame height or regression rate between the Al and AL-PTFE addition. The OCC allowed visualization of the hybrid rocket fuel flame zone at mass flux and pressure levels that are not known to be report for traditional slab burner configurations in literature. The OCC proved to be a new useful tool for investigated hybrid rocket propellant combustion characteristics.

  4. The development of reactive fuel grains for pyrophoric relight of in-space hybrid rocket thrusters

    NASA Astrophysics Data System (ADS)

    Steiner, Matthew Wellington

    This study presents and investigates a novel hybrid fuel grain that reacts pyrophorically with gaseous oxidizer to achieve restart of a hybrid rocket motor propulsion system while reducing cost and handling concerns. This reactive fuel grain (RFG) relies on the pyrophoric nature of finely divided metal particles dispersed in a solid dicyclopentadiene (DCPD) binder, which has been shown to encapsulate air-sensitive additives until they are exposed to combustion gases. An RFG is thus effectively inert in open air in the absence of an ignition source, though the particles encapsulated within remain pyrophoric. In practice, this means that an RFG that is ignited in the vacuum of space and then extinguished will expose unoxidized pyrophoric particles, which can be used to generate sufficient heat to relight the propellant when oxidizer is flowed. The experiments outlined in this work aim to develop a suitable pyrophoric material for use in an RFG, demonstrate pyrophoric relight, and characterize performance under conditions relevant to a hybrid rocket thruster. Magnesium, lithium, calcium, and an alloy of titanium, chromium, and manganese (TiCrMn) were investigated to determine suitability of pure metals as RFG additives. Additionally, aluminum hydride (AlH3), lithium aluminum hydride (LiAlH4), lithium borohydride (LiBH4), and magnesium hydride (MgH2) were investigated to determine suitability of metals hydrides as RFG additives or as precursors for pure-metal RFG additives. Pyrophoric metals have been previously investigated as additives for increasing the regression rate of hybrid fuels, but to the author's knowledge, these materials have not been specifically investigated for their ability to ignite a propellant pyrophorically. Commercial research-grade metals were obtained as coarse powders, then ball-milled to attempt to reduce particle size below a critical diameter needed for pyrophoricity. Magnesium hydride was ball-milled and then cycled in a hydride cycling apparatus to attempt to fracture the particles through hydrogen sorption and thermal stresses. These powders were then tested for pyrophoricity with atmospheric and pure concentrations of oxygen. The TiCrMn powder was chosen as the material for evaluation of propellant performance, and was mixed with DCPD in various weight ratios to determine the required additive loading needed for pyrophoricity of the bulk propellant. Weight percentages of 10, 20, 30, and 50 wt.% TiCrMn were used to evaluate relight capability and propellant performance, and weight loadings of 50, 70, and 90 wt.% TiCrMn were used to evaluate approximate maximum loading possible without rendering the propellant structurally unsound. Propellant tests were conducted in an opposed flow burner apparatus for sub-scale regression rate and relight experiments, and an optically accessible cylindrical combustion chamber (OCC) that allows high speed cameras to record the regressing propellant surface during combustion. Gaseous oxygen (GOX) was used as an oxidizer for all tests due to its ready availability and common use as a hybrid rocket oxidizer. Opposed flow burner experiments are an inexpensive means of rapidly testing various propellant formulations at different conditions, whereas OCC tests are useful for obtaining realistic data on how an RFG would likely operate as part of a propulsion system. Relight in the opposed flow burner was attempted by cycling oxygen and nitrogen flows with carefully timed solenoid valves to initiate and extinguish combustion, and to control the slow diffusion of oxygen to the surface of the propellant, which would render the TiCrMn non-pyrophoric. The opposed flow burner experiments did not conclusively demonstrate the pyrophoric relight capability of the RFG propellant due in part to the persistence of hot spots between oxygen and purge nitrogen cycles, as determined by high-speed imaging in the near infrared range. An opposed flow burner apparatus was then constructed within a vacuum chamber assembly thus preventing atmospheric oxygen from diffusing to the propellant surface, but these tests did not demonstrate pyrophoric relight. Future work is proposed to evaluate the effect of pyrophoric particle size in order to determine the role ignition delay of each particle has in the relight capability of RFGs. OCC experiments were conducted at a low and high GOX mass flux of approximately 150 and 300 kg/s/m2, respectively, at a nominal chamber pressure of 150 psia. Four strand compositions were used: pure DCPD, 30 wt.% pyrophoric TiCrMn powder with average particle diameters of approximately 1-10 microns, 30 wt.% oxidized TiCrMn powder with average particle diameters of approximately 1-10 microns, and 30 wt.% TiCrMn powder with average particle diameters of approximately 1-4 mm. Regression rate was measure by weight loss, average web thickness change at three axial locations on the strand, and through time-resolved tracking of the regressing propellant surface via high speed video. While visual observations suggest that the addition of TiCrMn significantly increases regression rate, initial data do not show a significant trend. Additionally, it is observed that the oxidized TiCrMn strands regress at the same rate as those loaded with pyrophoric TiCrMn, suggesting that erosive burning and heat addition of the added metal may be the cause of the observed increase in regression rate. The data are too sparse to make conclusions about the effect of particle size on regression rate, so further tests are recommended to develop a significant data set for the effect of pyrophoricity and particle size on regression rate. The test article was damaged at the end of the regression rate experimental campaign, which precluded the collection of relight data that was planned for strands loaded with 50 wt.% TiCrMn particles with an average diameter of approximately 1-4 mm. Though further tests are needed to demonstrate pyrophoric relight of an RFG, the current work establishes a baseline for RFG performance and suggests that pyrophoric relight is possible by tailoring the particle size of the pyrophoric metal additive to control heat release and ignition delay.

  5. Search for nitrates on Mars by the Sample Analysis at Mars (SAM) Instrument

    NASA Astrophysics Data System (ADS)

    Navarro-Gonzalez, Rafael

    One of the main goals of the Mars Science Laboratory is to determine whether the planet ever had environmental conditions capable of supporting microbial life. Nitrogen is a fundamental element for life, and is present in structural (e.g., proteins), catalytic (e.g., enzymes and ribozymes), energy transfer (e.g., ATP) and information storage (RNA and DNA) bio-molecules. Planetary models suggest that nitrogen was abundant in the early Martian atmosphere as dinitrogen (N _{2}). However, a fraction of N _{2} has been lost to space by sputtering and photochemical processes [1, 2], impact erosion [3], and chemical oxidation to nitrates [4, 5]. Nitrates produced early in Mars’ history by photochemistry may later decompose back into N _{2} by the current impact flux [6]. It is estimated that the Martian surface could contain soil nitrates at levels of 0.3 wt.% N, if mixed homogenously [6], or a layer of pure NaNO _{3} of about 3 m thickness [5] distributed globally. Nitrates are a fundamental source for nitrogen for terrestrial microorganisms. Therefore, the detection of soil nitrates is important to assess habitability in the Martian environment. The only previous attempt to search for soil nitrates was by TEGA and the MECA WCL on the Phoenix mission but no evolved N-containing species were detected [7]. Nitrates have been tentatively identified in two Martian meteorites: Nakhla [8] and EETA79001 [9]. SAM is capable of detecting nitrates by their thermal decomposition into nitric oxide, NO. SAM analyzed samples from Rocknest soil and two drill holes located at John Klein (JK) and Cumberland (CB) mudstones in the Sheepbed member of the Yellowknife Bay formation in Gale Crater. There appear to be several peaks associated with the release of m/z 30 in the temperature range from 150(°) °C to 600(°) °C. M/z 30 can be attributed to nitric oxide; however, other possible chemical interferences may be present, such as ethane (C _{2}H _{6}), formaldehyde (HCHO), diazene (N _{2}H _{2}), aluminum trihydride (AlH _{3}), and silylene (SiH _{2}), and they are assessed. The origin of nitric oxide is discussed and its thermal evolution is compared with analog studies of mixtures of nitrates and perchlorates [10]. [1] Luhmann, J.G., Johnson E. And Zhang, M.H.G.: 1992, Evolutionary impact of sputtering of the Martian atmosphere by O (+) pickup ions. Geophys. Res. Lett. 19, 2151-2154. [2] Jakosky, B.M. Pepin, R.O., Johnsom, R.E. and Fox, J.L: 1994, Mars atmospheric loss and isotopic fractionation by solar-wind-induced sputtering and photochemical escape. Icarus 111, 271-288. [3] Melosh, H.J. and Vickery, A.M.: 1989, Impact erosion of the primordial atmosphere of Mars. Nature 338, 487-489. [4] Mancinelli, R.L. and McKay, C.P. :1988, The evolution of nitrogen cycling. Origins Life 18, 311-325. [5] Manning, C.V., McKay, C.P., and Zahnle, K.J.: 2008, The nitrogen cycle on Mars: Impact decomposition of near-surface nitrates as a source for a nitrogen steady state. Icarus 197, 60-64. [6] Smith, M.L., Claire, M.W., Catling, D.C., and Zahnle, K.J.: 2014, The formation of sulfate, nitrate and perchlorate salts in the martian atmosphere. Icarus 231, 51-64. [7] Hecht, M. H., Kounaves, S.P., Quinn, R.C., West, S.J., Young, S.M.M., Ming, D.W.,Catling, D.C., Clark, B.C., Boynton, W.V.,Hoffman, J., DeFlores, L.P., Gospodinova, K., Kapit, J., and Smith,P.H.: 2009, Detection of Perchlorate and the Soluble Chemistry of Martian Soil at the Phoenix Lander Site. Science, 325, 64-67. [8] Grady, M.M., Wright, I. P., and Pillinger C. T.: 1995, Search for nitrates in Martian meteorite. J. Geophys. Res. 100, 5449. [9] Kounaves, S.P., Carrier, B.L., O’Neil, G.D., Stroble, S.T., Claire, M.W.: 2013, Evidence of martian perchlorate, chlorate, and nitrate in Mars meteorite EETA79001: implications for oxidants and organics, Icarus 229, 206. [10] Support from the following grants is acknowledged: IN106013 and CONACYT 98466.

  6. Complex Hydride Compounds with Enhanced Hydrogen Storage Capacity

    SciTech Connect

    Mosher, Daniel A.; Opalka, Susanne M.; Tang, Xia; Laube, Bruce L.; Brown, Ronald J.; Vanderspurt, Thomas H.; Arsenault, Sarah; Wu, Robert; Strickler, Jamie; Anton, Donald L.; Zidan, Ragaiy; Berseth, Polly

    2008-02-18

    The United Technologies Research Center (UTRC), in collaboration with major partners Albemarle Corporation (Albemarle) and the Savannah River National Laboratory (SRNL), conducted research to discover new hydride materials for the storage of hydrogen having on-board reversibility and a target gravimetric capacity of ≥ 7.5 weight percent (wt %). When integrated into a system with a reasonable efficiency of 60% (mass of hydride / total mass), this target material would produce a system gravimetric capacity of ≥ 4.5 wt %, consistent with the DOE 2007 target. The approach established for the project combined first principles modeling (FPM - UTRC) with multiple synthesis methods: Solid State Processing (SSP - UTRC), Solution Based Processing (SBP - Albemarle) and Molten State Processing (MSP - SRNL). In the search for novel compounds, each of these methods has advantages and disadvantages; by combining them, the potential for success was increased. During the project, UTRC refined its FPM framework which includes ground state (0 Kelvin) structural determinations, elevated temperature thermodynamic predictions and thermodynamic / phase diagram calculations. This modeling was used both to precede synthesis in a virtual search for new compounds and after initial synthesis to examine reaction details and options for modifications including co-reactant additions. The SSP synthesis method involved high energy ball milling which was simple, efficient for small batches and has proven effective for other storage material compositions. The SBP method produced very homogeneous chemical reactions, some of which cannot be performed via solid state routes, and would be the preferred approach for large scale production. The MSP technique is similar to the SSP method, but involves higher temperature and hydrogen pressure conditions to achieve greater species mobility. During the initial phases of the project, the focus was on higher order alanate complexes in the phase space between alkaline metal hydrides (AmH), Alkaline earth metal hydrides (AeH2), alane (AlH3), transition metal (Tm) hydrides (TmHz, where z=1-3) and molecular hydrogen (H2). The effort started first with variations of known alanates and subsequently extended the search to unknown compounds. In this stage, the FPM techniques were developed and validated on known alanate materials such as NaAlH4 and Na2LiAlH6. The coupled predictive methodologies were used to survey over 200 proposed phases in six quaternary spaces, formed from various combinations of Na, Li Mg and/or Ti with Al and H. A wide range of alanate compounds was examined using SSP having additions of Ti, Cr, Co, Ni and Fe. A number of compositions and reaction paths were identified having H weight fractions up to 5.6 wt %, but none meeting the 7.5 wt%H reversible goal. Similarly, MSP of alanates produced a number of interesting compounds and general conclusions regarding reaction behavior of mixtures during processing, but no alanate based candidates meeting the 7.5 wt% goal. A novel alanate, LiMg(AlH4)3, was synthesized using SBP that demonstrated a 7.0 wt% capacity with a desorption temperature of 150°C. The deuteride form was synthesized and characterized by the Institute for Energy (IFE) in Norway to determine its crystalline structure for related FPM studies. However, the reaction exhibited exothermicity and therefore was not reversible under acceptable hydrogen gas pressures for on-board recharging. After the extensive studies of alanates, the material class of emphasis was shifted to borohydrides. Through SBP, several ligand-stabilized Mg(BH4)2 complexes were synthesized. The Mg(BH4)2*2NH3 complex was found to change behavior with slightly different synthesis conditions and/or aging. One of the two mechanisms was an amine-borane (NH3BH3) like dissociation reaction which released up to 16 wt %H and more conservatively 9 wt%H when not including H2 released from the NH3. From FPM, the stability of the Mg(BH4)2*2NH3 compound was found to increase with the inclusion of NH3 groups in the inner-Mg coordination sphere, which in turn correlated with lowering the dimensionality of the Mg(BH4)2 network. Development of various Ak Tm-B-H compounds using SSP produced up to 12 wt% of H2 desorbed at temperatures of 400°C. However, the most active material can only be partially recharged to 2 wt% H2 at 220-300°C and 195 bar H2 pressure due to stable product formation. While gravimetric & volumetric targets are feasible, reversibility remains a persistent challenge.