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Sample records for hydride electrochemical hydrogen

  1. Significantly improved electrochemical hydrogen storage properties of magnesium nickel hydride modified with nano-nickel

    Science.gov (United States)

    Chen, Wei; Zhu, Yunfeng; Yang, Chen; Zhang, Jiguang; Li, Menghuai; Li, Liquan

    2015-04-01

    Magnesium nickel hydride (Mg2NiH4) used as negative electrode material in nickel-metal hydride (Ni-MH) secondary battery is modified by nano-nickel via mechanical milling. In this paper, we systematically investigate the microstructure and electrochemical properties of the modified system with different milling durations. X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM) analyses confirm the amorphous transformation of Mg2Ni-based hydride and a novel NiH0.75 nanocrystalline with a diameter of about 5 nm embedding or covering on the surface of the base particle has been observed. Its formation mechanism and positive effects on electrochemical properties of the Mg2NiH4 have also been elaborated. Electrochemical measurements show that the 5 h milled composite possesses markedly increased discharge capacity up to 896 mAh g-1. With prolonging the milling duration from 5 h to 40 h, the discharge capacity at the 10th cycle increases from 99 mAh g-1 to 359 mAh g-1. Besides, the discharging procedure changes from stepwise processes to one single-step process with increasing the milling duration. Tafel polarization test shows that the nano-nickel modified system exhibits a much better anti-corrosion ability during charging/discharging cycles. Meanwhile, both the charge-transfer reaction on the alloy surface and hydrogen diffusion inside the alloy bulk are enhanced with nano-nickel modification.

  2. Nickel-hydrogen. [metal hydrides, electrochemical corrosion, and structural design

    Science.gov (United States)

    Mchenry, E. J.

    1977-01-01

    Because of the disintegration of LaNi5 as the lattice expands on absorbing hydrogen, a nickel hydrogen cell similar to a nickel cadmium cell was designed. The positive electrode is wrapped in a microporous separator and the leads are insulated. A negative conducting grid is inserted and welded to the top of the can into an open ended container which is then turned upside down and filled so that LiNa5 powder occupies all the space not used by the rest of the components. The bottom of the can is then welded on. A fill tube is located either on the bottom or on the top of the can. When welded shut, the cell is put into a pressure bomb and the lanthanum nickel is activated at about 1,000 pounds of hydrogen. Electrolytes are added to the cell as well as whatever amount of hydrogen precharge desired, and the cell is sealed. Advantages and disadvantages of the cell are discussed.

  3. The electrochemical impedance of metal hydride electrodes

    DEFF Research Database (Denmark)

    Valøen, Lars Ole; Lasia, Andrzej; Jensen, Jens Oluf

    2002-01-01

    The electrochemical impedance responses for different laboratory type metal hydride electrodes were successfully modeled and fitted to experimental data for AB5 type hydrogen storage alloys as well as one MgNi type electrode. The models fitted the experimental data remarkably well. Several AC......, explaining the experimental impedances in a wide frequency range for electrodes of hydride forming materials mixed with copper powder, were obtained. Both charge transfer and spherical diffusion of hydrogen in the particles are important sub processes that govern the total rate of the electrochemical...... hydrogen absorption/desorption reaction. To approximate the experimental data, equations describing the current distribution in porous electrodes were needed. Indications of one or more parallel reduction/oxidation processes competing with the electrochemical hydrogen absorption/desorption reaction were...

  4. Mn in misch-metal based superlattice metal hydride alloy - Part 1 structural, hydrogen storage and electrochemical properties

    Science.gov (United States)

    Young, K.; Wong, D. F.; Wang, L.; Nei, J.; Ouchi, T.; Yasuoka, S.

    2015-03-01

    The structural, gaseous phase hydrogen storage, and electrochemical properties of a series of Mn-modified misch-metal based superlattice metal hydride alloys were investigated in part one of this two-part series of papers. X-ray diffraction analysis showed that these alloys are all multi-phased compositions with different abundances of AB2, AB3, A2B7, AB4, and AB5 phases. Substitution of Ni in the B-site by Mn promotes AB5 phase formation and decreases both gaseous phase and electrochemical capacities due to the reduction in the abundance of main hexagonal A2B7 phase. AC impedance and magnetic susceptibility measurement were employed to characterize the surface of Mn-free and Mn-modified alloys and show deterioration in surface catalytic ability as the Mn-content increases. Mn-modification adversely affected misch-metal based superlattice metal hydride alloy properties such as phase homogeneity, capacity, cycle stability, high-rate performance, and surface reaction.

  5. Electrochemical hydrogen Storage Systems

    Energy Technology Data Exchange (ETDEWEB)

    Dr. Digby Macdonald

    2010-08-09

    As the global need for energy increases, scientists and engineers have found a possible solution by using hydrogen to power our world. Although hydrogen can be combusted as a fuel, it is considered an energy carrier for use in fuel cells wherein it is consumed (oxidized) without the production of greenhouse gases and produces electrical energy with high efficiency. Chemical storage of hydrogen involves release of hydrogen in a controlled manner from materials in which the hydrogen is covalently bound. Sodium borohydride and aminoborane are two materials given consideration as chemical hydrogen storage materials by the US Department of Energy. A very significant barrier to adoption of these materials as hydrogen carriers is their regeneration from 'spent fuel,' i.e., the material remaining after discharge of hydrogen. The U.S. Department of Energy (DOE) formed a Center of Excellence for Chemical Hydrogen Storage, and this work stems from that project. The DOE has identified boron hydrides as being the main compounds of interest as hydrogen storage materials. The various boron hydrides are then oxidized to release their hydrogen, thereby forming a 'spent fuel' in the form of a lower boron hydride or even a boron oxide. The ultimate goal of this project is to take the oxidized boron hydrides as the spent fuel and hydrogenate them back to their original form so they can be used again as a fuel. Thus this research is essentially a boron hydride recycling project. In this report, research directed at regeneration of sodium borohydride and aminoborane is described. For sodium borohydride, electrochemical reduction of boric acid and sodium metaborate (representing spent fuel) in alkaline, aqueous solution has been investigated. Similarly to literature reports (primarily patents), a variety of cathode materials were tried in these experiments. Additionally, approaches directed at overcoming electrostatic repulsion of borate anion from the cathode, not

  6. Hydrogen Outgassing from Lithium Hydride

    Energy Technology Data Exchange (ETDEWEB)

    Dinh, L N; Schildbach, M A; Smith, R A; Balazs1, B; McLean II, W

    2006-04-20

    Lithium hydride is a nuclear material with a great affinity for moisture. As a result of exposure to water vapor during machining, transportation, storage and assembly, a corrosion layer (oxide and/or hydroxide) always forms on the surface of lithium hydride resulting in the release of hydrogen gas. Thermodynamically, lithium hydride, lithium oxide and lithium hydroxide are all stable. However, lithium hydroxides formed near the lithium hydride substrate (interface hydroxide) and near the sample/vacuum interface (surface hydroxide) are much less thermally stable than their bulk counterpart. In a dry environment, the interface/surface hydroxides slowly degenerate over many years/decades at room temperature into lithium oxide, releasing water vapor and ultimately hydrogen gas through reaction of the water vapor with the lithium hydride substrate. This outgassing can potentially cause metal hydriding and/or compatibility issues elsewhere in the device. In this chapter, the morphology and the chemistry of the corrosion layer grown on lithium hydride (and in some cases, its isotopic cousin, lithium deuteride) as a result of exposure to moisture are investigated. The hydrogen outgassing processes associated with the formation and subsequent degeneration of this corrosion layer are described. Experimental techniques to measure the hydrogen outgassing kinetics from lithium hydride and methods employing the measured kinetics to predict hydrogen outgassing as a function of time and temperature are presented. Finally, practical procedures to mitigate the problem of hydrogen outgassing from lithium hydride are discussed.

  7. Electrochemical and Optical Properties of Magnesium-Alloy Hydrides Reviewed

    Directory of Open Access Journals (Sweden)

    Thirugnasambandam G. Manivasagam

    2012-10-01

    Full Text Available As potential hydrogen storage media, magnesium based hydrides have been systematically studied in order to improve reversibility, storage capacity, kinetics and thermodynamics. The present article deals with the electrochemical and optical properties of Mg alloy hydrides. Electrochemical hydrogenation, compared to conventional gas phase hydrogen loading, provides precise control with only moderate reaction conditions. Interestingly, the alloy composition determines the crystallographic nature of the metal-hydride: a structural change is induced from rutile to fluorite at 80 at.% of Mg in Mg-TM alloy, with ensuing improved hydrogen mobility and storage capacity. So far, 6 wt.% (equivalent to 1600 mAh/g of reversibly stored hydrogen in MgyTM(1-yHx (TM: Sc, Ti has been reported. Thin film forms of these metal-hydrides reveal interesting electrochromic properties as a function of hydrogen content. Optical switching occurs during (dehydrogenation between the reflective metal and the transparent metal hydride states. The chronological sequence of the optical improvements in optically active metal hydrides starts with the rare earth systems (YHx, followed by Mg rare earth alloy hydrides (MgyGd(1-yHx and concludes with Mg transition metal hydrides (MgyTM(1-yHx. In-situ optical characterization of gradient thin films during (dehydrogenation, denoted as hydrogenography, enables the monitoring of alloy composition gradients simultaneously.

  8. Hydrogen, lithium, and lithium hydride production

    Energy Technology Data Exchange (ETDEWEB)

    Brown, Sam W.; Spencer, Larry S.; Phillips, Michael R.; Powell, G. Louis; Campbell, Peggy J.

    2017-06-20

    A method is provided for extracting hydrogen from lithium hydride. The method includes (a) heating lithium hydride to form liquid-phase lithium hydride; (b) extracting hydrogen from the liquid-phase lithium hydride, leaving residual liquid-phase lithium metal; (c) hydriding the residual liquid-phase lithium metal to form refined lithium hydride; and repeating steps (a) and (b) on the refined lithium hydride.

  9. Electrochemical hydrogen Storage Systems

    Energy Technology Data Exchange (ETDEWEB)

    Dr. Digby Macdonald

    2010-08-09

    As the global need for energy increases, scientists and engineers have found a possible solution by using hydrogen to power our world. Although hydrogen can be combusted as a fuel, it is considered an energy carrier for use in fuel cells wherein it is consumed (oxidized) without the production of greenhouse gases and produces electrical energy with high efficiency. Chemical storage of hydrogen involves release of hydrogen in a controlled manner from materials in which the hydrogen is covalently bound. Sodium borohydride and aminoborane are two materials given consideration as chemical hydrogen storage materials by the US Department of Energy. A very significant barrier to adoption of these materials as hydrogen carriers is their regeneration from 'spent fuel,' i.e., the material remaining after discharge of hydrogen. The U.S. Department of Energy (DOE) formed a Center of Excellence for Chemical Hydrogen Storage, and this work stems from that project. The DOE has identified boron hydrides as being the main compounds of interest as hydrogen storage materials. The various boron hydrides are then oxidized to release their hydrogen, thereby forming a 'spent fuel' in the form of a lower boron hydride or even a boron oxide. The ultimate goal of this project is to take the oxidized boron hydrides as the spent fuel and hydrogenate them back to their original form so they can be used again as a fuel. Thus this research is essentially a boron hydride recycling project. In this report, research directed at regeneration of sodium borohydride and aminoborane is described. For sodium borohydride, electrochemical reduction of boric acid and sodium metaborate (representing spent fuel) in alkaline, aqueous solution has been investigated. Similarly to literature reports (primarily patents), a variety of cathode materials were tried in these experiments. Additionally, approaches directed at overcoming electrostatic repulsion of borate anion from the cathode, not

  10. Electrochemical Detection of Transient Cobalt Hydride Intermediates of Electrocatalytic Hydrogen Production.

    Science.gov (United States)

    Wiedner, Eric S; Bullock, R Morris

    2016-07-06

    A large variety of molecular cobalt complexes are used as electrocatalysts for H2 production, but the key cobalt hydride intermediates are frequently difficult to detect and characterize due to their high reactivity. We report that a combination of variable scan rate cyclic voltammetry and foot-of-the-wave analysis (FOWA) can be used to detect transient Co(III)H and Co(II)H intermediates of electrocatalytic H2 production by [Co(II)(P(tBu)2N(Ph)2)(CH3CN)3](2+) and Co(II)(dmgBF2)2(CH3CN)2. In both cases, reduction of a transient catalytic intermediate occurs at a potential that coincides with the Co(II/I) couple. Each reduction displays quasireversible electron-transfer kinetics, consistent with reduction of a Co(III)H intermediate to Co(II)H, which is then protonated by acid to generate H2. A bridge-protonated Co(I) species was ruled out as a catalytic intermediate for Co(II)(dmgBF2)2(CH3CN)2 from voltammograms recorded at 1000 psi of H2. Density functional theory was used to calculate Co(III)-H and Co(II)-H bond strengths for both catalysts. Despite having very different ligands, the cobalt hydrides of both catalysts possess nearly identical heterolytic and homolytic Co-H bond strengths for the Co(III)H and Co(II)H intermediates.

  11. Effects of Nd-addition on the structural, hydrogen storage, and electrochemical properties of C14 metal hydride alloys

    Energy Technology Data Exchange (ETDEWEB)

    Wong, D.F. [BASF/Battery Materials-Ovonic, 2983 Waterview Drive, Rochester Hills, MI 48309 (United States); Department of Chemical Engineering, Wayne State University, Detroit, MI 48202 (United States); Young, K., E-mail: kwo.young@basf.com [BASF/Battery Materials-Ovonic, 2983 Waterview Drive, Rochester Hills, MI 48309 (United States); Department of Chemical Engineering, Wayne State University, Detroit, MI 48202 (United States); Nei, J.; Wang, L. [BASF/Battery Materials-Ovonic, 2983 Waterview Drive, Rochester Hills, MI 48309 (United States); Ng, K.Y.S. [Department of Chemical Engineering, Wayne State University, Detroit, MI 48202 (United States)

    2015-10-25

    Nd-addition to the AB{sub 2}-based alloy Ti{sub 12}Zr{sub 22.8−x}V{sub 10}Cr{sub 7.5}Mn{sub 8.1}Co{sub 7.0}Ni{sub 32.2}Al{sub 0.4}Nd{sub x} is studied for its effects on the structure, gaseous-phase hydrogen storage, and electrochemical properties. This study follows a series of Cu, Mo, Fe, Y, Si, and La doping studies in similar AB{sub 2}-based alloys. Limited solubility of Nd in the main Laves phase promotes the formation of secondary phases (AB and Zr{sub 7}Ni{sub 10}) to provide catalytic effects and synergies for improved capacity and high-rate dischargeability (HRD) performance. The main C14 storage phase has smaller lattice constants and cell volumes, and these effects reduce the storage capacity at higher Nd levels. Different hydrogen absorption mechanisms can occur in these multi-component, multi-phase alloys depending on the interfaces of the phases, and they have effects on the alloy properties. Higher Nd-levels improve the HRD performance despite having lower bulk diffusion and surface exchange current. Magnetic susceptibility measurements indicate large percentage of larger metallic nickel clusters are present in the surface oxide of alloys with higher Nd-content, and AC impedance studies show very low charge-transfer resistance with high catalytic capability in the alloys. The −40 °C charge-transfer resistance of 8.9 Ω g in this Nd-series of alloys is the lowest measured out of the studies investigating doped AB{sub 2}-based MH alloys for improved low-temperature characteristics. The improvement in HRD and low-temperature performance appears to be related to the proportion of the highly catalytic NdNi-phase at the surface, which must offset the increased bulk diffusion resistance in the alloy. - Graphical abstract: Schematics of hydrogen flow and corresponding PCT isotherms in funneling mode. - Highlights: • Structural and hydrogen storage properties of Nd-substituted AB{sub 2} metal hydride are reported. • Nd contributes to the lowest

  12. Hydride development for hydrogen storage

    Energy Technology Data Exchange (ETDEWEB)

    Thomas, G.J.; Guthrie, S.E.; Bauer, W.; Yang, N.Y.C. [Sandia National Lab., Livermore, CA (United States); Sandrock, G. [SunaTech, Inc., Ringwood, NJ (United States)

    1996-10-01

    The purpose of this project is to develop and demonstrate improved hydride materials for hydrogen storage. The work currently is organized into four tasks: hydride development, bed fabrication, materials support for engineering systems, and IEA Annex 12 activities. At the present time, hydride development is focused on Mg alloys. These materials generally have higher weight densities for storing hydrogen than rare earth or transition metal alloys, but suffer from high operating temperatures, slow kinetic behavior and material stability. The authors approach is to study bulk alloy additions which increase equilibrium overpressure, in combination with stable surface alloy modification and particle size control to improve kinetic properties. This work attempts to build on the considerable previous research in this area, but examines specific alloy systems in greater detail, with attention to known phase properties and structures. The authors have found that specific phases can be produced which have significantly improved hydride properties compared to previous studies.

  13. Hydrogen Storage in Metal Hydrides

    Science.gov (United States)

    1990-08-01

    Hydrogen Storage Capacity Hydride by weight (%) [1) by volume (g/ml) [2] MgH2 7.00 0.101 Mg2NiH4 3.84 0,081 Mg2CuH4 2.04 - - 27 ...Include Security Classification) Hydrogen Storage in Metal Hydrides (U) 12. PERSONAL AUTHOR(S) DelaRosa, Mark J. 13a. TYPE OF REPORT 13b. TIME...objective of this program was to develop an economical process for pr-ducing a lightweight hydrogen storage medium by the chemical vapor infiltration

  14. Hydrogen-storing hydride complexes

    Science.gov (United States)

    Srinivasan, Sesha S [Tampa, FL; Niemann, Michael U [Venice, FL; Goswami, D Yogi [Tampa, FL; Stefanakos, Elias K [Tampa, FL

    2012-04-10

    A ternary hydrogen storage system having a constant stoichiometric molar ratio of LiNH.sub.2:MgH.sub.2:LiBH.sub.4 of 2:1:1. It was found that the incorporation of MgH.sub.2 particles of approximately 10 nm to 20 nm exhibit a lower initial hydrogen release temperature of 150.degree. C. Furthermore, it is observed that the particle size of LiBNH quaternary hydride has a significant effect on the hydrogen sorption concentration with an optimum size of 28 nm. The as-synthesized hydrides exhibit two main hydrogen release temperatures, one around 160.degree. C. and the other around 300.degree. C., with the main hydrogen release temperature reduced from 310.degree. C. to 270.degree. C., while hydrogen is first reversibly released at temperatures as low as 150.degree. C. with a total hydrogen capacity of 6 wt. % to 8 wt. %. Detailed thermal, capacity, structural and microstructural properties have been demonstrated and correlated with the activation energies of these materials.

  15. Hydrogen storage in complex metal hydrides

    National Research Council Canada - National Science Library

    Bogdanovic, Borislav; Felderhoff, Michael; Streukens, Guido

    2009-01-01

    ...) are solid-state hydrogen-storage materials with high hydrogen capacities. They can be used in combination with fuel cells as a hydrogen source thus enabling longer operation times compared with classical metal hydrides...

  16. Electrochemical hydrogen storage properties of Mg100−xNix produced by hydriding combustion synthesis and mechanical milling

    Directory of Open Access Journals (Sweden)

    Delong Zhu

    2017-02-01

    Full Text Available In this work, Mg-based hydrogen storage composites with an initial 100-x: x (x=25, 32.3, 50, 66.7 of Mg:Ni molar ratio were prepared by HCS+MM and their phase compositions and electrochemical performances were investigated in detail. The results show that the composites with desirable constituents can be achieved by adjusting the molar ratio of the starting materials in the HCS process. Particularly, the HCS product of Mg67.7Ni32.3 consists of the principal phase Mg2NiH4 and minor phase Mg2NiH0.3. The dominate phase varies from Mg2NiH0.3 and MgH2 for the Mg enriched sample (x32.3. The MM modification not only brings about grain refinement of the alloys, but also leads to phase transformation of part Mg2NiH4 to Mg2NiH0.3 in the Mg67.7Ni32.3 sample. Electrochemical tests indicate that each sample can reach its maximum discharge capacity at the first cycle. Mg67.7Ni32.3 displays the highest discharge capacity as well as a superior electrochemical kinetics owing to its excellent H atom diffusion ability and lower charge-transfer resistance. The Mg67.7Ni32.3 provides the most optimized Mg/Ni atomic ratio considering the comprehensive electrochemical properties of all samples.

  17. Use of reversible hydrides for hydrogen storage

    Science.gov (United States)

    Darriet, B.; Pezat, M.; Hagenmuller, P.

    1980-01-01

    The addition of metals or alloys whose hydrides have a high dissociation pressure allows a considerable increase in the hydrogenation rate of magnesium. The influence of temperature and hydrogen pressure on the reaction rate were studied. Results concerning the hydriding of magnesium rich alloys such as Mg2Ca, La2Mg17 and CeMg12 are presented. The hydriding mechanism of La2Mg17 and CeMg12 alloys is given.

  18. Electrochemical process and production of novel complex hydrides

    Science.gov (United States)

    Zidan, Ragaiy

    2013-06-25

    A process of using an electrochemical cell to generate aluminum hydride (AlH.sub.3) is provided. The electrolytic cell uses a polar solvent to solubilize NaAlH.sub.4. The resulting electrochemical process results in the formation of AlH.sub.3. The AlH.sub.3 can be recovered and used as a source of hydrogen for the automotive industry. The resulting spent aluminum can be regenerated into NaAlH.sub.4 as part of a closed loop process of AlH.sub.3 generation.

  19. ALUMINUM HYDRIDE: A REVERSIBLE STORAGE MATERIAL FOR HYDROGEN STORAGE

    Energy Technology Data Exchange (ETDEWEB)

    Zidan, R; Christopher Fewox, C; Brenda Garcia-Diaz, B; Joshua Gray, J

    2009-01-09

    One of the challenges of implementing the hydrogen economy is finding a suitable solid H{sub 2} storage material. Aluminium (alane, AlH{sub 3}) hydride has been examined as a potential hydrogen storage material because of its high weight capacity, low discharge temperature, and volumetric density. Recycling the dehydride material has however precluded AlH{sub 3} from being implemented due to the large pressures required (>10{sup 5} bar H{sub 2} at 25 C) and the thermodynamic expense of chemical synthesis. A reversible cycle to form alane electrochemically using NaAlH{sub 4} in THF been successfully demonstrated. Alane is isolated as the triethylamine (TEA) adduct and converted to unsolvated alane by heating under vacuum. To complete the cycle, the starting alanate can be regenerated by direct hydrogenation of the dehydrided alane and the alkali hydride (NaH) This novel reversible cycle opens the door for alane to fuel the hydrogen economy.

  20. Nanostructured, complex hydride systems for hydrogen generation

    Directory of Open Access Journals (Sweden)

    Robert A. Varin

    2015-02-01

    Full Text Available Complex hydride systems for hydrogen (H2 generation for supplying fuel cells are being reviewed. In the first group, the hydride systems that are capable of generating H2 through a mechanical dehydrogenation phenomenon at the ambient temperature are discussed. There are few quite diverse systems in this group such as lithium alanate (LiAlH4 with the following additives: nanoiron (n-Fe, lithium amide (LiNH2 (a hydride/hydride system and manganese chloride MnCl2 (a hydride/halide system. Another hydride/hydride system consists of lithium amide (LiNH2 and magnesium hydride (MgH2, and finally, there is a LiBH4-FeCl2 (hydride/halide system. These hydride systems are capable of releasing from ~4 to 7 wt.% H2 at the ambient temperature during a reasonably short duration of ball milling. The second group encompasses systems that generate H2 at slightly elevated temperature (up to 100 °C. In this group lithium alanate (LiAlH4 ball milled with the nano-Fe and nano-TiN/TiC/ZrC additives is a prominent system that can relatively quickly generate up to 7 wt.% H2 at 100 °C. The other hydride is manganese borohydride (Mn(BH42 obtained by mechano-chemical activation synthesis (MCAS. In a ball milled (2LiBH4 + MnCl2 nanocomposite, Mn(BH42 co-existing with LiCl can desorb ~4.5 wt.% H2 at 100 °C within a reasonable duration of dehydrogenation. Practical application aspects of hydride systems for H2 generation/storage are also briefly discussed.

  1. Hydrogen storage in complex metal hydrides

    Directory of Open Access Journals (Sweden)

    BORISLAV BOGDANOVIĆ

    2009-02-01

    Full Text Available Complex metal hydrides such as sodium aluminohydride (NaAlH4 and sodium borohydride (NaBH4 are solid-state hydrogen-storage materials with high hydrogen capacities. They can be used in combination with fuel cells as a hydrogen source thus enabling longer operation times compared with classical metal hydrides. The most important point for a wide application of these materials is the reversibility under moderate technical conditions. At present, only NaAlH4 has favourable thermodynamic properties and can be employed as a thermally reversible means of hydrogen storage. By contrast, NaBH4 is a typical non- -reversible complex metal hydride; it reacts with water to produce hydrogen.

  2. ALUMINUM HYDRIDE: A REVERSIBLE MATERIAL FOR HYDROGEN STORAGE

    Energy Technology Data Exchange (ETDEWEB)

    Zidan, R; Christopher Fewox, C; Brenda Garcia-Diaz, B; Joshua Gray, J

    2009-01-09

    Hydrogen storage is one of the challenges to be overcome for implementing the ever sought hydrogen economy. Here we report a novel cycle to reversibly form high density hydrogen storage materials such as aluminium hydride. Aluminium hydride (AlH{sub 3}, alane) has a hydrogen storage capacity of 10.1 wt% H{sub 2}, 149 kg H{sub 2}/m{sup 3} volumetric density and can be discharged at low temperatures (< 100 C). However, alane has been precluded from use in hydrogen storage systems because of the lack of practical regeneration methods. The direct hydrogenation of aluminium to form AlH{sub 3} requires over 10{sup 5} bars of hydrogen pressure at room temperature and there are no cost effective synthetic means. Here we show an unprecedented reversible cycle to form alane electrochemically, using alkali metal alanates (e.g. NaAlH{sub 4}, LiAlH{sub 4}) in aprotic solvents. To complete the cycle, the starting alanates can be regenerated by direct hydrogenation of the dehydrided alane and the alkali hydride being the other compound formed in the electrochemical cell. The process of forming NaAlH{sub 4} from NaH and Al is well established in both solid state and solution reactions. The use of adducting Lewis bases is an essential part of this cycle, in the isolation of alane from the mixtures of the electrochemical cell. Alane is isolated as the triethylamine (TEA) adduct and converted to pure, unsolvated alane by heating under vacuum.

  3. ALUMINUM HYDRIDE: A REVERSIBLE MATERIAL FOR HYDROGEN STORAGE

    Energy Technology Data Exchange (ETDEWEB)

    Fewox, C; Ragaiy Zidan, R; Brenda Garcia-Diaz, B

    2008-12-31

    Hydrogen storage is one of the greatest challenges for implementing the ever sought hydrogen economy. Here we report a novel cycle to reversibly form high density hydrogen storage materials such as aluminium hydride. Aluminium hydride (AlH{sub 3}, alane) has a hydrogen storage capacity of 10.1 wt% H{sub 2}, 149 kg H{sub 2}/m{sup 3} volumetric density and can be discharged at low temperatures (< 100 C). However, alane has been precluded from use in hydrogen storage systems because of the lack of practical regeneration methods; the direct hydrogenation of aluminium to form AlH{sub 3} requires over 10{sup 5} bars of hydrogen pressure at room temperature and there are no cost effective synthetic means. Here we show an unprecedented reversible cycle to form alane electrochemically, using alkali alanates (e.g. NaAlH{sub 4}, LiAlH{sub 4}) in aprotic solvents. To complete the cycle, the starting alanates can be regenerated by direct hydrogenation of the dehydrided alane and the alkali hydride being the other compound formed in the electrochemical cell. The process of forming NaAlH{sub 4} from NaH and Al is well established in both solid state and solution reactions. The use of adducting Lewis bases is an essential part of this cycle, in the isolation of alane from the mixtures of the electrochemical cell. Alane is isolated as the triethylamine (TEA) adduct and converted to pure, unsolvated alane by heating under vacuum.

  4. Plasmonic hydrogen sensing with nanostructured metal hydrides.

    Science.gov (United States)

    Wadell, Carl; Syrenova, Svetlana; Langhammer, Christoph

    2014-12-23

    In this review, we discuss the evolution of localized surface plasmon resonance and surface plasmon resonance hydrogen sensors based on nanostructured metal hydrides, which has accelerated significantly during the past 5 years. We put particular focus on how, conceptually, plasmonic resonances can be used to study metal-hydrogen interactions at the nanoscale, both at the ensemble and at the single-nanoparticle level. Such efforts are motivated by a fundamental interest in understanding the role of nanosizing on metal hydride formation processes in the quest to develop efficient solid-state hydrogen storage materials with fast response times, reasonable thermodynamics, and acceptable long-term stability. Therefore, a brief introduction to the thermodynamics of metal hydride formation is also given. However, plasmonic hydrogen sensors not only are of academic interest as research tool in materials science but also are predicted to find more practical use as all-optical gas detectors in industrial and medical applications, as well as in a future hydrogen economy, where hydrogen is used as a carbon free energy carrier. Therefore, the wide range of different plasmonic hydrogen sensor designs already available is reviewed together with theoretical efforts to understand their fundamentals and optimize their performance in terms of sensitivity. In this context, we also highlight important challenges to be addressed in the future to take plasmonic hydrogen sensors from the laboratory to real applications in devices, including poisoning/deactivation of the active materials, sensor lifetime, and cross-sensitivity toward other gas species.

  5. The Current Status of Hydrogen Storage Alloy Development for Electrochemical Applications.

    Science.gov (United States)

    Young, Kwo-Hsiung; Nei, Jean

    2013-10-17

    In this review article, the fundamentals of electrochemical reactions involving metal hydrides are explained, followed by a report of recent progress in hydrogen storage alloys for electrochemical applications. The status of various alloy systems, including AB₅, AB₂, A₂B₇-type, Ti-Ni-based, Mg-Ni-based, BCC, and Zr-Ni-based metal hydride alloys, for their most important electrochemical application, the nickel metal hydride battery, is summarized. Other electrochemical applications, such as Ni-hydrogen, fuel cell, Li-ion battery, air-metal hydride, and hybrid battery systems, also have been mentioned.

  6. The Current Status of Hydrogen Storage Alloy Development for Electrochemical Applications

    Directory of Open Access Journals (Sweden)

    Kwo-hsiung Young

    2013-10-01

    Full Text Available In this review article, the fundamentals of electrochemical reactions involving metal hydrides are explained, followed by a report of recent progress in hydrogen storage alloys for electrochemical applications. The status of various alloy systems, including AB5, AB2, A2B7-type, Ti-Ni-based, Mg-Ni-based, BCC, and Zr-Ni-based metal hydride alloys, for their most important electrochemical application, the nickel metal hydride battery, is summarized. Other electrochemical applications, such as Ni-hydrogen, fuel cell, Li-ion battery, air-metal hydride, and hybrid battery systems, also have been mentioned.

  7. Application of thermal electrochemical equation to metal-hydride half-cell system

    Institute of Scientific and Technical Information of China (English)

    LIU Kai-yu; HUANG Bai-yun; ZHANG Ping-min; HE Yue-hui; ZHOU Ke-chao; SU Geng

    2006-01-01

    Application of thermal electrochemical equation to metal-hydride half-cell system was investigated, and the influence of state of charge on the thermal electrochemical performance of hydrogen storage materials was studied. The results show that both the absolute value of the molar enthalpy change and the internal resistance of evolution hydrogen reaction are less than that of absorption hydrogen reaction at the same state of charge. The molar reaction enthalpy change of absorption and evolution of hydride electrode change contrarily with the enhancement of filling degree of hydrogen in hydride electrode. The relation curve of molar reaction enthalpy change to state of charge, both absorption and evolution hydrogen reaction, is close to a constant when the state of charge is 10%-60%, and during state of charge below 10% or state of charge above 60%, the molar reaction enthalpy change varies sharply. Meanwhile, the internal resistance of electrode reaction has an ascending trend with the enhancement on filling degree of hydrogen in hydride electrode in both absorption and evolution hydrogen reaction.

  8. The Electrochemical Performance of Ml0.7Mm0.3Ni3.7Co0.7Mn0.4Al0.2 Nanocrystalline Hydrogen Storage Alloy as Metal Hydride Electrode

    Institute of Scientific and Technical Information of China (English)

    方守狮; 熊义辉; 等

    2002-01-01

    Ml0.7Mm0.3Ni3.7Co0.7Mn0.4Al0.2 nanocrystalline hydrogen storage materials are prepared by melt-spinning(MS).X-ray diffraction is used for the measurement of the nanocrystalline size.Compared to the electrode of polycrystalline alloys,the property of activation MH9metal hydride)electrode of the alloys with nanometer scale became worse and the inital discharge capacity decreased.It may be ascribed to the decrease of the total amount of rare earth metals and the increase of oxygen on the surface from the analysis of components of the alloys.After heat-treatment,the electrochemical performance of MH electrode of as-spun alloys could be improved,which could be attributed to the alleviation of the lattice strain.

  9. Hydrogen storage in the form of metal hydrides

    Science.gov (United States)

    Zwanziger, M. G.; Santana, C. C.; Santos, S. C.

    1984-01-01

    Reversible reactions between hydrogen and such materials as iron/titanium and magnesium/ nickel alloy may provide a means for storing hydrogen fuel. A demonstration model of an iron/titanium hydride storage bed is described. Hydrogen from the hydride storage bed powers a converted gasoline electric generator.

  10. Electrochemical Hydrogen Evolution

    DEFF Research Database (Denmark)

    Laursen, A.B.; Varela Gasque, Ana Sofia; Dionigi, F.

    2012-01-01

    The electrochemical hydrogen evolution reaction (HER) is growing in significance as society begins to rely more on renewable energy sources such as wind and solar power. Thus, research on designing new, inexpensive, and abundant HER catalysts is important. Here, we describe how a simple experimen...

  11. Sustainable Electrochemical Hydrogen Production

    DEFF Research Database (Denmark)

    Kibsgaard, Jakob; Jaramillo, Thomas F.; Chorkendorff, Ib

    production is through electrochemical processes coupled to renewable energy sources such as wind or solar. The hydrogen evolution reaction (HER, 2H+ + 2e− → H2) constitutes half of the water splitting reaction. To increase process efficiency, active catalysts for the HER are needed. Currently platinum...

  12. Hydrogen generation using silicon nanoparticles and their mixtures with alkali metal hydrides

    Science.gov (United States)

    Patki, Gauri Dilip

    Hydrogen is a promising energy carrier, for use in fuel cells, engines, and turbines for transportation or mobile applications. Hydrogen is desirable as an energy carrier, because its oxidation by air releases substantial energy (thermally or electrochemically) and produces only water as a product. In contrast, hydrocarbon energy carriers inevitably produce CO2, contributing to global warming. While CO2 capture may prove feasible in large stationary applications, implementing it in transportation and mobile applications is a daunting challenge. Thus a zero-emission energy carrier like hydrogen is especially needed in these cases. Use of H2 as an energy carrier also brings new challenges such as safe handling of compressed hydrogen and implementation of new transport, storage, and delivery processes and infrastructure. With current storage technologies, hydrogen's energy per volume is very low compared to other automobile fuels. High density storage of compressed hydrogen requires combinations of high pressure and/or low temperature that are not very practical. An alternative for storage is use of solid light weight hydrogenous material systems which have long durability, good adsorption properties and high activity. Substantial research has been conducted on carbon materials like activated carbon, carbon nanofibers, and carbon nanotubes due to their high theoretical hydrogen capacities. However, the theoretical values have not been achieved, and hydrogen uptake capacities in these materials are below 10 wt. %. In this thesis we investigated the use of silicon for hydrogen generation. Hydrogen generation via water oxidation of silicon had been ignored due to slow reaction kinetics. We hypothesized that the hydrogen generation rate could be improved by using high surface area silicon nanoparticles. Our laser-pyrolysis-produced nanoparticles showed surprisingly rapid hydrogen generation and high hydrogen yield, exceeding the theoretical maximum of two moles of H2 per

  13. Electrochemical Hydrogen Compressor

    Energy Technology Data Exchange (ETDEWEB)

    Lipp, Ludwig [FuelCell Energy, Inc., Torrington, CT (United States)

    2016-01-21

    Conventional compressors have not been able to meet DOE targets for hydrogen refueling stations. They suffer from high capital cost, poor reliability and pose a risk of fuel contamination from lubricant oils. This project has significantly advanced the development of solid state hydrogen compressor technology for multiple applications. The project has achieved all of its major objectives. It has demonstrated capability of Electrochemical Hydrogen Compression (EHC) technology to potentially meet the DOE targets for small compressors for refueling sites. It has quantified EHC cell performance and durability, including single stage hydrogen compression from near-atmospheric pressure to 12,800 psi and operation of EHC for more than 22,000 hours. Capital cost of EHC was reduced by 60%, enabling a path to meeting the DOE cost targets for hydrogen compression, storage and delivery ($2.00-2.15/gge by 2020).

  14. Investigation of metal hydride materials as hydrogen reservoirs for metal-hydrogen batteries

    Science.gov (United States)

    ONISCHAK

    1976-01-01

    The performance and suitability of various metal hydride materials were examined for use as possible hydrogen storage reservoirs for secondary metal-hydrogen batteries. Lanthanum pentanickel hydride appears as a probable candidate in terms of stable hydrogen supply under feasible thermal conditions. A kinetic model describing the decomposition rate data of the hydride has been developed.

  15. Nanostructured Magnesium Hydride for Reversible Hydrogen Storage

    Science.gov (United States)

    de Rango, P.; Chaise, A.; Fruchart, D.; Miraglia, S.; Marty, Ph.

    2013-05-01

    The aim of this work was to develop suitable materials to store hydrogen in a solid state. A systematic investigation of the co-milling process of magnesium hydride with a transition metal was undertaken in order to produce nanostructured and highly reactive powders. The initiating role of the transition metal was evidenced by in situ neutron diffraction experiments. High performances in terms of thermal and mechanical behavior were achieved introducing expanded graphite and compacting the mixture to form composite materials. Absorption and desorption kinetics have been measured versus temperature and H2 pressure.

  16. Evidence of stress-induced hydrogen ordering in zirconium hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Steuwer, A. [FaME38 at the ESRF-ILL, 6 rue J Horowitz, 38042 Grenoble (France); ESS Scandinavia, University of Lund, Stora Algatan 4, 22350 Lund (Sweden)], E-mail: steuwer@ill.fr; Santisteban, J.R. [Centro Atomico Bariloche, CNEA, San Carlos de Bariloche (Argentina); Preuss, M. [University of Manchester, Grosvenor Street, Manchester M1 7HS (United Kingdom); Peel, M.J.; Buslaps, T. [European Synchrotron Radiation Facility, 6 rue J Horowitz, 38042 Grenoble (France); Harada, M. [R and D Section, Chofu-Kita Plant, Kobe Special Tube Co, Shimonoseki 752-0953 (Japan)

    2009-01-15

    The formation of hydrides in zirconium alloys significantly affects their mechanical properties and is considered to play a critical role in their failure mechanisms, yet relatively little is known about the micromechanical behavior of hydrides in the bulk. This paper presents the result of in situ uniaxial mechanical tensioning experiments on hydrided zircaloy-2 and zircaloy-4 specimens using energy-dispersive synchrotron X-ray diffraction, which suggests that a stress-induced transformation of the {delta}-hydride to {gamma}-hydride via ordering of the hydrogen atoms occurs, akin to a Snoek-type relaxation. Subsequent annealing was found to reverse the ordering phenomenon.

  17. Technical and economic aspects of hydrogen storage in metal hydrides

    Science.gov (United States)

    Schmitt, R.

    1981-01-01

    The recovery of hydrogen from such metal hydrides as LiH, MgH2, TiH2, CaH2 and FeTiH compounds is studied, with the aim of evaluating the viability of the technique for the storage of hydrogen fuel. The pressure-temperature dependence of the reactions, enthalpies of formation, the kinetics of the hydrogen absorption and desorption, and the mechanical and chemical stability of the metal hydrides are taken into account in the evaluation. Economic aspects are considered. Development of portable metal hydride hydrogen storage reservoirs is also mentioned.

  18. The Effect of Hydrogen and Hydrides on the Integrity of Zirconium Alloy Components Delayed Hydride Cracking

    CERN Document Server

    Puls, Manfred P

    2012-01-01

    By drawing together the current theoretical and experimental understanding of the phenomena of delayed hydride cracking (DHC) in zirconium alloys, The Effect of Hydrogen and Hydrides on the Integrity of Zirconium Alloy Components: Delayed Hydride Cracking provides a detailed explanation focusing on the properties of hydrogen and hydrides in these alloys. Whilst the focus lies on zirconium alloys, the combination of both the empirical and mechanistic approaches creates a solid understanding that can also be applied to other hydride forming metals.   This up-to-date reference focuses on documented research surrounding DHC, including current methodologies for design and assessment of the results of periodic in-service inspections of pressure tubes in nuclear reactors. Emphasis is placed on showing that our understanding of DHC is supported by progress across a broad range of fields. These include hysteresis associated with first-order phase transformations; phase relationships in coherent crystalline metallic...

  19. Hydrogen desorption from nanostructured magnesium hydride composites

    Directory of Open Access Journals (Sweden)

    Brdarić Tanja P.

    2007-01-01

    Full Text Available The influence of 3d transition metal addition (Fe, Co and Ni on the desorption properties of magnesium hydride were studied. The ball milling of MgH2-3d metal blends was performed under Ar. Microstructural and morphological characterization were performed by XRD and SEM analysis, while the hydrogen desorption properties were investigated by DSC. The results show a strong correlation between the morphology and thermal stability of the composites. The complex desorption behavior (the existence of more than one desorption peak was correlated with the dispersion of the metal additive particles that appear to play the main role in the desorption. The desorption temperature can be reduced by more than 100 degrees if Fe is added as additive. The activation energy for H2 desorption from the MgH2-Fe composite is 120 kJ/mol, implying that diffusion controls the dehydration process.

  20. Hydrogen storage in sodium aluminum hydride.

    Energy Technology Data Exchange (ETDEWEB)

    Ozolins, Vidvuds; Herberg, J.L. (Lawrence Livermore National Laboratories, Livermore, CA); McCarty, Kevin F.; Maxwell, Robert S. (Lawrence Livermore National Laboratories, Livermore, CA); Stumpf, Roland Rudolph; Majzoub, Eric H.

    2005-11-01

    Sodium aluminum hydride, NaAlH{sub 4}, has been studied for use as a hydrogen storage material. The effect of Ti, as a few mol. % dopant in the system to increase kinetics of hydrogen sorption, is studied with respect to changes in lattice structure of the crystal. No Ti substitution is found in the crystal lattice. Electronic structure calculations indicate that the NaAlH{sub 4} and Na{sub 3}AlH{sub 6} structures are complex-ionic hydrides with Na{sup +} cations and AlH{sub 4}{sup -} and AlH{sub 6}{sup 3-} anions, respectively. Compound formation studies indicate the primary Ti-compound formed when doping the material at 33 at. % is TiAl{sub 3} , and likely Ti-Al compounds at lower doping rates. A general study of sorption kinetics of NaAlH{sub 4}, when doped with a variety of Ti-halide compounds, indicates a uniform response with the kinetics similar for all dopants. NMR multiple quantum studies of solution-doped samples indicate solvent interaction with the doped alanate. Raman spectroscopy was used to study the lattice dynamics of NaAlH{sub 4}, and illustrated the molecular ionic nature of the lattice as a separation of vibrational modes between the AlH{sub 4}{sup -} anion-modes and lattice-modes. In-situ Raman measurements indicate a stable AlH{sub 4}{sup -} anion that is stable at the melting temperature of NaAlH{sub 4}, indicating that Ti-dopants must affect the Al-H bond strength.

  1. Hydrogen, lithium, and lithium hydride production

    Science.gov (United States)

    Brown, Sam W; Spencer, Larry S; Phillips, Michael R; Powell, G. Louis; Campbell, Peggy J

    2014-03-25

    A method of producing high purity lithium metal is provided, where gaseous-phase lithium metal is extracted from lithium hydride and condensed to form solid high purity lithium metal. The high purity lithium metal may be hydrided to provide high purity lithium hydride.

  2. Effect of preparation method of metal hydride electrode on efficiency of hydrogen electrosorption process

    Energy Technology Data Exchange (ETDEWEB)

    Giza, Krystyna [Czestochowa University of Technology (Poland). Faculty of Production Engineering and Materials Technology; Drulis, Henryk [Trzebiatowski Institute of Low Temperatures and Structure Research PAS, Wroclaw (Poland)

    2016-02-15

    The preparation of negative electrodes for nickel-metal hydride batteries using LaNi{sub 4.3}Co{sub 0.4}Al{sub 0.3} alloy is presented. The constant current discharge technique is employed to determine the discharge capacity, the exchange current density and the hydrogen diffusion coefficient of the studied electrodes. The electrochemical performance of metal hydride electrode is strongly affected by preparation conditions. The results are compared and the advantages and disadvantages of preparation methods of the electrodes are also discussed.

  3. Electrochemical Hydrogen Peroxide Generator

    Science.gov (United States)

    Tennakoon, Charles L. K.; Singh, Waheguru; Anderson, Kelvin C.

    2010-01-01

    Two-electron reduction of oxygen to produce hydrogen peroxide is a much researched topic. Most of the work has been done in the production of hydrogen peroxide in basic media, in order to address the needs of the pulp and paper industry. However, peroxides under alkaline conditions show poor stabilities and are not useful in disinfection applications. There is a need to design electrocatalysts that are stable and provide good current and energy efficiencies to produce hydrogen peroxide under acidic conditions. The innovation focuses on the in situ generation of hydrogen peroxide using an electrochemical cell having a gas diffusion electrode as the cathode (electrode connected to the negative pole of the power supply) and a platinized titanium anode. The cathode and anode compartments are separated by a readily available cation-exchange membrane (Nafion 117). The anode compartment is fed with deionized water. Generation of oxygen is the anode reaction. Protons from the anode compartment are transferred across the cation-exchange membrane to the cathode compartment by electrostatic attraction towards the negatively charged electrode. The cathode compartment is fed with oxygen. Here, hydrogen peroxide is generated by the reduction of oxygen. Water may also be generated in the cathode. A small amount of water is also transported across the membrane along with hydrated protons transported across the membrane. Generally, each proton is hydrated with 3-5 molecules. The process is unique because hydrogen peroxide is formed as a high-purity aqueous solution. Since there are no hazardous chemicals or liquids used in the process, the disinfection product can be applied directly to water, before entering a water filtration unit to disinfect the incoming water and to prevent the build up of heterotrophic bacteria, for example, in carbon based filters. The competitive advantages of this process are: 1. No consumable chemicals are needed in the process. The only raw materials

  4. Mg-TM-Mm(TM=过渡金属,Mm=混合稀土)贮储氢合金的电化学性能%Electrochemical hydriding performance of Mg-TM-Mm (TM=transition metals, Mm=mischmetal) alloys for hydrogen storage

    Institute of Scientific and Technical Information of China (English)

    V. KNOTEK; D. VOJTĚCH

    2013-01-01

    Eighteen as-cast binary Mg−Ni, Mg−Mm and ternary Mg−Ni−Mm and Mg−Ni−TM (TM=transition metals (Cu, Zn, Mn and Co); Mm = mischmetal containing Ce, La, Nd and Pr) alloys were hydrided by an electrochemical process to determine the alloys with the most potential for electrochemical hydrogen storage. The alloys were hydrided in a 6 mol/L KOH solution at 80 °C for 480 min and at 100 A/m2. To assess the electrochemical hydriding performance of alloys, maximum hydrogen concentrations, hydrogen penetration depths and total mass of absorbed hydrogen in the alloys were measured by glow discharge spectrometry. In addition, the structures and phase compositions of the alloys both before and after hydriding were studied by optical and scanning electron microscopy, energy dispersive spectrometry and X-ray diffraction. It was determined that the highest total amount of hydrogen was absorbed by the Mg−25Ni−12Mm and Mg−26Ni (mass fraction,%) alloys. The maximum hydrogen concentrations in the Mg−25Ni−12Mm and Mg−26Ni alloys were 1.0% and 1.6%, respectively. The main hydriding product was the binary MgH2 hydride, and the ternary Mg2NiH4 hydride was also detected in the Mg−25Ni−12Mm alloy. The electrochemical hydriding parameters achieved are discussed in relation to the structures of alloys, alloying elements and hydriding mechanisms.%  对18种铸造态合金,包括二元合金Mg−Ni、Mg−Mm和三元合金Mg−Ni−Mm、Mg−Ni−TM(TM=过渡金属(Cu,Zn,Mn和Co);Mn=含Ce,La,Nd和Pr的混合稀土),采用电化学方法进行氢化,选取最具有潜力的电化学贮氢材料。将这些合金在80°C的6 mol/L KOH溶液中以电流密度100 A/m2氢化480 min。为了评价合金的电化学氢化性能,采用辉光放电光谱法测定氢化后合金的最大氢气浓度、氢渗透深度、总的吸氢质量。采用光学和扫描电子显微镜、能谱和X射线衍射测试分析合金的结构与相

  5. Mechanochemical synthesis of nanostructured chemical hydrides in hydrogen alloying mills

    Energy Technology Data Exchange (ETDEWEB)

    Wronski, Z. [CANMET' s Materials Technology Laboratory, Natural Resources Canada, Ottawa (Canada) and Department of Mechanical Engineering, University of Waterloo, Waterloo, Ont., Canada N2L 3G1 (Canada)]. E-mail: zwronski@nrcan.gc.ca; Varin, R.A. [Department of Mechanical Engineering, University of Waterloo, Waterloo, Ont., Canada N2L 3G1 (Canada); Chiu, C. [Department of Mechanical Engineering, University of Waterloo, Waterloo, Ont., Canada N2L 3G1 (Canada); Czujko, T. [Department of Mechanical Engineering, University of Waterloo, Waterloo, Ont., Canada N2L 3G1 (Canada); Calka, A. [Department of Materials Science and Engineering, University of Wollongong, NSW 2518 (Australia)

    2007-05-31

    Mechanical alloying of magnesium metal powders with hydrogen in specialized hydrogen ball mills can be used as a direct route for mechanochemical synthesis of emerging chemical hydrides and hydride mixtures for advanced solid-state hydrogen storage. In the 2Mg-Fe system, we have successfully synthesized the ternary complex hydride Mg{sub 2}FeH{sub 6} in a mixture with nanometric Fe particles. The mixture of complex magnesium-iron hydride and nano-iron released 3-4 wt.%H{sub 2} in a thermally programmed desorption experiment at the range 285-295 {sup o}C. Milling of the Mg-2Al powder mixture revealed a strong competition between formation of the Al(Mg) solid solution and the {beta}-MgH{sub 2} hydride. The former decomposes upon longer milling as the Mg atoms react with hydrogen to form the hydride phase, and drive the Al out of the solid solution. The mixture of magnesium dihydride and nano-aluminum released 2.1 wt.%H{sub 2} in the temperature range 329-340 {sup o}C in the differential scanning calorimetry experiment. The formation of MgH{sub 2} was suppressed in the Mg-B system; instead, a hydrogenated amorphous phase (Mg,B)H {sub x}, was formed in a mixture with nanometric MgB{sub 2}. Annealing of the hydrogen-stabilized amorphous mixture produced crystalline MgB{sub 2}.

  6. Theoretical study on hydrogenation catalysts containing a metal hydride as additional hydrogen supply

    NARCIS (Netherlands)

    Snijder, E.D.; Versteeg, G.F.; Swaaij, W.P.M. van

    1992-01-01

    A hypothetical hydrogenation catalyst consisting of porous, catalytically active particles embedded with metal hydride powder was evaluated. The metal hydride provides temporarily additional hydrogen if the mass transfer rate of the hydrogen to the internal of the particle is not sufficient. A numer

  7. Electrochemical Hydrogen Compressor

    Energy Technology Data Exchange (ETDEWEB)

    David P. Bloomfield; Brian S. MacKenzie

    2006-05-01

    The Electrochemical Hydrogen Compressor EHC was evaluated against DOE applications for compressing hydrogen at automobile filling stations, in future hydrogen pipelines and as a commercial replacement for conventional diaphragm hydrogen compressors. It was also evaluated as a modular replacement for the compressors used in petrochemical refineries. If the EHC can be made inexpensive, reliable and long lived then it can satisfy all these applications save pipelines where the requirements for platinum catalyst exceeds the annual world production. The research performed did not completely investigate Molybdenum as a hydrogen anode or cathode, it did show that photoetched 316 stainless steel is inadequate for an EHC. It also showed that: molybdenum bipolar plates, photochemical etching processes, and Gortex Teflon seals are too costly for a commercial EHC. The use of carbon paper in combination with a perforated thin metal electrode demonstrated adequate anode support strength, but is suspect in promoting galvanic corrosion. The nature of the corrosion mechanisms are not well understood, but locally high potentials within the unit cell package are probably involved. The program produced a design with an extraordinary high cell pitch, and a very low part count. This is one of the promising aspects of the redesigned EHC. The development and successful demonstration of the hydraulic cathode is also important. The problem of corrosion resistant metal bipolar plates is vital to the development of an inexpensive, commercial PEM fuel cell. Our research suggests that there is more to the corrosion process in fuel cells and electrochemical compressors than simple, steady state, galvanic stability. It is an important area for scientific investigation. The experiments and analysis conducted lead to several recommended future research directions. First, we need a better understanding of the corrosion mechanisms involved. The diagnosis of experimental cells with titration to

  8. Electrochemical hydriding and thermal dehydriding properties of nanostructured hydrogen storage MgNi26 alloy%纳米结构贮氢合金MgNi26的电化学氢化和热脱氢性能

    Institute of Scientific and Technical Information of China (English)

    V KNOTEK; O EKRT; M LHOTKA; D VOJTCH

    2016-01-01

    The MgNi26 alloy was prepared by three different methods of gravity casting (GC), mechanical alloying (MA) and rapid solidification (RS). All samples were electrochemically hydrided in a 6 mol/L KOH solution at 80 °C for 240 min. The structures and phase compositions of the alloys were studied using optical microscopy and scanning electron microscopy, energy dispersive spectrometry and X-ray diffraction. A temperature-programmed desorption technique was used to measure the absorbed hydrogen and study the dehydriding process. The content of hydrogen absorbed by the MgNi26-MA (approximately 1.3%, mass fraction) was 30 times higher than that of the MgNi26-GC. The MgNi26-RS sample absorbed only 0.1%of hydrogen. The lowest temperature for hydrogen evolution was exhibited by the MgNi26-MA. Compared with pure commercial MgH2, the decomposition temperature was reduced by more than 200 °C. The favourable phase and structural composition of the MgNi26-MA sample were the reasons for the best hydriding and dehydriding properties.%采用重力铸造(GC)、机械合金化(MA)和快速凝固(RS)3种工艺制备MgNi26合金。将所有样品在浓度为6 mol/L的KOH溶液中于80°C进行电化学氢化处理240 min。采用光学显微镜、扫描电镜、能量分散光谱及X射线衍射技术研究合金的组织和相组成。利用程序控温技术分析吸氢和脱氢过程。机械合金化法制备的MgNi26-MA合金样品所吸附的氢含量(约1.3%,质量分数)比重力铸造法制备的MgNi26-GC合金样品所吸附的氢含量高30倍。快速凝固法制备的MgNi26-RS合金样品所吸附的氢含量仅为0.1%。MgNi26-MA合金显示出最低的析氢温度。与工业纯MgH2相比,MgNi26-MA合金的分解温度至少降低了200°C。MgNi26-MA合金优异的氢化和脱氢性能归因于其有利的相组成和组织结构。

  9. Hydrogen Storage in Porous Materials and Magnesium Hydrides

    NARCIS (Netherlands)

    Grzech, A.

    2013-01-01

    In this thesis representatives of two different types of materials for potential hydrogen storage application are presented. Usage of either nanoporous materials or metal hydrides has both operational advantages and disadvantages. A main objective of this thesis is to characterize the hydrogen

  10. Hydrogen Storage in Porous Materials and Magnesium Hydrides

    NARCIS (Netherlands)

    Grzech, A.

    2013-01-01

    In this thesis representatives of two different types of materials for potential hydrogen storage application are presented. Usage of either nanoporous materials or metal hydrides has both operational advantages and disadvantages. A main objective of this thesis is to characterize the hydrogen stora

  11. Chemical Hydride Slurry for Hydrogen Production and Storage

    Energy Technology Data Exchange (ETDEWEB)

    McClaine, Andrew W

    2008-09-30

    The purpose of this project was to investigate and evaluate the attractiveness of using a magnesium chemical hydride slurry as a hydrogen storage, delivery, and production medium for automobiles. To fully evaluate the potential for magnesium hydride slurry to act as a carrier of hydrogen, potential slurry compositions, potential hydrogen release techniques, and the processes (and their costs) that will be used to recycle the byproducts back to a high hydrogen content slurry were evaluated. A 75% MgH2 slurry was demonstrated, which was just short of the 76% goal. This slurry is pumpable and storable for months at a time at room temperature and pressure conditions and it has the consistency of paint. Two techniques were demonstrated for reacting the slurry with water to release hydrogen. The first technique was a continuous mixing process that was tested for several hours at a time and demonstrated operation without external heat addition. Further work will be required to reduce this design to a reliable, robust system. The second technique was a semi-continuous process. It was demonstrated on a 2 kWh scale. This system operated continuously and reliably for hours at a time, including starts and stops. This process could be readily reduced to practice for commercial applications. The processes and costs associated with recycling the byproducts of the water/slurry reaction were also evaluated. This included recovering and recycling the oils of the slurry, reforming the magnesium hydroxide and magnesium oxide byproduct to magnesium metal, hydriding the magnesium metal with hydrogen to form magnesium hydride, and preparing the slurry. We found that the SOM process, under development by Boston University, offers the lowest cost alternative for producing and recycling the slurry. Using the H2A framework, a total cost of production, delivery, and distribution of $4.50/kg of hydrogen delivered or $4.50/gge was determined. Experiments performed at Boston

  12. Electrochemical Hydrogen Compressor

    Energy Technology Data Exchange (ETDEWEB)

    David P. Bloomfield; Brian S. MacKenzie

    2006-05-01

    The Electrochemical Hydrogen Compressor EHC was evaluated against DOE applications for compressing hydrogen at automobile filling stations, in future hydrogen pipelines and as a commercial replacement for conventional diaphragm hydrogen compressors. It was also evaluated as a modular replacement for the compressors used in petrochemical refineries. If the EHC can be made inexpensive, reliable and long lived then it can satisfy all these applications save pipelines where the requirements for platinum catalyst exceeds the annual world production. The research performed did not completely investigate Molybdenum as a hydrogen anode or cathode, it did show that photoetched 316 stainless steel is inadequate for an EHC. It also showed that: molybdenum bipolar plates, photochemical etching processes, and Gortex Teflon seals are too costly for a commercial EHC. The use of carbon paper in combination with a perforated thin metal electrode demonstrated adequate anode support strength, but is suspect in promoting galvanic corrosion. The nature of the corrosion mechanisms are not well understood, but locally high potentials within the unit cell package are probably involved. The program produced a design with an extraordinary high cell pitch, and a very low part count. This is one of the promising aspects of the redesigned EHC. The development and successful demonstration of the hydraulic cathode is also important. The problem of corrosion resistant metal bipolar plates is vital to the development of an inexpensive, commercial PEM fuel cell. Our research suggests that there is more to the corrosion process in fuel cells and electrochemical compressors than simple, steady state, galvanic stability. It is an important area for scientific investigation. The experiments and analysis conducted lead to several recommended future research directions. First, we need a better understanding of the corrosion mechanisms involved. The diagnosis of experimental cells with titration to

  13. CO2 hydrogenation on a metal hydride surface.

    Science.gov (United States)

    Kato, Shunsuke; Borgschulte, Andreas; Ferri, Davide; Bielmann, Michael; Crivello, Jean-Claude; Wiedenmann, Daniel; Parlinska-Wojtan, Magdalena; Rossbach, Peggy; Lu, Ye; Remhof, Arndt; Züttel, Andreas

    2012-04-28

    The catalytic hydrogenation of CO(2) at the surface of a metal hydride and the corresponding surface segregation were investigated. The surface processes on Mg(2)NiH(4) were analyzed by in situ X-ray photoelectron spectroscopy (XPS) combined with thermal desorption spectroscopy (TDS) and mass spectrometry (MS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS). CO(2) hydrogenation on the hydride surface during hydrogen desorption was analyzed by catalytic activity measurement with a flow reactor, a gas chromatograph (GC) and MS. We conclude that for the CO(2) methanation reaction, the dissociation of H(2) molecules at the surface is not the rate controlling step but the dissociative adsorption of CO(2) molecules on the hydride surface.

  14. Light metal hydrides and complex hydrides for hydrogen storage.

    Science.gov (United States)

    Schüth, F; Bogdanović, B; Felderhoff, M

    2004-10-21

    The availability of feasible methods for hydrogen storage is one of the key-maybe the key-requirements for the large scale application of PEM fuel cells in cars. There are in principle four different approaches, i.e. cryostorage in liquid form, high pressure storage, storage in the form of a chemical compound which is converted to hydrogen by on-board reforming, or reversible chemical storage in different kinds of storage materials. New developments in the field of chemical storage make such systems attractive compared to the other options. This review will discuss the different possibilities for chemical storage of hydrogen and the focus on the presently most advanced system with respect to storage capacity and kinetics, i.e. catalyzed alanates, especially NaAlH(4).

  15. Gas chromatographic separation of hydrogen isotopes using metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Aldridge, F.T.

    1984-05-09

    A study was made of the properties of metal hydrides which may be suitable for use in chromatographic separation of hydrogen isotopes. Sixty-five alloys were measured, with the best having a hydrogen-deuterium separation factor of 1.35 at 60/sup 0/C. Chromatographic columns using these alloys produced deuterium enrichments of up to 3.6 in a single pass, using natural abundance hydrogen as starting material. 25 references, 16 figures, 4 tables.

  16. Numerical simulation and performance test of metal hydride hydrogen storage system

    Directory of Open Access Journals (Sweden)

    Tzu-Hsiang Yen, Bin-Hao Chen, Bao-Dong Chen

    2011-05-01

    Full Text Available Metal hydride reactors are widely used in many industrial applications, such as hydrogen storage, thermal compression, heat pump, etc. According to the research requirement of metal hydride hydrogen storage, the thermal analyses have been implemented in the paper. The metal hydride reaction beds are considered as coupled cylindrical tube modules which combine the chemical absorption and desorption in metal hydride. The model is then used metal hydride LaNi5 as an example to predict the performance of metal hydride hydrogen storage devices, such as the position of hydration front and the thermal flux. Under the different boundary condition the characteristics of heat transfer and mass transfer in metal hydride have influence on the hydrogen absorption and desorption. The researches revealed that the scroll design can improve the temperature distribution in the reactor and the porous tube for directing hydrogen can increase the penetration depth of hydride reaction to decrease the hydrogen absorption time.

  17. Release of hydrogen from nanoconfined hydrides by application of microwaves

    Science.gov (United States)

    Sanz-Moral, Luis Miguel; Navarrete, Alexander; Sturm, Guido; Link, Guido; Rueda, Miriam; Stefanidis, Georgios; Martín, Ángel

    2017-06-01

    The release of hydrogen from solid hydrides by thermolysis can be improved by nanoconfinement of the hydride in a suitable micro/mesoporous support, but the slow heat transfer by conduction through the support can be a limitation. In this work, a C/SiO2 mesoporous material has been synthesized and employed as matrix for nanoconfinement of hydrides. The matrix showed high surface area and pore volume (386 m2/g and 1.41 cm3/g), which enabled the confinement of high concentrations of hydride. Furthermore, by modification of the proportion between C and SiO2, the dielectric properties of the complex could be modified, making it susceptible to microwave heating. As with this heating method the entire sample is heated simultaneously, the heat transfer resistances associated to conduction were eliminated. To demonstrate this possibility, ethane 1,2-diaminoborane (EDAB) was embedded on the C/SiO2 matrix at concentrations ranging from 11 to 31%wt using a wet impregnation method, and a device appropriate for hydrogen release from this material by application of microwaves was designed with the aid of a numerical simulation. Hydrogen liberation tests by conventional heating and microwaves were compared, showing that by microwave heating hydrogen release can be initiated and stopped in shorter times.

  18. Activity and Stability of Rare Earth-Based Hydride Alloys as Catalysts of Hydrogen Absorption-Oxidation Reactions

    Institute of Scientific and Technical Information of China (English)

    Ying Taokai(应桃开); Gao Xueping(高学平); Hu Weikang(胡伟康); Noréus Dag

    2004-01-01

    Rare earth-based AB5-type hydrogen storage alloys as catalysts of hydrogen-diffusion electrodes for hydrogen absorption and oxidation reactions in alkaline fuel cells were investigated. It is demonstrated that the meta-hydride hydrogen-diffusion electrodes could be charged by hydrogen gas and electrochemically discharged at the same time to retain a stable oxidation potential for a long period. The catalytic activities and stability are almost comparable with a Pt catalyst on the active carbon. Further improvement of performances is expected via reduction of catalyst size into nanometers.

  19. Chemical Hydride Slurry for Hydrogen Production and Storage

    Energy Technology Data Exchange (ETDEWEB)

    McClaine, Andrew W

    2008-09-30

    The purpose of this project was to investigate and evaluate the attractiveness of using a magnesium chemical hydride slurry as a hydrogen storage, delivery, and production medium for automobiles. To fully evaluate the potential for magnesium hydride slurry to act as a carrier of hydrogen, potential slurry compositions, potential hydrogen release techniques, and the processes (and their costs) that will be used to recycle the byproducts back to a high hydrogen content slurry were evaluated. A 75% MgH2 slurry was demonstrated, which was just short of the 76% goal. This slurry is pumpable and storable for months at a time at room temperature and pressure conditions and it has the consistency of paint. Two techniques were demonstrated for reacting the slurry with water to release hydrogen. The first technique was a continuous mixing process that was tested for several hours at a time and demonstrated operation without external heat addition. Further work will be required to reduce this design to a reliable, robust system. The second technique was a semi-continuous process. It was demonstrated on a 2 kWh scale. This system operated continuously and reliably for hours at a time, including starts and stops. This process could be readily reduced to practice for commercial applications. The processes and costs associated with recycling the byproducts of the water/slurry reaction were also evaluated. This included recovering and recycling the oils of the slurry, reforming the magnesium hydroxide and magnesium oxide byproduct to magnesium metal, hydriding the magnesium metal with hydrogen to form magnesium hydride, and preparing the slurry. We found that the SOM process, under development by Boston University, offers the lowest cost alternative for producing and recycling the slurry. Using the H2A framework, a total cost of production, delivery, and distribution of $4.50/kg of hydrogen delivered or $4.50/gge was determined. Experiments performed at Boston

  20. Hydrogen Desorption from Mg Hydride: An Ab Initio Study

    Directory of Open Access Journals (Sweden)

    Simone Giusepponi

    2012-07-01

    Full Text Available Hydrogen desorption from hydride matrix is still an open field of research. By means of accurate first-principle molecular dynamics (MD simulations an Mg–MgH2 interface is selected, studied and characterized. Electronic structure calculations are used to determine the equilibrium properties and the behavior of the surfaces in terms of structural deformations and total energy considerations. Furthermore, extensive ab-initio molecular dynamics simulations are performed at several temperatures to characterize the desorption process at the interface. The numerical model successfully reproduces the experimental desorption temperature for the hydride.

  1. Hydrogen storage as a hydride. Citations from the International Aerospace Abstracts data base

    Science.gov (United States)

    Zollars, G. F.

    1980-01-01

    These citations from the international literature concern the storage of hydrogen in various metal hydrides. Binary and intermetallic hydrides are considered. Specific alloys discussed are iron titanium, lanthanium nickel, magnesium copper and magnesium nickel among others.

  2. Hydrogen storage as a hydride. Citations from the International Aerospace Abstracts data base

    Science.gov (United States)

    Zollars, G. F.

    1980-01-01

    These citations from the international literature concern the storage of hydrogen in various metal hydrides. Binary and intermetallic hydrides are considered. Specific alloys discussed are iron titanium, lanthanium nickel, magnesium copper and magnesium nickel among others.

  3. Hydrogen storage and evolution catalysed by metal hydride complexes.

    Science.gov (United States)

    Fukuzumi, Shunichi; Suenobu, Tomoyoshi

    2013-01-07

    The storage and evolution of hydrogen are catalysed by appropriate metal hydride complexes. Hydrogenation of carbon dioxide by hydrogen is catalysed by a [C,N] cyclometalated organoiridium complex, [Ir(III)(Cp*)(4-(1H-pyrazol-1-yl-κN(2))benzoic acid-κC(3))(OH(2))](2)SO(4) [Ir-OH(2)](2)SO(4), under atmospheric pressure of H(2) and CO(2) in weakly basic water (pH 7.5) at room temperature. The reverse reaction, i.e., hydrogen evolution from formate, is also catalysed by [Ir-OH(2)](+) in acidic water (pH 2.8) at room temperature. Thus, interconversion between hydrogen and formic acid in water at ambient temperature and pressure has been achieved by using [Ir-OH(2)](+) as an efficient catalyst in both directions depending on pH. The Ir complex [Ir-OH(2)](+) also catalyses regioselective hydrogenation of the oxidised form of β-nicotinamide adenine dinucleotide (NAD(+)) to produce the 1,4-reduced form (NADH) under atmospheric pressure of H(2) at room temperature in weakly basic water. In weakly acidic water, the complex [Ir-OH(2)](+) also catalyses the reverse reaction, i.e., hydrogen evolution from NADH to produce NAD(+) at room temperature. Thus, interconversion between NADH (and H(+)) and NAD(+) (and H(2)) has also been achieved by using [Ir-OH(2)](+) as an efficient catalyst and by changing pH. The iridium hydride complex formed by the reduction of [Ir-OH(2)](+) by H(2) and NADH is responsible for the hydrogen evolution. Photoirradiation (λ > 330 nm) of an aqueous solution of the Ir-hydride complex produced by the reduction of [Ir-OH(2)](+) with alcohols resulted in the quantitative conversion to a unique [C,C] cyclometalated Ir-hydride complex, which can catalyse hydrogen evolution from alcohols in a basic aqueous solution (pH 11.9). The catalytic mechanisms of the hydrogen storage and evolution are discussed by focusing on the reactivity of Ir-hydride complexes.

  4. Hydrogen Storage in Nanostructured Light Metal Hydrides

    NARCIS (Netherlands)

    Singh, S.

    2009-01-01

    The global energy issues can be solved by the abundantly available hydrogen on earth. Light metals are a compact and safe medium for storing hydrogen. This makes them attractive for vehicular use. Unfortunately, hydrogen uptake and release is slow in light metals at practical temperature and pressur

  5. Hydrogen Storage in Nanostructured Light Metal Hydrides

    NARCIS (Netherlands)

    Singh, S.

    2009-01-01

    The global energy issues can be solved by the abundantly available hydrogen on earth. Light metals are a compact and safe medium for storing hydrogen. This makes them attractive for vehicular use. Unfortunately, hydrogen uptake and release is slow in light metals at practical temperature and

  6. Electrochemical Studies on LaNi(sub 5-x)Sn(sub x) Metal Hydride Alloys

    Science.gov (United States)

    Ratnakumar, B. V.; Witham, C.; Bowman, R. C., Jr.; Hightower, A.; Fultz, B.

    1996-01-01

    Electrochemical studies were performed on LaNi(sub 5-x)Sn(sub x) with 0(less than or equal to)x(less than or equal to)0.5. We measured the effect of the Sn substituent on the kinetics of charge transfer and diffusion during hydrogen absorption and desorption, and the cyclic lifetimes of LaNi(sub 5-x)Sn(sub x) electrodes in 250 mAh laboratory test cells. We report beneficial effects of making small substitutions of Sn for Ni in LaNi(sub 5) on the performance of metal hydride alloy anode in terms of cyclic lifetime, capacity and kinetics. The optimal concentration of Sn in LaNi(sub 5-x)Sn(sub x) alloys for negative electrodes in alkaline rechargable secondary cells was found to lie in the range 0.25(less than or equal to)x(less than or equal to)0.3.

  7. Modellization of Metal Hydride Canister for Hydrogen Storage

    Directory of Open Access Journals (Sweden)

    Rocio Maceiras

    2015-06-01

    Full Text Available Hydrogen shows very interesting features for its use on-board applications as fuel cell vehicles. This paper presents the modelling of a tank with a metal hydride alloy for on-board applications, which provides good performance under ambient conditions. The metal hydride contained in the tank is Ti0.98Zr0.02V0.43Fe0.09Cr0.05Mn1.5. A two-dimensional model has been performed for the refuelling process (absorption and the discharge process (desorption. For that, individual models of mass balance, energy balance, reaction kinetics and behaviour of hydrogen gas has been modelled. The model has been developed under Matlab / Simulink© environment. Finally, individual models have been integrated into a global model, and simulated under ambient conditions. With the aim to analyse the temperature influence on the state of charge and filling and emptying time, other simulations were performed at different temperatures. The obtained results allow to conclude that this alloy offers a good behaviour with the discharge process under normal ambient conditions. Keywords: Hydrogen storage; metal hydrides; fuel cell; simulation; board applications

  8. Performance study of a hydrogen powered metal hydride actuator

    Science.gov (United States)

    Mainul Hossain Bhuiya, Md; Kim, Kwang J.

    2016-04-01

    A thermally driven hydrogen powered actuator integrating metal hydride hydrogen storage reactor, which is compact, noiseless, and able to generate smooth actuation, is presented in this article. To test the plausibility of a thermally driven actuator, a conventional piston type actuator was integrated with LaNi5 based hydrogen storage system. Copper encapsulation followed by compaction of particles into pellets, were adopted to improve overall thermal conductivity of the reactor. The operation of the actuator was thoroughly investigated for an array of operating temperature ranges. Temperature swing of the hydride reactor triggering smooth and noiseless actuation over several operating temperature ranges were monitored for quantification of actuator efficiency. Overall, the actuator generated smooth and consistent strokes during repeated cycles of operation. The efficiency of the actuator was found to be as high as 13.36% for operating a temperature range of 20 °C-50 °C. Stress-strain characteristics, actuation hysteresis etc were studied experimentally. Comparison of stress-strain characteristics of the proposed actuator with traditional actuators, artificial muscles and so on was made. The study suggests that design modification and use of high pressure hydride may enhance the performance and broaden the application horizon of the proposed actuator in future.

  9. Hydrogen storage in metal hydrides and complex hydrides; Wasserstoffspeicherung in Metall- und komplexen Hydriden - Schlussbericht

    Energy Technology Data Exchange (ETDEWEB)

    Bielmann, M.; Zuettel, A.

    2007-07-01

    This final report for the Swiss Federal Office of Energy (SFOE), reports on work done in 2007 at the Swiss Federal Laboratories for Materials Science and Technology EMPA on the storage of hydrogen in metal hydrides and complex hydrides. In particular, the use of tetrahydroborates is noted. The potential of this class of materials is stressed. The structures at room-temperature were examined using neutron and X-ray diffraction methods. Thermodynamic methods helped determine the thermodynamic stability of the materials. Also, a complete energy diagram for the materials was developed. The use of silicon oxide to reduce activation energy and its catalytic effects are discussed. The challenges placed by desorption mechanisms are noted. The authors note that reversibility is basically proven.

  10. Hydrogen generation from magnesium hydride by using organic acid

    Science.gov (United States)

    Ho, Yen-Hsi

    In this paper, the hydrolysis of solid magnesium hydride has been studied with the high concentration of catalyst at the varying temperature. An organic acid (acetic acid, CH3COOH) has been chosen as the catalyst. The study has three objectives: first, using three different weights of MgH 2 react with aqueous solution of acid for the hydrogen generation experiments. Secondly, utilizing acetic acid as the catalyst accelerates hydrogen generation. Third, emphasizing the combination of the three operating conditions (the weight of MgH2, the concentration of acetic acid, and the varying temperature) influence the amount of hydrogen generation. The experiments results show acetic acid truly can increase the rate of hydrogen generation and the weight of MgH2 can affect the amount of hydrogen generation more than the varying temperature.

  11. Oxidation of Group 8 transition-Metal Hydrides and Ionic Hydrogenation of Ketones and Aldehydes

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Kjell-Tore

    1996-08-01

    Transition-metal hydrides have received considerable attention during the last decades because of their unusual reactivity and their potential as homogeneous catalysts for hydrogenation and other reactions of organic substrates. An important class of catalytic processes where transition-metal hydrides are involved is the homogeneous hydrogenation of alkenes, alkynes, ketones, aldehydes, arenes and nitro compounds. This thesis studies the oxidation of Group 8 transition-metal hydrides and the ionic hydrogenation of ketones and aldehydes.

  12. Complex hydrides for hydrogen storage - New perspectives

    DEFF Research Database (Denmark)

    Ley, Morten B.; Jepsen, Lars H.; Lee, Young-Su

    2014-01-01

    Since the 1970s, hydrogen has been considered as a possible energy carrier for the storage of renewable energy. The main focus has been on addressing the ultimate challenge: developing an environmentally friendly successor for gasoline. This very ambitious goal has not yet been fully reached...

  13. Effects of metastability on hydrogen sorption in fluorine substituted hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Pinatel, E.R.; Corno, M.; Ugliengo, P.; Baricco, M., E-mail: marcello.baricco@unito.it

    2014-12-05

    Highlights: • Fluorine substitution in simple metal hydrides has been modelled. • The stability of the MH{sub (1−x)}F{sub x} solid solutions has been discussed. • Conditions for reversibility of sorption reactions have been suggested. - Abstract: In this work ab initio calculations and Calphad modelling have been coupled to describe the effect of fluorine substitution on the thermodynamics of hydrogenation–dehydrogenation in simple hydrides (NaH, AlH{sub 3} and CaH{sub 2}). These example systems have been used to discuss the conditions required for the formation of a stable hydride–fluoride solid solution necessary to obtain a reversible hydrogenation reaction.

  14. Synthesis and Hydrogen Desorption Properties of Aluminum Hydrides.

    Science.gov (United States)

    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 (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.

  15. Heat transfer analysis of metal hydrides in metal-hydrogen secondary batteries

    Science.gov (United States)

    Onischak, M.; Dharia, D.; Gidaspow, D.

    1976-01-01

    The heat transfer between a metal-hydrogen secondary battery and a hydrogen-storing metal hydride was studied. Temperature profiles of the endothermic metal hydrides and the metal-hydrogen battery were obtained during discharging of the batteries assuming an adiabatic system. Two hydride materials were considered in two physical arrangements within the battery system. In one case the hydride is positioned in a thin annular region about the battery stack; in the other the hydride is held in a tube down the center of the stack. The results show that for a typical 20 ampere-hour battery system with lanthanum pentanickel hydride as the hydrogen reservoir the system could perform successfully.

  16. In situ electrochemical investigations of the kinetic and thermodynamic properties of nickel-metal hydride traction batteries

    Science.gov (United States)

    Yang, Xiao Guang; Liaw, Bor Yann

    Although large ampere hour nickel-metal hydride (Ni-MH) traction batteries are in the stage of being commercialized for electric and hybrid vehicle applications, little is known about their performance characteristics. By using a standard Hg/HgO reference electrode in a commercial Ni-MH battery, we were able to conduct in situ measurements to determine both kinetic and thermodynamic properties of the system, including the characteristics of individual electrodes. Using the galvanostatic intermittent titration technique (GITT), we simultaneously and effectively determined the open-circuit voltage of the battery, the equilibrium electrode potentials, and the diffusion coefficient of proton and hydrogen in the nickel and metal hydride electrode, respectively, as a function of the states of charge (SOC). Using the current-step excitation technique, we found that the internal resistance of the battery primarily comes from the metal hydride electrode, which is greater by one order of magnitude than that of the Ni electrode. The cyclic linear micro-polarization experiments, on the other hand, showed that the charge-transfer resistance of the electrochemical reaction at the metal hydride electrode is about twice larger than that of the Ni counterpart above 20% SOC. In comparison, the internal resistance is an order of magnitude smaller than those of the electrochemical charge-transfer reactions. The micro-polarization technique also allowed us to calculate the exchange current densities of the respective electrode electrochemical reactions and the associated specific exchange current densities. These in situ, simple but detailed, characterizations of the thermodynamic and kinetic properties of the Ni-MH system provided valuable information for better understanding of the battery performance.

  17. Electrochemical hydrogenation of thiophene on SPE electrodes

    Science.gov (United States)

    Huang, Haiyan; Yuan, Penghui; Yu, Ying; Chung, Keng H.

    2017-01-01

    Electrochemical reduction desulfurization is a promising technology for petroleum refining which is environmental friendly, low cost and able to achieve a high degree of automation. Electrochemical hydrogenation of thiophene was performed in a three-electrode system which SPE electrode was the working electrode. The electrochemical desulfurization was studied by cyclic voltammetry and bulk electrolysis with coulometry (BEC) techniques. The results of cyclic voltammetry showed that the electrochemical hydrogenation reduction reaction occurred at -0.4V. The BEC results showed that the currents generated from thiophene hydrogenation reactions increased with temperature. According to Arrhenius equation, activation energy of thiophene electrolysis was calculated and lower activation energy value indicated it was diffusion controlled reaction. From the products of electrolytic reactions, the mechanisms of electrochemical hydrogenation of thiophene were proposed, consisting of two pathways: openingring followed by hydrogenation, and hydrogenation followed by ring opening.

  18. Strategies for the improvement of the hydrogen storage properties of metal hydride materials.

    Science.gov (United States)

    Wu, Hui

    2008-10-24

    Metal hydrides are an important family of materials that can potentially be used for safe, efficient and reversible on-board hydrogen storage. Light-weight metal hydrides in particular have attracted intense interest due to their high hydrogen density. However, most of these hydrides have rather slow absorption kinetics, relatively high thermal stability, and/or problems with the reversibility of hydrogen absorption/desorption cycling. This paper discusses a number of different approaches for the improvement of the hydrogen storage properties of these materials, with emphasis on recent research on tuning the ionic mobility in mixed hydrides. This concept opens a promising pathway to accelerate hydrogenation kinetics, reduce the activation energy for hydrogen release, and minimize deleterious possible by-products often associated with complex hydride systems.

  19. Optical hydrogen sensors based on metal-hydrides

    Science.gov (United States)

    Slaman, M.; Westerwaal, R.; Schreuders, H.; Dam, B.

    2012-06-01

    For many hydrogen related applications it is preferred to use optical hydrogen sensors above electrical systems. Optical sensors reduce the risk of ignition by spark formation and are less sensitive to electrical interference. Currently palladium and palladium alloys are used for most hydrogen sensors since they are well known for their hydrogen dissociation and absorption properties at relatively low temperatures. The disadvantages of palladium in sensors are the low optical response upon hydrogen loading, the cross sensitivity for oxygen and carbon, the limited detection range and the formation of micro-cracks after some hydrogen absorption/desorption cycles. In contrast to Pd, we find that the use of magnesium or rear earth bases metal-hydrides in optical hydrogen sensors allow tuning of the detection levels over a broad pressure range, while maintaining a high optical response. We demonstrate a stable detection layer for detecting hydrogen below 10% of the lower explosion limit in an oxygen rich environment. This detection layer is deposited at the bare end of a glass fiber as a micro-mirror and is covered with a thin layer of palladium. The palladium layer promotes the hydrogen uptake at room temperature and acts as a hydrogen selective membrane. To protect the sensor for a long time in air a final layer of a hydrophobic fluorine based coating is applied. Such a sensor can be used for example as safety detector in automotive applications. We find that this type of fiber optic hydrogen sensor is also suitable for hydrogen detection in liquids. As example we demonstrate a sensor for detecting a broad range of concentrations in transformer oil. Such a sensor can signal a warning when sparks inside a high voltage power transformer decompose the transformer oil over a long period.

  20. Atomistic simulation of hydrogen dynamics near dislocations in vanadium hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Ogawa, Hiroshi, E-mail: h.ogawa@aist.go.jp

    2015-10-05

    Highlights: • Hydrogen–dislocation interaction was simulated by molecular dynamics method. • Different distribution of H atoms were observed at edge and screw dislocation. • Planner distribution of hydrogen may be caused by partialized edge dislocation. • Hydrogen diffusivity was reduced in both edge and screw dislocation models. • Pipe diffusion was observed for edge dislocation but not for screw dislocation. - Abstract: Kinetics of interstitial hydrogen atoms near dislocation cores were analyzed by atomistic simulation. Classical molecular dynamics method was applied to model structures of edge and screw dislocations in α-phase vanadium hydride. Simulation showed that hydrogen atoms aggregate near dislocation cores. The spatial distribution of hydrogen has a planner shape at edge dislocation due to dislocation partialization, and a cylindrical shape at screw dislocation. Simulated self-diffusion coefficients of hydrogen atoms in dislocation models were a half- to one-order lower than that of dislocation-free model. Arrhenius plot of self-diffusivity showed slightly different activation energies for edge and screw dislocations. Directional dependency of hydrogen diffusion near dislocation showed high and low diffusivity along edge and screw dislocation lines, respectively, hence so called ‘pipe diffusion’ possibly occur at edge dislocation but does not at screw dislocation.

  1. Solar conversion by concentration cells with hydrides. [Based on hydrogen pressure differential across protonic conductor

    Energy Technology Data Exchange (ETDEWEB)

    Salomon, R.E.

    1979-01-01

    The efficiency of solar energy conversion in an electrochemical concentration cell which uses a metal hydride chemisorber is evaluated. It is shown that both constant volume and constant pressure cells can achieve the Carnot efficiency in principle. (SPH)

  2. Capture of liquid hydrogen boiloff with metal hydride absorbers

    Science.gov (United States)

    Rosso, M. J.; Golben, P. M.

    1984-01-01

    A procedure which uses metal hydrides to capture some of this low pressure (,1 psig) hydrogen for subsequent reliquefaction is described. Of the five normally occurring sources of boil-off vapor the stream associated with the off-loading of liquid tankers during dewar refill was identified as the most cost effective and readily recoverable. The design, fabrication and testing of a proof-of-concept capture device, operating at a rate that is commensurate with the evolution of vapor by the target stream, is described. Liberation of the captured hydrogen gas at pressure .15 psig at normal temperatures (typical liquefier compressor suction pressure) are also demonstrated. A payback time of less than three years is projected.

  3. Metal hydride hydrogen compression: recent advances and future prospects

    Science.gov (United States)

    Yartys, Volodymyr A.; Lototskyy, Mykhaylo; Linkov, Vladimir; Grant, David; Stuart, Alastair; Eriksen, Jon; Denys, Roman; Bowman, Robert C.

    2016-04-01

    Metal hydride (MH) thermal sorption compression is one of the more important applications of the MHs. The present paper reviews recent advances in the field based on the analysis of the fundamental principles of this technology. The performances when boosting hydrogen pressure, along with two- and three-step compression units, are analyzed. The paper includes also a theoretical modelling of a two-stage compressor aimed at describing the performance of the experimentally studied systems, their optimization and design of more advanced MH compressors. Business developments in the field are reviewed for the Norwegian company HYSTORSYS AS and the South African Institute for Advanced Materials Chemistry. Finally, future prospects are outlined presenting the role of the MH compression in the overall development of the hydrogen-driven energy systems. The work is based on the analysis of the development of the technology in Europe, USA and South Africa.

  4. Improved hydrogen desorption from lithium hydrazide by alkali metal hydride

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Liang, E-mail: liangzeng@hiroshima-u.ac.jp [Institute for Advanced Materials Research, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima 739-8530 (Japan); Miyaoka, Hiroki [Institute for Sustainable Sciences and Development, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima 739-8530 (Japan); Ichikawa, Takayuki; Kojima, Yoshitsugu [Institute for Advanced Materials Research, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima 739-8530 (Japan)

    2013-12-15

    Highlights: •LiH can dramatically improve the hydrogen desorption properties of LiNHNH{sub 2}. •KH doping had positive effect in promoting the hydrogen desorption properties of LiNHNH{sub 2}–LiH mixture. •The reaction mechanism between LiNHNH{sub 2} and LiH was studied and discussed. -- Abstract: Lithium hydrazide (LiNHNH{sub 2}), which is a white solid with 8.0 mass% of theoretical hydrogen content, was synthesized from a reaction between anhydrous hydrazine and n-butyllithium in diethyl ether. The thermodynamic properties of this compound and its detailed decomposition pathways had been investigated in our previous work. However, a number of undesired gaseous products such as hydrazine (N{sub 2}H{sub 4}) and ammonia (NH{sub 3}) were generated during the thermal decomposition of LiNHNH{sub 2}. In this work, alkali metal hydride was used to suppress the impurities in the desorbed hydrogen and improved the hydrogen desorption properties. The reaction mechanism between LiNHNH{sub 2} and LiH was also studied and discussed in this paper.

  5. Hydrogen and Dihydrogen Bonds in the Reactions of Metal Hydrides.

    Science.gov (United States)

    Belkova, Natalia V; Epstein, Lina M; Filippov, Oleg A; Shubina, Elena S

    2016-08-10

    The dihydrogen bond-an interaction between a transition-metal or main-group hydride (M-H) and a protic hydrogen moiety (H-X)-is arguably the most intriguing type of hydrogen bond. It was discovered in the mid-1990s and has been intensively explored since then. Herein, we collate up-to-date experimental and computational studies of the structural, energetic, and spectroscopic parameters and natures of dihydrogen-bonded complexes of the form M-H···H-X, as such species are now known for a wide variety of hydrido compounds. Being a weak interaction, dihydrogen bonding entails the lengthening of the participating bonds as well as their polarization (repolarization) as a result of electron density redistribution. Thus, the formation of a dihydrogen bond allows for the activation of both the MH and XH bonds in one step, facilitating proton transfer and preparing these bonds for further transformations. The implications of dihydrogen bonding in different stoichiometric and catalytic reactions, such as hydrogen exchange, alcoholysis and aminolysis, hydrogen evolution, hydrogenation, and dehydrogenation, are discussed.

  6. Hydrogen Storage Engineering Center of Excellence Metal Hydride Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Motyka, T. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2014-05-31

    The Hydrogen Storage Engineering Center of Excellence (HSECoE) was established in 2009 by the U.S. Department of Energy (DOE) to advance the development of materials-based hydrogen storage systems for hydrogen-fueled light-duty vehicles. The overall objective of the HSECoE is to develop complete, integrated system concepts that utilize reversible metal hydrides, adsorbents, and chemical hydrogen storage materials through the use of advanced engineering concepts and designs that can simultaneously meet or exceed all the DOE targets. This report describes the activities and accomplishments during Phase 1 of the reversible metal hydride portion of the HSECoE, which lasted 30 months from February 2009 to August 2011. A complete list of all the HSECoE partners can be found later in this report but for the reversible metal hydride portion of the HSECoE work the major contributing organizations to this effort were the United Technology Research Center (UTRC), General Motors (GM), Pacific Northwest National Laboratory (PNNL), the National Renewable Energy Laboratory (NREL) and the Savannah River National Laboratory (SRNL). Specific individuals from these and other institutions that supported this effort and the writing of this report are included in the list of contributors and in the acknowledgement sections of this report. The efforts of the HSECoE are organized into three phases each approximately 2 years in duration. In Phase I, comprehensive system engineering analyses and assessments were made of the three classes of storage media that included development of system level transport and thermal models of alternative conceptual storage configurations to permit detailed comparisons against the DOE performance targets for light-duty vehicles. Phase 1 tasks also included identification and technical justifications for candidate storage media and configurations that should be capable of reaching or exceeding the DOE targets. Phase 2 involved bench-level testing and

  7. Kinetics of hydrogen desorption from MgH2 and AlH3 hydrides

    Science.gov (United States)

    Terent'ev, P. B.; Gerasimov, E. G.; Mushnikov, N. V.; Uimin, M. A.; Maikov, V. V.; Gaviko, V. S.; Golovatenko, V. D.

    2015-12-01

    Kinetic parameters of the process of thermal decomposition of the MgH2 hydride (obtained by the method of the mechanoactivation of magnesium in a hydrogen atmosphere) and of the commercial AlH3 hydride have been studied upon the rapid heating in the range of temperatures of 150-510°C at hydrogen pressures of 0-2 atm. The time dependences of the amount of hydrogen released by the metal hydrides at different temperatures and pressures have been determined. It has been shown that the activation energies of the hydrogen desorption are 135 kJ/mol for MgH2 and 107 kJ/mol for AlH3. The maximum rates of hydrogen desorption from the investigated metal hydrides have been established, and the temperatures and initial pressures that ensure the maximum rate and maximum volume of the hydrogen release have been determined.

  8. Computational study of sodium magnesium hydride for hydrogen storage applications

    Science.gov (United States)

    Soto Valle, Fernando Antonio

    Hydrogen offers considerable potential benefits as an energy carrier. However, safe and convenient storage of hydrogen is one of the biggest challenges to be resolved in the near future. Sodium magnesium hydride (NaMgH 3) has attracted attention as a hydrogen storage material due to its light weight and high volumetric hydrogen density of 88 kg/m3. Despite the advantages, hydrogen release in this material occurs at approximately 670 K, which is well above the operable range for on-board hydrogen storage applications. In this regard, hydrogen release may be facilitated by substitution doping of transition-metals. This dissertation describes first-principles computational methods that enable an examination of the hydrogen storage properties of NaMgH3. The novel contribution of this dissertation includes a combination of crystal, supercell, and surface slab calculations that provides new and relevant insights about the thermodynamic and kinetic properties of NaMgH3. First-principles calculations on the pristine crystal structure provide a starting reference point for the study of this material as a hydrogen storage material. To the best of our knowledge, it is reported for the first time that a 25% mol doping concentration of Ti, V, Cu, and Zn dopants reduce the reaction enthalpy of hydrogen release for NaMgH3. The largest decrease in the DeltaH(298 K) value corresponds to the Zn-doped model (67.97 kJ/(mol H2)). Based on cohesive energy calculations, it is reported that at the 6.25% mol doping concentration, Ti and Zn dopants are the only transition metals that destabilize the NaMgH3 hydride. In terms of hydrogen removal energy, it is quantified that the energy cost to remove a single H from the Ti-doped supercell model is 0.76 eV, which is lower with respect to the pristine model and other prototypical hydrogen storage materials. From the calculation of electronic properties such as density of states, electron density difference, and charge population analysis

  9. Electronic Principles of Hydrogen Incorporation and Dynamics in Metal Hydrides

    Directory of Open Access Journals (Sweden)

    Ljiljana Matović

    2012-08-01

    Full Text Available An approach to various metal hydrides based on electronic principles is presented. The effective medium theory (EMT is used to illustrate fundamental aspects of metal-hydrogen interaction and clarify the most important processes taking place during the interaction. The elaboration is extended using the numerous existing results of experiment and calculations, as well as using some new material. In particular, the absorption/desorption of H in the Mg/MgH2 system is analyzed in detail, and all relevant initial structures and processes explained. Reasons for the high stability and slow sorption in this system are noted, and possible solutions proposed. The role of the transition-metal impurities in MgH2 is briefly discussed, and some interesting phenomena, observed in complex intermetallic compounds, are mentioned. The principle mechanism governing the Li-amide/imide transformation is also discussed. Latterly, some perspectives for the metal-hydrides investigation from the electronic point of view are elucidated.

  10. ACCEPTABILITY ENVELOPE FOR METAL HYDRIDE-BASED HYDROGEN STORAGE SYSTEMS

    Energy Technology Data Exchange (ETDEWEB)

    Hardy, B.; Corgnale, C.; Tamburello, D.; Garrison, S.; Anton, D.

    2011-07-18

    The design and evaluation of media based hydrogen storage systems requires the use of detailed numerical models and experimental studies, with significant amount of time and monetary investment. Thus a scoping tool, referred to as the Acceptability Envelope, was developed to screen preliminary candidate media and storage vessel designs, identifying the range of chemical, physical and geometrical parameters for the coupled media and storage vessel system that allow it to meet performance targets. The model which underpins the analysis allows simplifying the storage system, thus resulting in one input-one output scheme, by grouping of selected quantities. Two cases have been analyzed and results are presented here. In the first application the DOE technical targets (Year 2010, Year 2015 and Ultimate) are used to determine the range of parameters required for the metal hydride media and storage vessel. In the second case the most promising metal hydrides available are compared, highlighting the potential of storage systems, utilizing them, to achieve 40% of the 2010 DOE technical target. Results show that systems based on Li-Mg media have the best potential to attain these performance targets.

  11. Fracture mechanism of TiAl intermetallics caused by hydride and atomic hydrogen

    Institute of Scientific and Technical Information of China (English)

    高克玮; 王燕斌; 林志; 乔利杰; 褚武扬

    1999-01-01

    Hydrogen embrittlement (HE) of TiAl intermetallics was studied at room temperature. The results showed that there were two forms of HE in TiAl intermetallics, i.e. hydride HE and atomic HE. Most of hydrogen in TiAl intermetallics was transformed into hydrides at room temperature. The hydride exists as (TiAl)Hx for a low hydrogen concentration while it exists in several forms for a higher hydrogen concentration. Stress intensity factor KIC decreased with increase in hydride concentration. KIC decreased further when TiAl intermetallics were charged cathodically with hydrogen in 1 mol/L H2SO4 solution. Stress intensity factor during hydrogen charging KIH was about 50% KIC. 20% of the decrease was caused by hydrides while 30% was caused by atomic hydrogen. Mechanism of HE caused hydrides was the same as any other second phase in nature. Delayed fracture caused by atomic hydrogen resulted from hydrogen induced local plastic deformation.

  12. Hydrogenation reaction characteristics and properties of its hydrides for magnetic regenerative material HoCu2

    Institute of Scientific and Technical Information of China (English)

    金滔; 吴梦茜; 黄迦乐; 汤珂; 陈立新

    2016-01-01

    The hydrogenation reaction characteristics and the properties of its hydrides for the magnetic regenerative material HoCu2 (CeCu2-type) of a cryocooler were investigated. The XRD testing reveals that the hydrides of HoCu2 were a mixture of Cu, unknown hydride I, and unknown hydride II. Based on the PCT (pressure−concentration−temperature) curves under different reaction temperatures, the relationships among reaction temperature, equilibrium pressure, and maximum hydrogen absorption capacity were analyzed and discussed. The enthalpy changeΔH and entropy changeΔS as a result of the whole hydrogenation process were also calculated from the PCT curves. The magnetization and volumetric specific heat capacity of the hydride were also measured by SQUID magnetometer and PPMS, respectively.

  13. Solid hydrides as hydrogen storage reservoirs; Hidruros solidos como acumuladores de hidrogeno

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez, A.; Sanchez, C.; Friedrichs, O.; Ares, J. R.; Leardini, F.; Bodega, J.; Fernandez, J. F.

    2010-07-01

    Metal hydrides as hydrogen storage materials are briefly reviewed in this paper. Fundamental properties of metal-hydrogen (gas) system such as Pressure-Composition-Temperature (P-C-T) characteristics are discussed on the light of the metal-hydride thermodynamics. Attention is specially paid to light metal hydrides which might have application in the car and transport sector. The pros and cons of MgH{sub 2} as a light material are outlined. Researches in course oriented to improve the behaviour of MgH{sub 2} are presented. Finally, other very promising alternative materials such as Al compounds (alanates) or borohydrides as light hydrogen accumulators are also considered. (Author)

  14. The storage of hydrogen in the form of metal hydrides: An application to thermal engines

    Science.gov (United States)

    Gales, C.; Perroud, P.

    1981-01-01

    The possibility of using LaNi56, FeTiH2, or MgH2 as metal hydride storage sytems for hydrogen fueled automobile engines is discussed. Magnesium copper and magnesium nickel hydrides studies indicate that they provide more stable storage systems than pure magnesium hydrides. Several test engines employing hydrogen fuel have been developed: a single cylinder motor originally designed for use with air gasoline mixture; a four-cylinder engine modified to run on an air hydrogen mixture; and a gas turbine.

  15. Determination of Inorganic Arsenic Species by Electrochemical Hydride Generation Atomic Absorption Spectrometry with Selective Electrochemical Reduction

    Institute of Scientific and Technical Information of China (English)

    LI Xun; WANG Zheng-Hao

    2007-01-01

    A new direct procedure for the determination of inorganic arsenic species was developed by electrochemical hydride generation atomic absorption spectrometry (EcHG-AAS) with selective electrochemical reduction. The determination of inorganic arsenic species is based on the fact that As(Ⅲ) shows significantly higher absorbance at low electrolytic currents than As(Ⅴ) in 0.3 mol·L-1 H2SO4.The electrolytic current used for the determination of As(Ⅲ) without considerable interferences of As(V) was 0.4 A, whereas the current for the determination of As(Ⅲ)and As(V) was 1.2 A. For equal concentrations of As(Ⅲ) and As(V) in a sample, the interferences of As(V) during the As(Ⅲ) determination were smaller than 5%. The absorbance for As(V) could be calculated by subtracting that for As(Ⅲ) measured at 0.4 A from the total absorbance for As(Ⅲ) and As(V) measured at 1.2 A, and then the concentration of As(V) can be obtained by its calibration curve at 1.2 A. The methodology developed provided the detection limits of 0.3 and 0.6 ng·ml-1 for As(Ⅲ) and As(V) respectively.The relative standrad deviations were of 3.5% for 20 ng·ml-1 As(Ⅲ) and 302% for 20 ng·ml-1 As(V).The method was successfully applied to determination of soluble inorganic arsenic species in Chinese medicine.

  16. Hydrogen transmission/storage with a metal hydride/organic slurry

    Energy Technology Data Exchange (ETDEWEB)

    Breault, R.W.; Rolfe, J.; McClaine, A. [Thermo Power Corp., Waltham, MA (United States)

    1998-08-01

    Thermo Power Corporation has developed a new approach for the production, transmission, and storage of hydrogen. In this approach, a chemical hydride slurry is used as the hydrogen carrier and storage media. The slurry protects the hydride from unanticipated contact with moisture in the air and makes the hydride pumpable. At the point of storage and use, a chemical hydride/water reaction is used to produce high-purity hydrogen. An essential feature of this approach is the recovery and recycle of the spent hydride at centralized processing plants, resulting in an overall low cost for hydrogen. This approach has two clear benefits: it greatly improves energy transmission and storage characteristics of hydrogen as a fuel, and it produces the hydrogen carrier efficiently and economically from a low cost carbon source. The preliminary economic analysis of the process indicates that hydrogen can be produced for $3.85 per million Btu based on a carbon cost of $1.42 per million Btu and a plant sized to serve a million cars per day. This compares to current costs of approximately $9.00 per million Btu to produce hydrogen from $3.00 per million Btu natural gas, and $25 per million Btu to produce hydrogen by electrolysis from $0.05 per Kwh electricity. The present standard for production of hydrogen from renewable energy is photovoltaic-electrolysis at $100 to $150 per million Btu.

  17. Tailoring Thermodynamics and Kinetics for Hydrogen Storage in Complex Hydrides towards Applications.

    Science.gov (United States)

    Liu, Yongfeng; Yang, Yaxiong; Gao, Mingxia; Pan, Hongge

    2016-02-01

    Solid-state hydrogen storage using various materials is expected to provide the ultimate solution for safe and efficient on-board storage. Complex hydrides have attracted increasing attention over the past two decades due to their high gravimetric and volumetric hydrogen densities. In this account, we review studies from our lab on tailoring the thermodynamics and kinetics for hydrogen storage in complex hydrides, including metal alanates, borohydrides and amides. By changing the material composition and structure, developing feasible preparation methods, doping high-performance catalysts, optimizing multifunctional additives, creating nanostructures and understanding the interaction mechanisms with hydrogen, the operating temperatures for hydrogen storage in metal amides, alanates and borohydrides are remarkably reduced. This temperature reduction is associated with enhanced reaction kinetics and improved reversibility. The examples discussed in this review are expected to provide new inspiration for the development of complex hydrides with high hydrogen capacity and appropriate thermodynamics and kinetics for hydrogen storage.

  18. In situ probing of surface hydrides on hydrogenated amorphous silicon using attenuated total reflection infrared spectroscopy

    CERN Document Server

    Kessels, W M M; Sanden, M C M; Aydil, E S

    2002-01-01

    An in situ method based on attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) is presented for detecting surface silicon hydrides on plasma deposited hydrogenated amorphous silicon (a-Si:H) films and for determining their surface concentrations. Surface silicon hydrides are desorbed by exposing the a-Si:H films to low energy ions from a low density Ar plasma and by comparing the infrared spectrum before and after this low energy ion bombardment, the absorptions by surface hydrides can sensitively be separated from absorptions by bulk hydrides incorporated into the film. An experimental comparison with other methods that utilize isotope exchange of the surface hydrogen with deuterium showed good agreement and the advantages and disadvantages of the different methods are discussed. Furthermore, the determination of the composition of the surface hydrogen bondings on the basis of the literature data on hydrogenated crystalline silicon surfaces is presented, and quantification of the h...

  19. A review of catalyst-enhanced magnesium hydride as a hydrogen storage material

    Science.gov (United States)

    Webb, C. J.

    2015-09-01

    Magnesium hydride remains an attractive hydrogen storage material due to the high hydrogen capacity and low cost of production. A high activation energy and poor kinetics at practical temperatures for the pure material have driven research into different additives to improve the sorption properties. This review details the development of catalytic additives and their effect on the activation energy, kinetics and thermodynamic properties of magnesium hydride.

  20. Comparison of C14- and C15-Predomiated AB2 Metal Hydride Alloys for Electrochemical Applications

    Directory of Open Access Journals (Sweden)

    Kwo-Hsiung Young

    2017-07-01

    Full Text Available Herein, we present a comparison of the electrochemical hydrogen-storage characteristics of two state-of-art Laves phase-based metal hydride alloys (Zr21.5Ti12.0V10.0Cr7.5Mn8.1Co8.0Ni32.2Sn0.3Al0.4 vs. Zr25.0Ti6.5V3.9Mn22.2Fe3.8Ni38.0La0.3 prepared by induction melting and hydrogen decrepitation. The relatively high contents of lighter transition metals (V and Cr in the first composition results in an average electron density below the C14/C15 threshold ( e / a ~ 6.9 and produces a C14-predominated structure, while the average electron density of the second composition is above the C14/C15 threshold and results in a C15-predominated structure. From a combination of variations in composition, main phase structure, and degree of homogeneity, the C14-predominated alloy exhibits higher storage capacities (in both the gaseous phase and electrochemical environment, a slower activation, inferior high-rate discharge, and low-temperature performances, and a better cycle stability compared to the C15-predominated alloy. The superiority in high-rate dischargeability in the C15-predominated alloy is mainly due to its larger reactive surface area. Annealing of the C15-predominated alloy eliminates the ZrNi secondary phase completely and changes the composition of the La-containing secondary phase. While the former change sacrifices the synergetic effects, and degrades the hydrogen storage performance, the latter may contribute to the unchanged surface catalytic ability, even with a reduction in total volume of metallic nickel clusters embedded in the activated surface oxide layer. In general, the C14-predominated alloy is more suitable for high-capacity and long cycle life applications, and the C15-predominated alloy can be used in areas requiring easy activation, and better high-rate and low-temperature performances.

  1. In-situ X-ray diffraction study on MlNi3.75 Co0.75 Mn0.3 Al0.2 during electrochemical hydriding-dehydriding process

    Institute of Scientific and Technical Information of China (English)

    袁志庆; 吕光烈; 顾建明; 屠小燕; 王新喜

    2004-01-01

    Phase transformations and lattice expansions of M1Ni3.75 Co0.75 Mn0.3 Al0.2 during the electrochemical hydriding-dehydriding process were investigated using in-situ X-ray diffraction. An intermediate hydride γ phase between the hydrogen solid solution a phase and fully hydrided β phase can be observed during the cycling. The formation of γ phase is related to the diffusion of hydrogen in the crystal grains. The lower the charge rate is, the higher the content of γ phase is. The phase transformations during the hydriding-dehydriding process can be described as α(→←)α+γ+β(→←)β(→←)γ+α(→←)α. The lattice expansion from a toβ is discrete, while that from γ to β is continuous. The formation of γ phase can reduce the discrete lattice expansion from a toβ by 30 %.

  2. Predicted energy densitites for nickel-hydrogen and silver-hydrogen cells embodying metallic hydrides for hydrogen storage

    Science.gov (United States)

    Easter, R. W.

    1974-01-01

    Simplified design concepts were used to estimate gravimetric and volumetric energy densities for metal hydrogen battery cells for assessing the characteristics of cells containing metal hydrides as compared to gaseous storage cells, and for comparing nickel cathode and silver cathode systems. The silver cathode was found to yield superior energy densities in all cases considered. The inclusion of hydride forming materials yields cells with very high volumetric energy densities that also retain gravimetric energy densities nearly as high as those of gaseous storage cells.

  3. Complex Hydride Compounds with Enhanced Hydrogen Storage Capacity

    Energy Technology Data Exchange (ETDEWEB)

    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

  4. Storing hydrogen in the form of light alloy hydrides

    Science.gov (United States)

    Freund, E.; Gillerm, C.

    1981-01-01

    Different hydrides are investigated to find a system with a sufficiently high storage density (at least 3%). The formation of hydrides with light alloys is examined. Reaction kinetics for hydride formation were defined and applied to the systems Mg-Al-H, Mg-Al-Cu-H, Ti-Al-H, Ti-Al-Cu-H, and Ti-Al-Ni-H. Results indicate that the addition of Al destabilizes MgH2 and TiH2 hydrides while having only a limited effect on the storage density.

  5. Complex Metal Hydrides for hydrogen storage and solid-state ion conductors

    DEFF Research Database (Denmark)

    Payandeh GharibDoust, SeyedHosein

    and electricity in batteries. However, both hydrogen and electricity must be stored in a very dense way to be useful, e.g. for mobile applications. Complex metal hydrides have high hydrogen density and have been studied during the past twenty years in hydrogen storage systems. Moreover, they have shown high ionic...... conductivities which promote their application as solid electrolytes in batteries. This dissertation presents the synthesis and characterization of a variety of complex metal hydrides and explores their hydrogen storage properties and ionic conductivity. Five halide free rare earth borohydrides RE(BH4)3, (RE...... = La, Ce, Pr, Nd, Er) have been synthesized, which pave the way for studying the polymorphic transition in these compounds, obtaining new bimetallic borohydrides and designing new reactive hydride composites with improved hydrogen storage capacities. Two novel polymorphs of Pr(BH4)3 are identified...

  6. Superhalogens as Building Blocks of Complex Hydrides for Hydrogen Storage

    CERN Document Server

    Srivastava, Ambrish Kumar

    2016-01-01

    Superhalogens are species whose electron affinity (EA) or vertical detachment energy (VDE) exceed to those of halogen. These species typically consist of a central electropositive atom with electronegative ligands. The EA or VDE of species can be further increased by using superhalogen as ligands, which are termed as hyperhalogen. Having established BH4- as a superhalogen, we have studied BH4-x(BH4)x- (x = 1 to 4) hyperhalogen anions and their Li-complexes, LiBH4-x(BH4)x using density functional theory. The VDE of these anions is larger than that of BH4-, which increases with the increase in the number of peripheral BH4 moieties (x). The hydrogen storage capacity of LiBH4-x(BH4)x complexes is higher but binding energy is smaller than that of LiBH4, a typical complex hydride. The linear correlation between dehydrogenation energy of LiBH4-x(BH4)x complexes and VDE of BH4-x(BH4)x- anions is established. These complexes are found to be thermodynamically stable against dissociation into LiBH4 and borane. This stud...

  7. Carbene-metal hydrides can be much less acidic than phosphine-metal hydrides: significance in hydrogenations.

    Science.gov (United States)

    Zhu, Ye; Fan, Yubo; Burgess, Kevin

    2010-05-05

    Acidities of iridium hydride intermediates were shown to be critical in some transformations mediated by the chiral analogues of Crabtree's catalyst, 1-3. To do this, several experiments were undertaken to investigate the acidities of hydrogenation mixtures formed using these iridium-oxazoline complexes. DFT calculations indicated that the acidity difference for Ir-H intermediates in these hydrogenations were astounding; iridium hydride from the N-heterocyclic carbene catalyst 1 was calculated to be around seven pK(a) units less acidic than those from the P-based complexes 2 and 3. Consistent with this, the carbene complex 1 was shown to be more effective for hydrogenations of acid-sensitive substrates. In deuteration experiments, less "abnormal" deuteration was observed, corresponding to fewer complications from acid-mediated alkene isomerization preceding the D(2)-addition step. Finally, simple tests with pH indicators provided visual evidence that phosphine-based catalyst precursors give significantly more acidic reaction mixtures than the corresponding N-heterocyclic carbene ones. These observations indicate carbene-for-phosphine (and similar) ligand substitutions may impact the outcome of catalytic reactions by modifying the acidities of the metal hydrides formed.

  8. Complex rare-earth aluminum hydrides: mechanochemical preparation, crystal structure and potential for hydrogen storage.

    Science.gov (United States)

    Weidenthaler, Claudia; Pommerin, André; Felderhoff, Michael; Sun, Wenhao; Wolverton, Christopher; Bogdanović, Borislav; Schüth, Ferdi

    2009-11-25

    A novel type of complex rare-earth aluminum hydride was prepared by mechanochemical preparation. The crystal structure of the REAlH(6) (with RE = La, Ce, Pr, Nd) compounds was calculated by DFT methods and confirmed by preliminary structure refinements. The trigonal crystal structure consists of isolated [AlH(6)](3-) octahedra bridged via [12] coordinated RE cations. The investigation of the rare-earth aluminum hydrides during thermolysis shows a decrease of thermal stability with increasing atomic number of the RE element. Rare-earth hydrides (REH(x)) are formed as primary dehydrogenation products; the final products are RE-aluminum alloys. The calculated decomposition enthalpies of the rare-earth aluminum hydrides are at the lower end for reversible hydrogenation under moderate conditions. Even though these materials may require somewhat higher pressures and/or lower temperatures for rehydrogenation, they are interesting examples of low-temperature metal hydrides for which reversibility might be reached.

  9. Influence of lanthanon hydride catalysts on hydrogen storage properties of sodium alanates

    Institute of Scientific and Technical Information of China (English)

    WU Zhe; CHEN Lixin; XIAO Xuezhang; FAN Xiulin; LI Shouquan; WANG Qidong

    2013-01-01

    NaAlH4 complex hydrides doped with lanthanon hydrides were prepared by hydrogenation of the ball-milled NaH/Al+xmol.% RE-H composites (RE=La,Ce; x=2,4,6) using NaHl and A1 powder as raw materials.The influence of lanthanon hydride catalysts on the hydriding and dehydriding behaviors of the as-synthesized composites were investigated.It was found that the composite doped with 2 mol.% La.H3.01 displayed the highest hydrogen absorption capacity of 4.78 wt.% and desorption capacity of 4.66wt.%,respectively.Moreover,the composite doped with 6 mol% CeH2.51 showed the best hydriding/dehydriding reaction kinetics.The proposed catalytic mechanism for reversible hydrogen storage properties of the composite was attributed to the presence of active LaH3.01 and CeH2.51 particles,which were scattering on the surface of NaH and A1 particles,acting as the catalytic active sites for hydrogen diffusion and playing an important catalytic role in the improved hydriding/dehydriding reaction.

  10. NUMERICAL ANALYSIS FOR HYDRIDING IN METAL HYDRIDE HYDROGEN STORAGE TANK%金属氢化物储氢器吸氢过程的数值分析

    Institute of Scientific and Technical Information of China (English)

    叶建华; 蒋利军; 李志念; 刘晓鹏; 王树茂

    2011-01-01

    Based on the principle of hydride adsorption, a one-dimensional mathematical model for hydriding in a cylindrical metal hydride hydrogen storage tank was established. The heat and mass transfer of metal hydride beds was computed by finite difference method. The variation in temperature and hydrogen concentration at different radial positions of the hydride layer was analyzed during the process of hydriding. The effects of supply pressure, heat convection coefficient and hydride layer radial thickness on the hydriding was studied. It is shown that hydride formation initially takes place uniformly all over the metal hydride layer, but with the process of hydriding, the hydriding rate at the core region is gradually slower than one at surface region. The increase of supply pressure and heat convection coefficient can accelerate the hydriding of the hydrogen storage tank. The effect of hydride layer radial thickness is significant on the hydriding rate, and the thinner hydride layer, the higher the hydriding rate.%基于金属氢化物吸氢基本特性,建立圆柱形金属氢化物储氢器吸氢过程的-维数学物理模型.采用有限差分法对金属氢化物床体的传热传质进行计算.分别研究金属氢化物床体各处温度和氢含量在吸氢过程中的变化以及氢气压力、对流传热系数和金属氢化物床体径向厚度对金属氢化物吸氢过程的影响.计算结果表明:初始阶段金属氢化物床均匀吸氢,但随着氢化过程的进行,其中心区域的吸氢速率逐渐低于边缘区域;增加吸氢压力、提高对流传热系数均可促进储氢器的吸氢;金属氢化物床的径向厚度对吸氢速率影响很大,金属氢化物床越薄,氢化反应的速度越快.

  11. The Electrochemical Performance of Ml0.7 Mm0.3 Ni3.7 Co0.7 Mn0.4 Al0.2 Nanocrystalline Hydrogen Storage Alloy as Metal Hydride Electrode%纳米储氢合金Ml0.7Mm0.3Ni3.7Co0.7Mn0.4Al0.2制作的储氢电极的电化学性能

    Institute of Scientific and Technical Information of China (English)

    方守狮; 熊义辉; 林根文; 张金龙; 葛建生

    2002-01-01

    Ml0.7Mm0.3Ni3.7Co0.7Mn0.4Al0.2 nanocrystalline hydrogen storage materials are prepared by melt-spinning (MS). X-ray diffraction is used for the measurement of the nanocrystalline size. Compared to the electrode of polycrystalline alloys, the property of activation MH (metal hydride) electrode of the alloys with nanometer scale became worse and the initial discharge capacity decreased.It may be ascribed to the decrease of the total amount of rare earth metals and the increase of oxygen on the surface from the analysis of components of the alloys. After heat-treatment, the electrochemical performance of MH electrode of as-spun alloys could be improved, which could be attributed to the alleviation of the lattice strain.

  12. High Density Hydrogen Storage System Demonstration Using NaAlH4 Based Complex Compound Hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Daniel A. Mosher; Xia Tang; Ronald J. Brown; Sarah Arsenault; Salvatore Saitta; Bruce L. Laube; Robert H. Dold; Donald L. Anton

    2007-07-27

    This final report describes the motivations, activities and results of the hydrogen storage independent project "High Density Hydrogen Storage System Demonstration Using NaAlH4 Based Complex Compound Hydrides" performed by the United Technologies Research Center under the Department of Energy Hydrogen Program, contract # DE-FC36-02AL67610. The objectives of the project were to identify and address the key systems technologies associated with applying complex hydride materials, particularly ones which differ from those for conventional metal hydride based storage. This involved the design, fabrication and testing of two prototype systems based on the hydrogen storage material NaAlH4. Safety testing, catalysis studies, heat exchanger optimization, reaction kinetics modeling, thermochemical finite element analysis, powder densification development and material neutralization were elements included in the effort.

  13. Alloys for hydrogen storage in nickel/hydrogen and nickel/metal hydride batteries

    Science.gov (United States)

    Anani, Anaba; Visintin, Arnaldo; Petrov, Konstantin; Srinivasan, Supramaniam; Reilly, James J.; Johnson, John R.; Schwarz, Ricardo B.; Desch, Paul B.

    1993-01-01

    Since 1990, there has been an ongoing collaboration among the authors in the three laboratories to (1) prepare alloys of the AB(sub 5) and AB(sub 2) types, using arc-melting/annealing and mechanical alloying/annealing techniques; (2) examine their physico-chemical characteristics (morphology, composition); (3) determine the hydrogen absorption/desorption behavior (pressure-composition isotherms as a function of temperature); and (4) evaluate their performance characteristics as hydride electrodes (charge/discharge, capacity retention, cycle life, high rate capability). The work carried out on representative AB(sub 5) and AB(sub 2) type modified alloys (by partial substitution or with small additives of other elements) is presented. The purpose of the modification was to optimize the thermodynamics and kinetics of the hydriding/dehydriding reactions and enhance the stabilities of the alloys for the desired battery applications. The results of our collaboration, to date, demonstrate that (1) alloys prepared by arc melting/annealing and mechanical alloying/annealing techniques exhibit similar morphology, composition and hydriding/dehydriding characteristics; (2) alloys with the appropriate small amounts of substituent or additive elements: (1) retain the single phase structure, (2) improve the hydriding/dehydriding reactions for the battery applications, and (3) enhance the stability in the battery environment; and (3) the AB(sub 2) type alloys exhibit higher energy densities than the AB(sub 5) type alloys but the state-of-the-art, commercialized batteries are predominantly manufactured using Ab(sub 5) type alloys.

  14. The impact of carbon materials on the hydrogen storage properties of light metal hydrides

    NARCIS (Netherlands)

    Adelhelm, P.A.|info:eu-repo/dai/nl/313907854; de Jongh, P.E.|info:eu-repo/dai/nl/186125372

    2011-01-01

    The safe and efficient storage of hydrogen is still one of the remaining challenges towards fuel cell powered cars. Metal hydrides are a promising class of materials as they allow the storage of large amounts of hydrogen in a small volume at room temperature and low pressures. However, usually the

  15. The impact of carbon materials on the hydrogen storage properties of light metal hydrides

    NARCIS (Netherlands)

    Adelhelm, P.A.; de Jongh, P.E.

    2011-01-01

    The safe and efficient storage of hydrogen is still one of the remaining challenges towards fuel cell powered cars. Metal hydrides are a promising class of materials as they allow the storage of large amounts of hydrogen in a small volume at room temperature and low pressures. However, usually the k

  16. Improved Electrochemical Performance of Surface-Modified Metal Hydride Electrodes

    Institute of Scientific and Technical Information of China (English)

    YANG Kai; WU Feng; CHEN Shi; ZHANG Cun-zhong

    2005-01-01

    A novel plating process was applied to the surface modification of the metal hydride (MH) electrode of the MH/Ni batteries. The electrode was plated with a thin nickel film about 0.1 μm thick by using multi-arc ion plating technique. The X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscope (SEM) were used to analyze the electrodes. Influence of the surface modification on the performance of the MH/Ni batteries was studied. It is shown that the surface modification could enhance the electrode conductivity and decrease the batteries ohimic resistance by 28.2 %. After surface modification, the discharge capacity of modification also improves the cyclic durability of the batteries. The inner pressure of the batteries with modified electrode during overcharging is much lower than that with unmodified electrode. The experimental results demonstrate that this process is an effective way for the surface modification of the electrode of MH/Ni batteries.

  17. Mechanism of negative hydrogen ion emission from heated saline hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Kawano, Hiroyuki; Serizawa, Naoshi; Takeda, Makiko; Hasegawa, Seiji [Ehime Univ., Matsuyama (Japan). Faculty of Science

    1997-02-01

    To find a clue to the mechanism of negative hydrogen ion emission from a heated sample ({approx}10 mg) of powdery saline hydride (LiH or CaH{sub 2}) deposited on a molybdenum ribbon ({approx}0.1 cm{sup 2}), both the ionic and electronic emission currents were measured as a function of sample temperature ({approx}700 - 800 K), thereby yielding {approx}10{sup -15} - 10{sup -12} A of H{sup -} after mass analysis and {approx}10{sup -7} - 10{sup -5} A of thermal electron. Thermophysical analysis of these data indicates that the desorption energy (E{sup -}) of H{sup -} and work function ({phi}) of the emitting sample surface are 5.1 {+-} 0.3 and 3.1 {+-} 0.2 eV for LiH, respectively, while E{sup -} is 7.7 {+-} 0.3 eV and {phi} is 5.0 {+-} 0.2 eV for CaH{sub 2}. Thermochemical analysis based on our simple model on the emissions indicates that the values of E{sup -} - {phi} are 2.35 and 2.31 eV for LiH and CaH{sub 2}, respectively, which are in fair agreement with the respective values (2.1 {+-} 0.3 and 2.6 {+-} 0.3 eV) determined experimentally. This agreement indicates that the emission of H{sup -} is reasonably explained by our model from the viewpoint of reaction energy. (author)

  18. Electrochemical cell comprising stable hydride-forming material

    Energy Technology Data Exchange (ETDEWEB)

    Willems, J. J. G. S. A.; van Beek, J. R. G. C. M.; Buschow, K. H. J.

    1984-12-11

    An electrochemical cell having a negative electrode comprising a compound derived from LaNi/sub 5/, in which La is optionally substituted by a plateau pressure-increasing element and in which Ni is substituted entirely or partly by a plateau pressure-reducing element, for example, Co and/or Cu, with the object of considerably reducing volume steps and hence crack formation of the intermetallic compound during charging and discharging. Moreover, the corrosion of the intermetallic compound is counteracted by adding small quantities of Al, Cr and/or Si, Which metals enhance the formation of a protecting oxide layer.

  19. Degradation Behavior of Electrochemical Performance of Sealed-Type Nickel/Metal Hydride Batteries

    Institute of Scientific and Technical Information of China (English)

    李丽; 吴锋; 杨凯

    2003-01-01

    The degradation mechanism of electrochemical performance of sealed-type nickel/metal hydride batteries was investigated. The results indicate that the degradation behavior of Ni/MH battery is not only owing to the lack of electrolyte, but also the deterioration of the active materials on the positive and negative electrodes of Ni/MH batteries. Scanning electron micrographs (SEM), X-ray diffraction (XRD) and laser granularity analyses are presented. The particle pulverization and oxidation during charge/discharge are identified as the main causes for deterioration of the negative and positive electrode in nickel/metal hydride batteries, as well as the cross-section cracking of both anode and cathode.

  20. Nanostructured hydrotreating catalysts for electrochemical hydrogen evolution.

    Science.gov (United States)

    Morales-Guio, Carlos G; Stern, Lucas-Alexandre; Hu, Xile

    2014-09-21

    Progress in catalysis is driven by society's needs. The development of new electrocatalysts to make renewable and clean fuels from abundant and easily accessible resources is among the most challenging and demanding tasks for today's scientists and engineers. The electrochemical splitting of water into hydrogen and oxygen has been known for over 200 years, but in the last decade and motivated by the perspective of solar hydrogen production, new catalysts made of earth-abundant materials have emerged. Here we present an overview of recent developments in the non-noble metal catalysts for electrochemical hydrogen evolution reaction (HER). Emphasis is given to the nanostructuring of industrially relevant hydrotreating catalysts as potential HER electrocatalysts. The new syntheses and nanostructuring approaches might pave the way for future development of highly efficient catalysts for energy conversion.

  1. Multislice simulations for in-situ HRTEM studies of nanostructured magnesium hydride at ambient hydrogen pressure.

    Science.gov (United States)

    Surrey, Alexander; Schultz, Ludwig; Rellinghaus, Bernd

    2017-01-31

    The use of transmission electron microscopy (TEM) for the structural characterization of many nanostructured hydrides, which are relevant for solid state hydrogen storage, is hindered due to a rapid decomposition of the specimen upon irradiation with the electron beam. Environmental TEM allows to stabilize the hydrides by applying a hydrogen back pressure of up to 4.5 bar in a windowed environmental cell. The feasibility of high-resolution TEM (HRTEM) investigations of light weight metals and metal hydrides in such a "nanoreactor" is studied theoretically by means of multislice HRTEM contrast simulations using Mg and its hydride phase, MgH2, as model system. Such a setup provides the general opportunity to study dehydrogenation and hydrogenation reactions at the nanoscale under technological application conditions. We analyze the dependence of both the spatial resolution and the HRTEM image contrast on parameters such as the defocus, the metal/hydride thickness, and the hydrogen pressure in order to explore the possibilities and limitations of in-situ experiments with windowed environmental cells. Such simulations may be highly valuable to pre-evaluate future experimental studies.

  2. Properties of hydrogen permeation barrier on the surface of zirconium hydride

    Institute of Scientific and Technical Information of China (English)

    CHEN Weidong; WANG Lijun; HAN Lin; CHEN Song

    2008-01-01

    A hydrogen permeation barrier was manufactured by the in situ reaction of zirconium hydride with oxygen.A reduction in the hydrogen permeation of the oxide films was detected by measuring the mass difference of the zirconium hydride samples after the dehydrogenation experiment.The reaction of zirconium hydride with oxygen occurs only under the condition that the temperature is higher than 673 K in the oxygen partial pressure of 0.1 MPa.The oxide film is composed of two layers,a permeable oxide layer and a dense oxide layer,and the main phase of the oxide film is ZrO2 with baddeleyite structure.The XPS analysis shows that O-H bonds exist in the oxide film,which are helpful for resisting hydrogen diffusion through the oxide film.

  3. Thermodynamics of various F420 coenzyme models as sources of electrons, hydride ions, hydrogen atoms and protons in acetonitrile.

    Science.gov (United States)

    Xia, Ke; Shen, Guang-Bin; Zhu, Xiao-Qing

    2015-06-14

    32 F420 coenzyme models with alkylation of the three different N atoms (N1, N3 and N10) in the core structure (XFH(-)) were designed and synthesized and the thermodynamic driving forces (defined in terms of the molar enthalpy changes or the standard redox potentials in this work) of the 32 XFH(-) releasing hydride ions, hydrogen atoms and electrons, the thermodynamic driving forces of the 32 XFH˙ releasing protons and hydrogen atoms and the thermodynamic driving forces of XF(-)˙ releasing electrons in acetonitrile were determined using titration calorimetry and electrochemical methods. The effects of the methyl group at N1, N3 and N10 and a negative charge on N1 and N10 atoms on the six thermodynamic driving forces of the F420 coenzyme models and their related reaction intermediates were examined; the results show that seating arrangements of the methyl group and the negative charge have remarkably different effects on the thermodynamic properties of the F420 coenzyme models and their related reaction intermediates. The effects of the substituents at C7 and C8 on the six thermodynamic driving forces of the F420 coenzyme models and their related reaction intermediates were also examined; the results show that the substituents at C7 and C8 have good Hammett linear free energy relationships with the six thermodynamic parameters. Meanwhile, a reasonable determination of possible reactions between members of the F420 family and NADH family in vivo was given according to a thermodynamic analysis platform constructed using the elementary step thermodynamic parameter of F420 coenzyme model 2FH(-) and NADH model MNAH releasing hydride ions in acetonitrile. The information disclosed in this work can not only fill a gap in the chemical thermodynamics of F420 coenzyme models as a class of very important organic sources of electrons, hydride ions, hydrogen atoms and protons, but also strongly promote the fast development of the chemistry and applications of F420 coenzyme.

  4. Synthesis and Characterization of Metal Hydride/Carbon Aerogel Composites for Hydrogen Storage

    Directory of Open Access Journals (Sweden)

    Kuen-Song Lin

    2012-01-01

    Full Text Available Two materials currently of interest for onboard lightweight hydrogen storage applications are sodium aluminum hydride (NaAlH4, a complex metal hydride, and carbon aerogels (CAs, a light porous material connected by several spherical nanoparticles. The objectives of the present work have been to investigate the synthesis, characterization, and hydrogenation behavior of Pd-, Ti- or Fe-doped CAs, NaAlH4, and MgH2 nanocomposites. The diameters of Pd nanoparticles onto CA’s surface and BET surface area of CAs were 3–10 nm and 700–900 m2g−1, respectively. The H2 storage capacity of metal hydrides has been studied using high-pressure TGA microbalance and they were 4.0, 2.7, 2.1, and 1.2 wt% for MgH2-FeTi-CAs, MgH2-FeTi, CAs-Pd, and 8 mol% Ti-doped NaAlH4, respectively, at room temperature. Carbon aerogels with higher surface area and mesoporous structures facilitated hydrogen diffusion and adsorption, which accounted for its extraordinary hydrogen storage phenomenon. The hydrogen adsorption abilities of CAs notably increased after inclusion of metal hydrides by the “hydrogen spillover” mechanisms.

  5. Boron-nitrogen based hydrides and reactive composites for hydrogen storage

    DEFF Research Database (Denmark)

    Jepsen, Lars H.; Ley, Morten B.; Lee, Young-Su;

    2014-01-01

    Hydrogen forms chemical compounds with most other elements and forms a variety of different chemical bonds. This fascinating chemistry of hydrogen has continuously provided new materials and composites with new prospects for rational design and the tailoring of properties. This review highlights ...... a range of new boron and nitrogen based hydrides and illustrates how hydrogen release and uptake properties can be improved. © 2014 Elsevier Ltd....

  6. High Density Hydrogen Storage in Metal Hydride Composites with Air Cooling

    OpenAIRE

    Dieterich, Mila; Bürger, Inga; Linder, Marc

    2015-01-01

    INTRODUCTION In order to combine fluctuating renewable energy sources with the actual demand of electrical energy, storages are essential. The surplus energy can be stored as hydrogen to be used either for mobile use, chemical synthesis or reconversion when needed. One possibility to store the hydrogen gas at high volumetric densities, moderate temperatures and low pressures is based on a chemical reaction with metal hydrides. Such storages must be able to absorb and desorb the hydrogen qu...

  7. Numerical simulation of hydrogen desorption from high-density metal hydride hydrogen storage vessels

    Science.gov (United States)

    Sang-Kun, O.; Yi, Kyung-Woo; Cho, Sung-Wook

    2017-07-01

    Metal hydride (MH) alloys are a promising type of material in hydrogen storage applications, allowing for low-pressure, high-density storage. However, while many studies are being performed on enhancing the hydrogen storage properties of such alloys, there has been little research on large-scale storage vessels which make use of the alloys. In particular, large-scale, high-density storage devices must make allowances for the temperature variations caused by the heat of reaction between hydrogen and MH alloys, which may impact the storage characteristics. In this study, we propose a numerical model for the design and evaluation of hydrogen storage devices using MH alloys. Hydrogen desorption reaction behavior for an alloy is observed in terms of temperature and reaction rate. This behavioral correlation is used as the basis for a comprehensive simulation model of the alloy system. Calculated results are found to be in good agreement with experimentally measured data, indicating that the model may be applied to multiple system geometries, scales, and alloy compositions.

  8. Compensation Effect in the Hydrogenation/Dehydrogenation Kinetics of Metal Hydrides

    DEFF Research Database (Denmark)

    Andreasen, A.; Vegge, T.; Pedersen, Allan Schrøder

    2005-01-01

    The possible existence of a compensation effect, i.e. concurrent changes in activation energy and prefactor, is investigated for the hydrogenation and dehydrogenation kinetics of metal hydrides, by analyzing a series of reported kinetic studies on Mg and LaNi5 based hydrides. For these systems, we...... find a clear linear relation between apparent prefactors and apparent activation energies, as obtained from an Arrhenius analysis, indicating the existence of a compensation effect. Large changes in apparent activation energies in the case of Mg based hydrides are rationalized in terms of a dependency...... analysis rather than a physical phenomenon. In the case of LaNi5 based hydrides, observed scatter in reported apparent activation energies is less pronounced supporting the general experience that LaNi5 is less sensitive toward surface contamination....

  9. Electrochemical storage of hydrogen on carbon electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Jurewicz, K.; Frackowiak, E. [ICTE, Poznan University of Technology (Poland); Gautier, S.; Beguin, F. [CRMD, CNRS Universite, 45 - Orleans (France)

    2000-07-01

    Amount of hydrogen reversibly stored on an activated carbon electrode using electro-decomposition of 6 mol.l{sup -1} KOH aqueous solution has been investigated and compared data obtained under a high pressure of dihydrogen (70 bars) at 273 K. In the electrochemical method, 1.5 wt% of hydrogen was released from carbon during the oxidation process, with a well-defined plateau at ca. - 0.5 V vs Hg/HgO. Relatively smaller values were obtained for the sorption ability under a high pressure of gas. This means that the formation of nascent hydrogen during water reduction favours its easy penetration in the carbon nano-structure, even at ambient pressure and temperature. Our results show that not only carbon nano-tubes should be considered for hydrogen reservoir and that low cost materials such as activated carbons could be convenient in appropriate conditions.

  10. Catalyzed light hydride nanomaterials embedded in a micro-channels hydrogen storage container.

    Science.gov (United States)

    Dehouche, Zahir; Peretti, Hernán A; Yoo, Yeong; Belkacemi, Khaled; Goyette, Jacques

    2009-01-01

    Activated alloys synthesized by arc-melting were examined as catalysts for improving the hydrogen sorption characteristics of nanostructured magnesium hydride, proposed as a reversible hydrogen storage material. The MgH(2)-catalyst absorbing materials were prepared by ball milling of pure MgH(2) with hydrided Zr(47)Ni(53), Zr(9)Ni(11), and other alloys investigated. The nanostructured MgH(2)-intermetallic systems were tested at 250 degrees C and catalyst addition of eutectoid Zr(47)Ni(53) resulted in the fastest desorption time and highest initial desorption rate. The catalyzed Mg-hydride with activated Zr(9)Ni(11) and Zr(7)Ni(10) phases showed fast desorption kinetics. Moreover, the results demonstrated that the composition of dispersed Zr(x)Ni(y)catalysts has a strong influence on the amount of accumulated hydrogen and desorption rate of Mg-nanocomposite. Part two covers advanced micro-channels hydrogen storage module design based on the results of semi-empirical computer simulations of heat and mass transfers in the container. The micro-channels reservoir concept offers many advantages over the conventional metal hydride hydrogen storage system. It is a micro-structured system that can pack a lot of power into a small space and dissipate effectively the heat of the sorption reactions. This review summarizes recent patents related to CNTS.

  11. Calibration of Thermal Desorption System (TDS) Response to Hydrogen for Analysis of Titanium Subhydride and Titanium Hydride

    Energy Technology Data Exchange (ETDEWEB)

    Mills, Bernice E. [Sandia National Lab. (SNL-CA), Livermore, CA (United States)

    2013-07-01

    The equipment and method for and results of calibration of the Sandia/CA TDS system for hydrogen quantification is presented. This technique for calibration can be used to quantify the hydrogen content titanium subhydride, titanium hydride, and any other hydrogen-containing material that desorbs its hydrogen in the form of molecular hydrogen below 1450°C.

  12. Hydrogen adsorption on palladium and palladium hydride at 1 bar

    DEFF Research Database (Denmark)

    Johansson, Martin; Skulason, Egill; Nielsen, Gunver

    2010-01-01

    The dissociative sticking probability for H-2 on Pd films supported on sputtered Highly Ordered Pyrolytic Graphite (HOPG) has been derived from measurements of the rate of the H-D exchange reaction at 1 bar. The sticking probability for H-2, S. is higher on Pd hydride than on Pd (a factor of 1...

  13. Determination of thermodynamic affinities of various polar olefins as hydride, hydrogen atom, and electron acceptors in acetonitrile.

    Science.gov (United States)

    Cao, Ying; Zhang, Song-Chen; Zhang, Min; Shen, Guang-Bin; Zhu, Xiao-Qing

    2013-07-19

    A series of 69 polar olefins with various typical structures (X) were synthesized and the thermodynamic affinities (defined in terms of the molar enthalpy changes or the standard redox potentials in this work) of the polar olefins obtaining hydride anions, hydrogen atoms, and electrons, the thermodynamic affinities of the radical anions of the polar olefins (X(•-)) obtaining protons and hydrogen atoms, and the thermodynamic affinities of the hydrogen adducts of the polar olefins (XH(•)) obtaining electrons in acetonitrile were determined using titration calorimetry and electrochemical methods. The pure C═C π-bond heterolytic and homolytic dissociation energies of the polar olefins (X) in acetonitrile and the pure C═C π-bond homolytic dissociation energies of the radical anions of the polar olefins (X(•-)) in acetonitrile were estimated. The remote substituent effects on the six thermodynamic affinities of the polar olefins and their related reaction intermediates were examined using the Hammett linear free-energy relationships; the results show that the Hammett linear free-energy relationships all hold in the six chemical and electrochemical processes. The information disclosed in this work could not only supply a gap of the chemical thermodynamics of olefins as one class of very important organic unsaturated compounds but also strongly promote the fast development of the chemistry and applications of olefins.

  14. Advanced chemical hydride-based hydrogen generation/storage system for fuel cell vehicles

    Energy Technology Data Exchange (ETDEWEB)

    Breault, R.W.; Rolfe, J. [Thermo Power Corp., Waltham, MA (United States)

    1998-08-01

    Because of the inherent advantages of high efficiency, environmental acceptability, and high modularity, fuel cells are potentially attractive power supplies. Worldwide concerns over clean environments have revitalized research efforts on developing fuel cell vehicles (FCV). As a result of intensive research efforts, most of the subsystem technology for FCV`s are currently well established. These include: high power density PEM fuel cells, control systems, thermal management technology, and secondary power sources for hybrid operation. For mobile applications, however, supply of hydrogen or fuel for fuel cell operation poses a significant logistic problem. To supply high purity hydrogen for FCV operation, Thermo Power`s Advanced Technology Group is developing an advanced hydrogen storage technology. In this approach, a metal hydride/organic slurry is used as the hydrogen carrier and storage media. At the point of use, high purity hydrogen will be produced by reacting the metal hydride/organic slurry with water. In addition, Thermo Power has conceived the paths for recovery and regeneration of the spent hydride (practically metal hydroxide). The fluid-like nature of the spent hydride/organic slurry will provide a unique opportunity for pumping, transporting, and storing these materials. The final product of the program will be a user-friendly and relatively high energy storage density hydrogen supply system for fuel cell operation. In addition, the spent hydride can relatively easily be collected at the pumping station and regenerated utilizing renewable sources, such as biomass, natural, or coal, at the central processing plants. Therefore, the entire process will be economically favorable and environmentally friendly.

  15. Enhancement of Hydrogen Storage Behavior of Complex Hydrides via Bimetallic Nanocatalysts Doping

    Directory of Open Access Journals (Sweden)

    Prakash C. Sharma

    2012-10-01

    Full Text Available Pristine complex quaternary hydride (LiBH4/2LiNH2 and its destabilized counterpart (LiBH4/2LiNH2/nanoMgH2 have recently shown promising reversible hydrogen storage capacity under moderate operating conditions. The destabilization of complex hydride via nanocrystalline MgH2 apparently lowers the thermodynamic heat values and thus enhances the reversible hydrogen storage behavior at moderate temperatures. However, the kinetics of these materials is rather low and needs to be improved for on-board vehicular applications. Nanocatalyst additives such as nano Ni, nano Fe, nano Co, nano Mn and nano Cu at low concentrations on the complex hydride host structures have demonstrated a reduction in the decomposition temperature and overall increase in the hydrogen desorption reaction rates. Bi-metallic nanocatalysts such as the combination of nano Fe and nano Ni have shown further pronounced kinetics enhancement in comparison to their individual counterparts. Additionally, the vital advantage of using bi-metallic nanocatalysts is to enable the synergistic effects and characteristics of the two transitional nanometal species on the host hydride matrix for the optimized hydrogen storage behavior.

  16. Investigation of the hydrogen neutrals in a discharge source used for production of metal hydrides

    Science.gov (United States)

    Bozhinova, I.; Iordanova, S.; Pashov, A.

    2016-03-01

    The paper discusses the possible mechanisms for production of metal hydrides (MH) in a DC discharge source. The results of different experiments suggest that the molecules are sputtered directly from the surface of the cathode, where they are formed after adsorption of atomic hydrogen. This hypothesis allows one to understand the operation of the source studied and to optimize its working conditions.

  17. Hydriding and microstructure nanocrystallization of ZK60 Mg alloy by reaction milling in hydrogen

    Institute of Scientific and Technical Information of China (English)

    YUAN Yuan; WANG Heng; HU Lian-xi; SUN Hong-fei; FANG Wen-bin

    2009-01-01

    The hydriding of as-cast Mg-5.5%Zn-0.6%Zr (ZK60 Mg) (mass fraction) alloy was achieved by room-temperature reaction milling in hydrogen, with the mechanical energy serving as the driving force for the process. The hydriding progress during milling was examined by hydrogen absorption measurement, and the microstructure change was characterized by X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), respectively. The results show that, by room-temperature reaction milling in hydrogen, the as-cast ZK60 Mg alloy can be fully hydrided to form a nanocrystalline MgH2 single-phase microstructure. In particular, the average grain size of the MgH2 phase obtained by room-temperature reaction milling in hydrogen for 16.2 h is about 8-10 nm, and the average particle size of the as-milled hydrided powders is 2-3 μm.

  18. Cooldown-induced hydride reorientation of hydrogen-charged zirconium alloy cladding tubes

    Science.gov (United States)

    Won, Ju-Jin; Min, Su-Jeong; Kim, Kyu-Tae

    2015-01-01

    Radial hydride precipitation behaviors of Zr-Nb alloy cladding tubes were investigated using 250 and 500 ppm hydrogen-charged Zr-Nb alloy cladding tubes, cooldown processes from 400 to 300, 200°C and room temperature with five kinds of cooling rates of 0.3, 2.0, 4.0, 7.0 15.0 °C/min under a tensile hoop stress of 150 MPa, which can simulate various cooldown processes during an interim dry storage of PWR nuclear fuel. The slower cooling rate and the lower terminal cooldown temperature generated the more hydrides precipitated during the cooldown as well as the larger fraction and the longer length of radial hydrides. These phenomena can be explained by the difference in the terminal solid solubility of hydrogen for dissolution and precipitation occurring during the heatup and cooldown processes and the cooling rate-dependent hydride nucleation and growth rates. In addition, a drastic decrease in ultimate tensile strength and plastic strain of the tensile tested specimens experiencing the cool-down processes appear to be correlated with the amount of the radial hydrides precipitated during the cooldown.

  19. Hydrogen quantum effects in hydride LaNi(5)H(7).

    Science.gov (United States)

    Kaneko, Tomoaki; Tezuka, Akinori; Ogawa, Hiroshi; Ikeshoji, Tamio

    2011-09-15

    Energy eigenvalues and wave functions of hydrogen atoms in hydride LaNi(5)H(7) are calculated. First-principles electronic structure calculations are employed to obtain the three-dimensional potential energy structure of each hydrogen site. These quantum effects are not negligibly small in evaluation of enthalpy of formation, an important property of hydrogen storage. Including the temperature effect from hydrogen gas, experimental values are well reproduced. The excitation probability of inelastic neutron scattering is also calculated using the wave functions obtained.

  20. Metal hydrides as electrode/catalyst materials for oxygen evolution/reduction in electrochemical devices

    Science.gov (United States)

    Bugga, Ratnakumar V. (Inventor); Halpert, Gerald (Inventor); Fultz, Brent (Inventor); Witham, Charles K. (Inventor); Bowman, Robert C. (Inventor); Hightower, Adrian (Inventor)

    1997-01-01

    An at least ternary metal alloy of the formula, AB.sub.(5-Y)X(.sub.y), is claimed. In this formula, A is selected from the rare earth elements, B is selected from the elements of groups 8, 9, and 10 of the periodic table of the elements, and X includes at least one of the following: antimony, arsenic, and bismuth. Ternary or higher-order substitutions, to the base AB.sub.5 alloys, that form strong kinetic interactions with the predominant metals in the base metal hydride are used to form metal alloys with high structural integrity after multiple cycles of hydrogen sorption.

  1. A REVIEW: THE EFFECT OF OPERATING CONDITIONS AND THERMAL MANAGEMENT ON THE PERFORMANCES OF METAL HYDRIDE HYDROGEN STORAGE TANK

    Directory of Open Access Journals (Sweden)

    Taurista Perdana Syawitri

    2016-12-01

    Full Text Available For safety and operability concerns, the use of metal hydrides to store hydrogen appears to be particularly promising option for alternative energy at present. However, the process of adding, removing and distributing heat during the hydrogen charging/ discharging process is problematic due to the poor effective thermal conductivity of the metal hydride porous bed and the high enthalpies of H2 adsorption/desorption. Therefore, heat transfer is a critical factor affecting the performance of metal hydride hydrogen (MHR storage tanks. Over decade, many researches focused on MHR’s operating conditions and its thermal management to improve its performance.

  2. Using first principles calculations to identify new destabilized metal hydride reactions for reversible hydrogen storage.

    Science.gov (United States)

    Alapati, Sudhakar V; Karl Johnson, J; Sholl, David S

    2007-03-28

    Hydrides of period 2 and 3 elements are promising candidates for hydrogen storage, but typically have heats of reaction that are too high to be of use for fuel cell vehicles. Recent experimental work has focused on destabilizing metal hydrides through mixing metal hydrides with other compounds. A very large number of possible destabilized metal hydride reaction schemes exist, but the thermodynamic data required to assess the enthalpies of these reactions are not available in many cases. We have used density functional theory calculations to predict the reaction enthalpies for more than 300 destabilization reactions that have not previously been reported. The large majority of these reactions are predicted not to be useful for reversible hydrogen storage, having calculated reaction enthalpies that are either too high or too low, and hence these reactions need not be investigated experimentally. Our calculations also identify multiple promising reactions that have large enough hydrogen storage capacities to be useful in practical applications and have reaction thermodynamics that appear to be suitable for use in fuel cell vehicles and are therefore promising candidates for experimental work.

  3. Formation of novel transition metal hydride complexes with ninefold hydrogen coordination

    Science.gov (United States)

    Takagi, Shigeyuki; Iijima, Yuki; Sato, Toyoto; Saitoh, Hiroyuki; Ikeda, Kazutaka; Otomo, Toshiya; Miwa, Kazutoshi; Ikeshoji, Tamio; Orimo, Shin-ichi

    2017-01-01

    Ninefold coordination of hydrogen is very rare, and has been observed in two different hydride complexes comprising rhenium and technetium. Herein, based on a theoretical/experimental approach, we present evidence for the formation of ninefold H- coordination hydride complexes of molybdenum ([MoH9]3−), tungsten ([WH9]3−), niobium ([NbH9]4−) and tantalum ([TaH9]4−) in novel complex transition-metal hydrides, Li5MoH11, Li5WH11, Li6NbH11 and Li6TaH11, respectively. All of the synthesized materials are insulated with band gaps of approximately 4 eV, but contain a sufficient amount of hydrogen to cause the H 1s-derived states to reach the Fermi level. Such hydrogen-rich materials might be of interest for high-critical-temperature superconductivity if the gaps close under compression. Furthermore, the hydride complexes exhibit significant rotational motions associated with anharmonic librations at room temperature, which are often discussed in relation to the translational diffusion of cations in alkali-metal dodecahydro-closo-dodecaborates and strongly point to the emergence of a fast lithium conduction even at room temperature. PMID:28287143

  4. Formation of novel transition metal hydride complexes with ninefold hydrogen coordination.

    Science.gov (United States)

    Takagi, Shigeyuki; Iijima, Yuki; Sato, Toyoto; Saitoh, Hiroyuki; Ikeda, Kazutaka; Otomo, Toshiya; Miwa, Kazutoshi; Ikeshoji, Tamio; Orimo, Shin-Ichi

    2017-03-13

    Ninefold coordination of hydrogen is very rare, and has been observed in two different hydride complexes comprising rhenium and technetium. Herein, based on a theoretical/experimental approach, we present evidence for the formation of ninefold H- coordination hydride complexes of molybdenum ([MoH9](3-)), tungsten ([WH9](3-)), niobium ([NbH9](4-)) and tantalum ([TaH9](4-)) in novel complex transition-metal hydrides, Li5MoH11, Li5WH11, Li6NbH11 and Li6TaH11, respectively. All of the synthesized materials are insulated with band gaps of approximately 4 eV, but contain a sufficient amount of hydrogen to cause the H 1s-derived states to reach the Fermi level. Such hydrogen-rich materials might be of interest for high-critical-temperature superconductivity if the gaps close under compression. Furthermore, the hydride complexes exhibit significant rotational motions associated with anharmonic librations at room temperature, which are often discussed in relation to the translational diffusion of cations in alkali-metal dodecahydro-closo-dodecaborates and strongly point to the emergence of a fast lithium conduction even at room temperature.

  5. Study on Kinetics of Hydrogen Absorption by Metal Hydride Slurries Ⅰ. Absorption of Hydrogen by Hydrogen Storage Alloy MlNi5 Suspended in Benzene

    Institute of Scientific and Technical Information of China (English)

    安越; 陈长聘; 徐国华; 蔡官明; 王启东

    2002-01-01

    The absorption of hydrogen was studied in metal hydride slurry, which is formed by benzene and hydrogen storage alloy powder. The influence of temperature on the rate of absorption was discussed using three-phase mass transfer model. It is also concluded that the suitable absorption temperature is 313 K.

  6. Electrochemical and metallurgical characterization of ZrCr{sub 1-x}NiMo{sub x} AB{sub 2} metal hydride alloys

    Energy Technology Data Exchange (ETDEWEB)

    Erika, Teliz [Universidad de la República, Facultad de Ciencias, Laboratorio de Electroquímica Fundamental, Núcleo Interdisciplinario Ingeniería Electroquímica, Igua 4225, CP 11400 Montevideo (Uruguay); Ricardo, Faccio [Universidad de la República, Crystallography, Solid State and Materials Laboratory (Cryssmat-Lab), DETEMA, Centro NanoMat, Polo Tecnológico de Pando, Espacio Interdisciplinario, Facultad de Química, Montevideo (Uruguay); Fabricio, Ruiz [Consejo Nacional de Investigaciones Científicas y Técnicas , CONICET, Av. Rivadavia 1917, C1033AAJ Ciudad de Buenos Aires (Argentina); Centro Atómico Bariloche , Comisión Nacional de Energía Atómica (CAB-CNEA), Av. Bustillo 9500, CP 8400 S.C. de Bariloche, RN (Argentina); Fernando, Zinola [Universidad de la República, Facultad de Ciencias, Laboratorio de Electroquímica Fundamental, Núcleo Interdisciplinario Ingeniería Electroquímica, Igua 4225, CP 11400 Montevideo (Uruguay); and others

    2015-11-15

    The effects of partial replacement of chromium by molybdenum was studied on the structure and electrochemical kinetic properties of ZrCr{sub 1-x}NiMo{sub x}(x = 0.0, 0.3 and 0.6) metal hydride alloys. The arc-melting prepared alloys were metallurgically characterized by X-ray diffraction and energy dispersive spectroscopy microanalysis, which showed AB{sub 2} (with hexagonal C14 structure) and Zr{sub x}Ni{sub y} (Zr{sub 7}Ni{sub 10}, Zr{sub 9}Ni{sub 11}) phases. After a partial substitution of chromium by molybdenum, secondary phases monotonically increase with the C14 unit cell volume indicating that most of molybdenum atoms locate in the B-site. The alloys were electrochemically characterized using charge/discharge cycling, electrochemical impedance spectroscopy and rate capability experiments that allowed the determination of hydriding reaction kinetic parameters. The presence of molybdenum produces a positive effect for hydrogen diffusion in the alloy lattice, and ZrCr{sub 0.7}NiMo{sub 0.3} alloy depicts the better kinetics associated with a fast activation, lower charge transfer resistance and the best high rate discharge behavior. This fact would be related to a lower diffusion time constant and a bigger value of the product between exchange density current and surface active area. There is a trade-off in the amounts of secondary phase and Laves phases in order to improve the kinetic performance. - Highlights: • Metallurgical characterization evidences the presence of Zr{sub x}Ni{sub y} and C14 phases. • The partial replacement of Cr by Mo promotes the segregation of Zr{sub x}Ni{sub y} phase. • The incorporation of molybdenum improves the kinetics for the hydriding process. • Mo produces a decrease in the diffusion time constant.

  7. Hydrogen concentration limit and critical temperatures for delayed hydride cracking in zirconium alloys

    Energy Technology Data Exchange (ETDEWEB)

    Shi, S.Q. [Atomic Energy of Canada Ltd., Pinawa, Manitoba (Canada). Mater. and Mech. Branch; Shek, G.K. [Materials Technology Unit, Ontario Hydro Technologies, 800 Kipling Avenue, Toronto, Ontario (Canada); Puls, M.P. [Atomic Energy of Canada Ltd., Pinawa, Manitoba (Canada). Mater. and Mech. Branch

    1995-02-01

    An experimental study was carried out to determine the hydrogen concentration limit as a function of temperature at which delayed hydride cracking (DHC) commences in Zr-2.5Nb pressure tube material. For a given hydrogen content of the specimen, two critical temperatures were observed in this work - a DHC initiation temperature, T{sub c}, at which DHC would initiate when approaching the test temperature from above the solvus (or terminal solid solubility) for hydride dissolution (TSSD) and a DHC arrest temperature, T{sub h}, obtained by heating the same specimen from T{sub c} after DHC had started. Both of T{sub c} and T{sub h} are close to, but below, the temperatures defined by TSSD for the specific hydrogen content of the specimen. A theoretical analysis was carried out to quantitatively derive the hydrogen concentration limit and these critical temperatures. The theoretical prediction for T{sub c} depends sensitively on the particular solvus or terminal solid solubility curve for hydride precipitation (TSSP) used, since there is a wide range of values for TSSP depending on the thermal-mechanical history of the material. It is also suggested that T{sub h} is governed by the TSSP for hydride growth, in contrast to T{sub c}, which is governed by the TSSP for hydride nucleation. A model for a previously observed critical temperature (T{sub A}) is also proposed. T{sub A} is a DHC arrest temperature, obtained by approaching the test temperature from a lower temperature. The model suggests that T{sub A} is controlled by the energy difference between TSSD, TSSP and the hydrostatic stress at the crack tip. ((orig.))

  8. Geoneutrinos and Hydridic Earth (or primordially Hydrogen-Rich Planet)

    CERN Document Server

    Bezrukov, L

    2014-01-01

    Geoneutrino is a new channel of information about geochemical composition of the Earth. We alnalysed here the following problem. What statistics do we need to distinguish between predictions of Bulk Silicate Earth model and Hydridic Earth model for Th/U signal ratio? We obtained the simple formula for estimation of error of Th/U signal ratio. Our calculations show that we need more than $22 kt \\cdot year$ exposition for Gran-Sasso underground laboratory and Sudbury Neutrino Observatory. We need more than $27 kt \\cdot year$ exposition for Kamioka site in the case of stopping of all Japanese nuclear power plants.

  9. Electrochemical Evaluation of LaNi(sub 5-x)Ge(sub x) Metal Hydride Alloys

    Science.gov (United States)

    Whitham, C.; Ratnakumar, B. V.; Bowman, R. C., Jr.; Hightower, A.; Fultz, B.

    1996-01-01

    We report a detailed evaluation of Ge-substituted LaNi(sub 5) for electrochemical application as a negative electrode inalkaline rechargeable cells. Alloys with small substitutions of Ge for Ni show operating pressures, chargeability, cyclic lifetime, and kinetics for hydrogen absorption and desorption all superior to those found in many substituted LaNi(sub 5) alloys.

  10. Recent advances in additive-enhanced magnesium hydride for hydrogen storage

    Directory of Open Access Journals (Sweden)

    Ying Wang

    2017-02-01

    Full Text Available The discovery of new hydrogen storage materials has greatly driven the entire hydrogen storage technology forward in the past decades. Magnesium hydride, which has a high hydrogen capacity and low cost, has been considered as one of the most promising candidates for hydrogen storage. Unfortunately, extensive efforts are still needed to better improve its hydrogen storage performance, since MgH2 suffers from high operation temperature, poor dehydrogenation kinetic, and unsatisfactory thermal management. In this paper, we present an overview of recent progress in improving the hydrogenation/de-hydrogenation performance of MgH2, with special emphases on the additive-enhanced MgH2 composites. Other widely used strategies (e. g. alloying, nanoscaling, nanoconfinement in tuning the kinetics and thermodynamics of MgH2 are also presented. A realistic perspective regarding to the challenges and opportunities for further researches in MgH2 is proposed.

  11. Mechanism for electrochemical hydrogen insertion in carbonaceous materials

    Science.gov (United States)

    Qu, Deyang

    The mechanism for safe and reversible storage of hydrogen in porous carbonaceous materials by electrochemical decomposition of water in alkaline electrolyte is proposed. Atomic H was found to be inserted into the microdomains of defective graphene layers. Hydrogen storage capacity increases with increasing interlayer distance between carbon sheets. Hydrogen insertion in carbonaceous materials occurs at ambient conditions. Static potential acts as an electrochemical valve which can retain the hydrogen in the carbon structure, thus preventing leakage during storage.

  12. IMPROVEMENT OF ELECTROCHEMICAL PROCESSES IN HYDROGEN POWER ENGINEERING

    OpenAIRE

    Covaliova O.V.; Covaliov V.V.; Duca Gh.G.; Ivanov M. V.

    2011-01-01

    The possibility is studied of using the three-dimensional voluminous-porous electrodes made of the carbonic-fibrous materials and foamy metals, which surface is covered with Ni-Re alloy, for hydrogen electrochemical generation. Electrode surface modification makes it possible to obtain high reactive surface with low overvoltage of hydrogen evolution. The design is given of the developed compact electrochemical reactors for hydrogen power engineering. The method is described of oxygen-hydrogen...

  13. An electrochemical study of hydrogen uptake and elimination by bare and gold-plated waspaloy

    Science.gov (United States)

    Danford, M. D.; Deramus, G. E., Jr.; Lowery, J. R.

    1984-01-01

    Two electrochemical methods for the determination of hydrogen concentrations in metals are discussed and evaluated. The take-up of hydrogen at a pressure of 5000 psi by Waspaloy metal was determined experimentally at 24 C. It was found that the metal becomes saturated with hydrogen after an exposure time of about 1 hr. For samples charged with hydrogen at high pressure, most of the hydrogen is contained in the interstitial solid solution of the metal. For electrolytically charged samples, most of the hydrogen is contained as surface and subsurface hydrides. Hydrogen elimination rates were determined for these two cases, with the rate for electrolytically charged samples being greater by over a factor of two. Theoretical effects of high temperature and pressure on hydrogen take-up and elimination by bare and gold plated Waspaloy metal was considered. The breakthrough point for hydrogen at 5000 psi, determined experimentally, lies between a gold thickness of 0.0127 mm (0.0005 in.) and 0.0254 mm (0.001 in.) at 24 C. Electropolishing was found to greatly reduce the uptake of hydrogen at high pressure by Waspaloy metal at 24 C. Possible implications of the results obtained, as they apply to the turbine disk of the space shuttle main engine, are discussed.

  14. Structure improvement and electrochemical studies of bipolar nickel metal hydride batteries for hybrid electric vehicles

    Institute of Scientific and Technical Information of China (English)

    DENG Chao; SHI Peng-fei

    2006-01-01

    Nickel metal hydride battery in bipolar design offers some advantages for its application as a power storage system for electric and hybrid vehicles. This paper deals with the structure design and electrochemical studies of bipolar Ni/MH batteries for hybrid vehicles. An improvement is applied in bipolar battery design,and such bipolar Ni/MH batteries with 5 sub-cells have been assembled and investigated. Testing results show that bipolar batteries with improved structure have better compression tolerance and cycle performance than conventional ones. In addition, the improved bipolar batteries display excellent large current discharge ability and high power density. As simulating working conditions for hybrid vehicles, the batteries show good stability during pulse cycles, which verifies the possibility of being used as a power storage device on hybrid vehicles.

  15. Effect of Overcharge on Electrochemical Performance of Sealed-Type Nickel/Metal Hydride Batteries

    Institute of Scientific and Technical Information of China (English)

    LI Li; WU Feng; CHEN Ren-jie; CHEN Shi

    2005-01-01

    The effects of overcharge on electrochemical performance of AA size sealed-type nickel/metal hydride(Ni/MH) batteries and its degradation mechanism were investigated. The results indicated that the relationship between the effects of different overcharge currents on the increasing velocity of inner pressure and the degradation velocity of cycle life and discharge voltage remains in almost direct proportion. After overcharge cycles, the positive electrode materials remain the original structure, but there occur some breaks because of the irreversible expand of crystal lattice. And the negative electrode alloy particles have inconspicuous pulverization, but are covered with lots of corrosive products and its main component is rare earth hydroxide or oxide. These are all the main reasons leading to the degradation behavior of the discharge capacity and cycle life of Ni/MH batteries.

  16. The renaissance of hydrides as energy materials

    Science.gov (United States)

    Mohtadi, Rana; Orimo, Shin-Ichi

    2017-02-01

    Materials based on hydrides have been the linchpin in the development of several practical energy storage technologies, of which the most prominent example is nickel-metal hydride batteries. Motivated by the need to meet the future's energy demand, the past decade has witnessed substantial advancements in the research and development of hydrides as media for hydrogen energy storage. More recently, new and rapidly evolving discoveries have positioned hydrides as highly promising materials for future electrochemical energy storage, such as electrolytes for mono- and divalent batteries, and anodes for lithium-ion batteries. In addition, the potential of hydrides in efficient power transmission has been recently revealed. In this Review, we highlight key advances and illustrate how the versatility of hydrides has not only yielded a meaningful past, but also ensures a very bright future.

  17. Nanometer-scale hydrogen 'portals' for the control of magnesium hydride formation.

    Science.gov (United States)

    Chung, Chia-Jung; Nivargi, Chinmay; Clemens, Bruce

    2015-11-21

    Magnesium and Mg-based material systems are attractive candidates for hydrogen storage but limited by unsuitable thermodynamic and kinetic properties. In particular, the kinetics are too slow at room temperature and atmospheric pressure. To study the hydride formation kinetics in a controlled way, we have designed a unique 'nanoportal' structure of Pd nanoparticles deposited on epitaxial Mg thin films, through which the hydride will nucleate only under Pd nanoparticles. We propose a growth mechanism for the hydrogenation reaction in the nanoportal structure, which is supported by scanning electron microscopy (SEM) images of hydrogenated samples exhibiting consistent results. Interestingly, the grain boundaries of Mg films play an important role in hydride nucleation and growth processes. Kinetic modeling based on the Johnson-Mehl-Avrami-Kolmogorov (JMAK) formalism seems to agree with the two-dimensional nucleation and growth mechanism hypothesized and the overall reaction rate is limited by hydrogen flux through the interface between the Pd nanoparticle and the underlying Mg film. The fact that in our structure Mg can be transformed completely into MgH2 with only a small percentage of Pd nanoparticles offers possibilities for future on-board storage applications.

  18. OPTIMIZATION OF INTERNAL HEAT EXCHANGERS FOR HYDROGEN STORAGE TANKS UTILIZING METAL HYDRIDES

    Energy Technology Data Exchange (ETDEWEB)

    Garrison, S.; Tamburello, D.; Hardy, B.; Anton, D.; Gorbounov, M.; Cognale, C.; van Hassel, B.; Mosher, D.

    2011-07-14

    Two detailed, unit-cell models, a transverse fin design and a longitudinal fin design, of a combined hydride bed and heat exchanger are developed in COMSOL{reg_sign} Multiphysics incorporating and accounting for heat transfer and reaction kinetic limitations. MatLab{reg_sign} scripts for autonomous model generation are developed and incorporated into (1) a grid-based and (2) a systematic optimization routine based on the Nelder-Mead downhill simplex method to determine the geometrical parameters that lead to the optimal structure for each fin design that maximizes the hydrogen stored within the hydride. The optimal designs for both the transverse and longitudinal fin designs point toward closely-spaced, small cooling fluid tubes. Under the hydrogen feed conditions studied (50 bar), a 25 times improvement or better in the hydrogen storage kinetics will be required to simultaneously meet the Department of Energy technical targets for gravimetric capacity and fill time. These models and methodology can be rapidly applied to other hydrogen storage materials, such as other metal hydrides or to cryoadsorbents, in future work.

  19. Standardized hydrogen storage module with high utilization factor based on metal hydride-graphite composites

    Science.gov (United States)

    Bürger, Inga; Dieterich, Mila; Pohlmann, Carsten; Röntzsch, Lars; Linder, Marc

    2017-02-01

    In view of hydrogen based backup power systems or small-scale power2gas units, hydrogen storages based on metal hydrides offer a safe and reliable solution. By using Hydralloy C5 as suitable hydride forming alloy, the present tank design guarantees very simple operating conditions: pressures between 4 bar and 30 bar, temperatures between 15 °C and 40 °C and minimal efforts for thermal management in combination with fast and constant charging and discharging capabilities. The modular tank consists of 4 layers with 5 reactor tubes each that are filled with metal hydride-graphite composites of a diameter of 21 mm. Experiments show that each layer of this tank is able to desorb the desired amount of hydrogen for a fuel cell operation at electrical power of 160 Wel for 100 min reaching a utilization factor of 93% of the stored hydrogen at RC. Furthermore, the experimental results of modularity, increasing loads and the electric air ventilation are presented.

  20. Hydrogen storage over alkali metal hydride and alkali metal hydroxide composites

    Institute of Scientific and Technical Information of China (English)

    Pei Yu; Yong Shen Chua; Hujun Cao; Zhitao Xiong; Guotao Wu; Ping Chen

    2014-01-01

    Alkali metal hydroxide and hydride composite systems contain both protic (H bonded with O) and hydridic hydrogen. The interaction of these two types of hydrides produces hydrogen. The enthalpy of dehydrogenation increased with the increase of atomic number of alkali metals, i.e.,-23 kJ/molH2 for LiOH-LiH, 55.34 kJ/molH2 for NaOH-NaH and 222 kJ/molH2 for KOH-KH. These thermodynamic calculation results were consistent with our experimental results. H2 was released from LiOH-LiH system during ball milling. The dehydrogenation temperature of NaOH-NaH system was about 150◦C; whereas KOH and KH did not interact with each other during the heating process. Instead, KH decomposed by itself. In these three systems, NaOH-NaH was the only reversible hydrogen storage system, the enthalpy of dehydrogenation was about 55.65 kJ/molH2 , and the corresponding entropy was ca. 101.23 J/(molH2 ·K), so the temperature for releasing 1.0 bar H2 was as high as 518◦C, showing unfavorable thermodynamic properties. The activation energy for hydrogen desorption of NaOH-NaH was found to be 57.87 kJ/mol, showing good kinetic properties.

  1. Influence of surface contaminations on the hydrogen storage behaviour of metal hydride alloys.

    Science.gov (United States)

    Schülke, Mark; Paulus, Hubert; Lammers, Martin; Kiss, Gábor; Réti, Ferenc; Müller, Karl-Heinz

    2008-03-01

    Hydrogen storage in metal hydrides is a promising alternative to common storage methods. The surface of a metal hydride plays an important part in the absorption of hydrogen, since important partial reaction steps take place here. The development of surface contaminations and their influence on hydrogen absorption is examined by means of absorption experiments and surface analysis, using X-ray photoelectron spectroscopy (XPS), thermal desorption mass spectrometry (TDMS) and secondary neutral mass spectrometry (SNMS), in this work. All investigations were carried out on a modern AB(2) metal hydride alloy, namely Ti(0.96)Zr(0.04)Mn(1.43)V(0.45)Fe(0.08). Surface analysis (SNMS, XPS) shows that long-term air storage (several months) leads to oxide layers about 15 nm thick, with complete oxidation of all main alloy components. By means of in situ oxygen exposure at room temperature and XPS analysis, it can be shown that an oxygen dose of about 100 Langmuirs produces an oxide layer comparable to that after air storage. Manganese enrichment (segregation) is also clearly observed and is theoretically described here. This oxide layer hinders hydrogen absorption, so an activation procedure is necessary in order to use the full capacity of the metal hydride. This procedure consists of heating (T = 120 degrees C) in vacuum and hydrogen flushing at pressures like p = 18 bar. During the activation process the alloy is pulverized to particles of approximately 20 microm through lattice stretches. It is shown that this pulverization of the metal hydride (creating clean surface) during hydrogen flushing is essential for complete activation of the material. Re-activation of powder contaminated by small doses of air (p approximately 0.1 bar) does not lead to full absorption capacity. In ultrahigh vacuum, hydrogen is only taken up by the alloy after sputtering of the surface (which is done in order to remove oxide layers from it), thus creating adsorption sites for the hydrogen. This

  2. Phane Nomenclature. Part II: Modification of the Degree of Hydrogenation and Substitution Derivatives of Phane Parent Hydrides

    Directory of Open Access Journals (Sweden)

    Šumanovac Ramljak, T.

    2010-06-01

    Full Text Available Cyclophane and linear phane systems are considered as parent hydrides. Their derivatives are named in conformity with the principles, rules, and conventions prescribed for naming organic compounds. The following nomenclatural features are described: indicated and added hydrogen, order of seniority for numbering, substituents expressed as suffixes, substituents cited as prefixes, phane parent hydrides modified by addition or subtraction of hydrogen atoms, and polyfunctional derivatives.

  3. First-principles predictions of potential hydrogen storage materials: Nanosized Ti(core)/Mg(shell) hydrides

    Science.gov (United States)

    Tao, S. X.; Notten, P. H. L.; van Santen, R. A.; Jansen, A. P. J.

    2011-05-01

    MgH2 is one of the most promising hydrogen storage materials. However MgH2 is thermodynamicly too stable, leading to a too high desorption temperature of 300°C at atmospheric pressure, which is a major impediment for practical applications. In this study, aiming to tune the thermodynamic stability of the MgH2, nanosized two-dimensional Mg/Ti/Mg sandwich and three-dimensional Ti(core)/Mg(shell) hydrides have been investigated by using density functional theory calculations. For both structures, four types of hydrogen atoms can be distinguished: on the surface of the Mg (Hsurf), within the Mg (HMg), at the Mg/Ti interface (HMgTi), and within the Ti (HTi). For the dehydrogenation reaction, the hydrogen desorption from the hydride is in the order Hsurf, HMg, HMgTi, HTi. The desorption energy of Hsurf is unexpectedly high. As expected, due to the well-preserved fluorite structure of the partially hydrogenated hydride, the desorption energy of HMg is significantly lower than that of bulk rutile MgH2. The further desorption of HMgTi and HTi becomes more difficult due to the strong Ti-H bonding. We propose that partial hydrogenation without adsorption of Hsurf and partial dehydrogenation without desorption of HMgTi and HTi would keep the fluorite symmetry with its favorable thermodynamics. The reversible hydrogen capacity (HMg) of the Mg/Ti/Mg sandwich structure is low, whereas the reversible hydrogen capacity of the Ti(core)/Mg(shell) is calculated to be reasonable high. Our results predicted Ti(core)/Mg(shell) structures are potential useful materials for hydrogen storage application.

  4. Complex hydrides for hydrogen storage – new perspectives

    Directory of Open Access Journals (Sweden)

    Morten B. Ley

    2014-04-01

    Full Text Available Since the 1970s, hydrogen has been considered as a possible energy carrier for the storage of renewable energy. The main focus has been on addressing the ultimate challenge: developing an environmentally friendly successor for gasoline. This very ambitious goal has not yet been fully reached, as discussed in this review, but a range of new lightweight hydrogen-containing materials has been discovered with fascinating properties. State-of-the-art and future perspectives for hydrogen-containing solids will be discussed, with a focus on metal borohydrides, which reveal significant structural flexibility and may have a range of new interesting properties combined with very high hydrogen densities.

  5. Protonation equilibrium and hydrogen production by a dinuclear cobalt-hydride complex reduced by cobaltocene with trifluoroacetic acid.

    Science.gov (United States)

    Mandal, Sukanta; Shikano, Shinya; Yamada, Yusuke; Lee, Yong-Min; Nam, Wonwoo; Llobet, Antoni; Fukuzumi, Shunichi

    2013-10-16

    A dinuclear Co complex with bis(pyridyl)pyrazolato (bpp(-)) and terpyridine (trpy) ligands, [Co(III)2(trpy)2(μ-bpp)(OH)(OH2)](4+) (1(4+)), undergoes three-electron reduction by cobaltocene in acetonitrile to produce 1(+), which is in the protonation equilibrium with the Co(II)Co(III)-hydride complex, and the further protonation of the hydride by trifluoroacetic acid yields hydrogen quantitatively. The kinetic study together with the detection of the Co(II)Co(III)-hydride complex revealed the mechanism of the hydrogen production by the reaction of 1(+) with trifluoroacetic acid.

  6. Hydrogen storage systems based on magnesium hydride: from laboratory tests to fuel cell integration

    Science.gov (United States)

    de Rango, P.; Marty, P.; Fruchart, D.

    2016-02-01

    The paper reviews the state of the art of hydrogen storage systems based on magnesium hydride, emphasizing the role of thermal management, whose effectiveness depends on the effective thermal conductivity of the hydride, but also depends of other limiting factors such as wall contact resistance and convective exchanges with the heat transfer fluid. For daily cycles, the use of phase change material to store the heat of reaction appears to be the most effective solution. The integration with fuel cells (1 kWe proton exchange membrane fuel cell and solid oxide fuel cell) highlights the dynamic behaviour of these systems, which is related to the thermodynamic properties of MgH2. This allows for "self-adaptive" systems that do not require control of the hydrogen flow rate at the inlet of the fuel cell.

  7. Scaling up effects of Mg hydride in a temperature and pressure-controlled hydrogen storage device

    Energy Technology Data Exchange (ETDEWEB)

    Verga, M.; Armanasco, F.; Guardamagna, C.; Valli, C. [CESI RICERCA S.p.A., Via Rubattino 54, 20134 Milano (Italy); Bianchin, A.; Lo Russo, S. [Dipartimento di Fisica, Universita di Padova, via Marzolo 8, 35131 Padova (Italy); Agresti, F.; Maddalena, A.; Principi, G. [Settore Materiali, Dipartimento di Ingegneria Meccanica, via Marzolo 9, 35131 Padova (Italy)

    2009-05-15

    A research program addressed to evaluate the magnesium hydride storage scaling up effects is being developed by CESI RICERCA, Milano, and the Hydrogen Group of Padova University. A storage device containing 500 g of magnesium hydride powder (manufactured by Venezia Tecnologie S.p.A. using high-energy ball milling) has been designed and tested in different operating conditions. A number of absorption and desorption cycles at different temperatures and pressures has been carried out in order to see if the results are comparable with laboratory data obtained on small amounts (fractions of grams) of powder samples. A sensible performance degradation that reduced the overall storage capacity of about 50% has been noticed after 20 cycles, presumably due to local powder heating, fragmentation and subsequent compaction. Further tests on a smaller tank equipped also with a porous baffle gave useful indications for the design of an improved large hydrogen reservoir. (author)

  8. THE ABSORPTION OF HYDROGEN ON LOW PRESSURE HYDRIDE MATERIALS

    Energy Technology Data Exchange (ETDEWEB)

    Morgan, G.; Korinko, P.

    2012-04-03

    For this study, hydrogen getter materials (Zircaloy-4 and pure zirconium) that have a high affinity for hydrogen (and low overpressure) have been investigated to determine the hydrogen equilibrium pressure on Zircaloy-4 and pure zirconium. These materials, as with most getter materials, offered significant challenges to overcome given the low hydrogen equilibrium pressure for the temperature range of interest. Hydrogen-zirconium data exists for pure zirconium at 500 C and the corresponding hydrogen overpressure is roughly 0.01 torr. This manuscript presents the results of the equilibrium pressures for the absorption and desorption of hydrogen on zirconium materials at temperatures ranging from 400 C to 600 C. The equilibrium pressures in this temperature region range from 150 mtorr at 600 C to less than 0.1 mtorr at 400 C. It has been shown that the Zircaloy-4 and zirconium samples are extremely prone to surface oxidation prior to and during heating. This oxidation precludes the hydrogen uptake, and therefore samples must be heated under a minimum vacuum of 5 x 10{sup -6} torr. In addition, the Zircaloy-4 samples should be heated at a sufficiently low rate to maintain the system pressure below 0.5 mtorr since an increase in pressure above 0.5 mtorr could possibly hinder the H{sub 2} absorption kinetics due to surface contamination. The results of this study and the details of the testing protocol will be discussed.

  9. Mathematical Modeling of Pneumatic Artificial Muscle Actuation via Hydrogen Driving Metal Hydride-LaNi5

    Institute of Scientific and Technical Information of China (English)

    Thananchai Leephakpreeda

    2012-01-01

    Quantitative understanding of mechanical actuation of intricate Pneumatic Artificial Muscle (PAM) actuators is technically required in control system design for effective real-time implementation.This paper presents mathematical modeling of the PAM driven by hydrogen-gas pressure due to absorption and desorption of metal hydride.Empirical models of both mechanical actuation of industrial PAM and chemical reaction of the metal hydride-LaNi5 are derived systematically where their interactions comply with the continuity principle and energy balance in describing actual dynamic behaviors of the PAM actuator (PAM and hydriding/dehydriding-reaction bed).Simulation studies of mechanical actuation under various loads are conducted so as to present dynamic responses of the PAM actuators.From the promising results,it is intriguing that the heat input for the PAM actuator can be supplied to,or pumped from the reaction bed,in such a way that absorption and desorption of hydrogen gas take place,respectively,in controlling the pressure of hydrogen gas within the PAM actuator.Accordingly,this manipulation results in desired mechanical actuation of the PAM actuator in practical uses.

  10. Syntheses and properties of several metastable and stable hydrides derived from intermetallic compounds under high hydrogen pressure

    Science.gov (United States)

    Filipek, S. M.; Paul-Boncour, V.; Liu, R. S.; Jacob, I.; Tsutaoka, T.; Budziak, A.; Morawski, A.; Sugiura, H.; Zachariasz, P.; Dybko, K.; Diduszko, R.

    2016-12-01

    Brief summary of our former work on high hydrogen pressure syntheses of novel hydrides and studies of their properties is supplemented with new results. Syntheses and properties of a number of hydrides (unstable, metastable or stable in ambient conditions) derived under high hydrogen pressure from intermetallic compounds, like MeT2, MeNi5, Me7T3, Y6Mn23 and YMn12 (where Me = zirconium, yttrium or rare earth; T = transition metal) are presented. Stabilization of ZrFe2H4 due to surface phenomena was revealed. Unusual role of manganese in hydride forming processes is pointed out. Hydrogen induced phase transitions, suppression of magnetism, antiferromagnetic-ferromagnetic and metal-insulator or semimetal-metal transitions are described. Equations of state (EOS) of hydrides submitted to hydrostatic pressures up to 30 GPa are presented and discussed.

  11. Enhanced hydrogen storage property of magnesium hydride by high surface area Raney nickel

    Energy Technology Data Exchange (ETDEWEB)

    Bhat, Vinay; Rougier, Aline; Aymard, Luc; Tarascon, Jean-Marie [University of Picardie, Amiens (France); Nazri, Gholam-Abbas [GMR and D, Chemical and Environmental Sciences Lab, Warren, MI (United States)

    2007-12-15

    This paper describes the improvement of hydrogen sorption capacity and kinetics of MgH{sub 2} by addition of high surface area ({approx}100m{sup 2}/g) Raney nickel (RN). Herein, we demonstrate that enhanced hydrogen sorption by MgH{sub 2} due to RN is not only linked to the catalytic nature of Ni, but also correlates well with the BET surface area for the MgH{sub 2}-Ni composites. The Raney Ni also tends to form the less stable Mg{sub 2}NiH{sub 4} hydrides, which desorb hydrogen at much higher pressure as compared with that of the MgH{sub 2}. We have observed a significant improvement in hydrogen sorption capacity and increase in pressure of hydrogen desorption for MgH{sub 2} catalyzed by RN. (author)

  12. High H- ionic conductivity in barium hydride

    Science.gov (United States)

    Verbraeken, Maarten C.; Cheung, Chaksum; Suard, Emmanuelle; Irvine, John T. S.

    2015-01-01

    With hydrogen being seen as a key renewable energy vector, the search for materials exhibiting fast hydrogen transport becomes ever more important. Not only do hydrogen storage materials require high mobility of hydrogen in the solid state, but the efficiency of electrochemical devices is also largely determined by fast ionic transport. Although the heavy alkaline-earth hydrides are of limited interest for their hydrogen storage potential, owing to low gravimetric densities, their ionic nature may prove useful in new electrochemical applications, especially as an ionically conducting electrolyte material. Here we show that barium hydride shows fast pure ionic transport of hydride ions (H-) in the high-temperature, high-symmetry phase. Although some conductivity studies have been reported on related materials previously, the nature of the charge carriers has not been determined. BaH2 gives rise to hydride ion conductivity of 0.2 S cm-1 at 630 °C. This is an order of magnitude larger than that of state-of-the-art proton-conducting perovskites or oxide ion conductors at this temperature. These results suggest that the alkaline-earth hydrides form an important new family of materials, with potential use in a number of applications, such as separation membranes, electrochemical reactors and so on.

  13. P-hydrogen-substituted 1,3,2-diazaphospholenes: molecular hydrides.

    Science.gov (United States)

    Burck, Sebastian; Gudat, Dietrich; Nieger, Martin; Du Mont, Wolf-Walther

    2006-03-29

    P-Hydrogen-substituted 1,3,2-diazaphospholenes 1 were prepared by an improved procedure from diazadienes and were characterized by spectroscopy and in one case by X-ray diffraction. A unique hydride-type reactivity of the P-H bonds was documented by extensive reactivity studies. Aldehydes and ketones were readily reduced to diazaphospholene derivatives of the corresponding alcohols, with alkyl-substituted ketones being converted at much lower rates than aldehydes or diaryl ketones. Reactions with the tetrachlorides of group 14 elements proceeded via hydride/chloride metathesis to give either partially chlorinated derivatives EH(n)Cl(4-n) (n = 0-3 for E = C, Si) or HCl and phosphenium salts 16c[ECl3] (for E = Ge, Sn) which were characterized by spectroscopic and X-ray diffraction studies. Tin dichloride was readily reduced to the element. Reactions of 1c with the P-chloro-diazaphospholene 3c and the salt 16c[OTf] allowed the first experimental detection of intermolecular exchange of a hydride, rather than a proton, between phosphine derivatives. Computational studies indicated that the hydride transfer between 1c and the cation 16c involves a transient H-bridged species with bonding properties similar to those of B2H7-. The preference for the formation of these bridged intermediates over P-P bonded phosphenium-phosphine adducts is attributed to the low electrophilicity of the diazaphospholenium cations and characterizes a novel reaction mode for phosphenium ions.

  14. Compensation effect in the hydrogenation/dehydrogenation kinetics of metal hydrides.

    Science.gov (United States)

    Andreasen, Anders; Vegge, Tejs; Pedersen, Allan S

    2005-03-03

    The possible existence of a compensation effect, i.e. concurrent changes in activation energy and prefactor, is investigated for the hydrogenation and dehydrogenation kinetics of metal hydrides, by analyzing a series of reported kinetic studies on Mg and LaNi(5) based hydrides. For these systems, we find a clear linear relation between apparent prefactors and apparent activation energies, as obtained from an Arrhenius analysis, indicating the existence of a compensation effect. Large changes in apparent activation energies in the case of Mg based hydrides are rationalized in terms of a dependency of observed apparent activation energy on the degree of surface oxidation, i.e., a physical effect. On the other hand, we find the large concurrent changes in apparent prefactors to be a direct result of the Arrhenius analysis. Thus, we find the observed compensation effect to be an artifact of the data analysis rather than a physical phenomenon. In the case of LaNi(5) based hydrides, observed scatter in reported apparent activation energies is less pronounced supporting the general experience that LaNi(5) is less sensitive toward surface contamination.

  15. Electrochemical impedance spectroscopy study of the metal hydride alloy/electrolyte junction

    Energy Technology Data Exchange (ETDEWEB)

    Khaldi, Chokri [Laboratoire de Mecanique, Materiaux et Procedes, ESSTT, 5 Avenue Taha Hussein, 1008 Tunis (Tunisia)], E-mail: chokri.khaldi@esstt.rnu.tn; Mathlouthi, Hamadi; Lamloumi, Jilani [Laboratoire de Mecanique, Materiaux et Procedes, ESSTT, 5 Avenue Taha Hussein, 1008 Tunis (Tunisia)

    2009-06-24

    The behaviour of the LaNi{sub 3.55}Mn{sub 0.4}Al{sub 0.3}Co{sub 0.75} alloy, used as a negative electrode in the Ni-MH batteries, was studied by the electrochemical impedance spectroscopy (EIS), measured at different potentials. The modeling of the EIS spectra allows us to model the interface electrolyte/Ni-MH electrode by a succession of interfaces electrolyte/corrosion film/alloy particles. The various processes and the physics parameters of each interface are discussed and evaluated. When the potential shifts to more negative values, two reactions are in competition: the hydrogen molecular evolution and the hydrogen atomic absorption. The hydrogen diffuses in the bulk of the alloy and the diffusion is not the limiting factor for the hydrogen absorption.

  16. Kinetic Modification on Hydrogen Desorption of Lithium Hydride and Magnesium Amide System

    OpenAIRE

    Hiroki Miyaoka; Yongming Wang,; Satoshi Hino; Shigehito Isobe; Kazuhiko Tokoyoda; Takayuki Ichikawa; Yoshitsugu Kojima

    2015-01-01

    Various synthesis and rehydrogenation processes of lithium hydride (LiH) and magnesium amide (Mg(NH2)2) system with 8:3 molar ratio are investigated to understand the kinetic factors and effectively utilize the essential hydrogen desorption properties. For the hydrogen desorption with a solid-solid reaction, it is expected that the kinetic properties become worse by the sintering and phase separation. In fact, it is experimentally found that the low crystalline size and the close contact of L...

  17. Possibility of obtaining atomic metallic hydrogen by electrochemical method

    OpenAIRE

    Galushkin, Nikolay E.; Yazvinskaya, Nataliya N.; Galushkin, Dmitriy N.

    2013-01-01

    In this work we show, that atomic metallic hydrogen (AMH) is formed inside of sintered oxide-nickel electrodes of nickel-cadmium battery over a long period of electrochemical hydrogenation (more than five years). It was established that density AMH is 12 times higher, than the density of liquid molecular hydrogen, the specific energy of hydrogen recombination is 20 times higher than of liquid hydrogen-oxygen fuel. At the room temperature AMH is a good conductor, but not a superconductor.

  18. Improved metal hydride technology for the storage of hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Sapru, K.; Ming, L.; Ramachandran, S. [Energy Conversion Devices, Inc., Troy, MI (United States)] [and others

    1995-09-01

    Low cost, high density storage of hydrogen will remove the most serious barrier to large-scale utilization of hydrogen as a non-polluting, zero-emission fuel. An important challenge for the practical use of Mg-based, high capacity hydrogen storage alloys has been the development of a low-cost, bulk production technique. Two difficulties in preparation of Mg-based alloys are the immiscibility of Mg with many transition metals and the relatively high volatility of Mg compared to many transition metals. These factors preclude the use of conventional induction melting techniques for the Mg-based alloy preparation. A mechanical alloying technique, in which Mg immiscibility and volatility do not present a problem, was developed and shows great promise for production of Mg-based alloys. A number of Mg-based alloys were prepared via modified induction melting and mechanical alloying methods. The alloys were tested for gas phase hydrogen storage properties, composition, structure and morphology. The mechanically alloyed samples are multi-component, multi-phase, highly disordered materials in their as-prepared state. These unoptimized alloys have shown reversible H-storage capacity of more than 5 wt.% hydrogen. After 2000 absorption/desorption cycles, the alloys show no decline in storage capacity or desorption kinetics. The alloys have also demonstrated resistance to CH{sub 4} and CO poisoning in preliminary testing. Upon annealing, with an increase in crystallinity, the H-storage capacity decreases, indicating the importance of disorder.

  19. Improved hydrogen sorption kinetics in wet ball milled Mg hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Meng, Li

    2011-05-04

    In this work, wet ball milling method is used in order to improve hydrogen sorption behaviour due to its improved microstructure of solid hydrogen materials. Compared to traditional ball milling method, wet ball milling has benefits on improvement of MgH{sub 2} microstructure and further influences on its hydrogen sorption behavior. With the help of solvent tetrahydrofuran (THF), wet ball milled MgH{sub 2} powder has much smaller particle size and its specific surface area is 7 times as large as that of dry ball milled MgH{sub 2} powder. Although after ball milling the grain size is decreased a lot compared to as-received MgH{sub 2} powder, the grain size of wet ball milled MgH{sub 2} powder is larger than that of dry ball milled MgH{sub 2} powder due to the lubricant effect of solvent THF during wet ball milling. The improved particle size and specific surface area of wet ball milled MgH{sub 2} powder is found to be determining its hydrogen sorption kinetics especially at relatively low temperatures. And it also shows good cycling sorption behavior, which decides on its industrial applicability. With three different catalysts MgH{sub 2} powder shows improved hydrogen sorption behavior as well as the cyclic sorption behavior. Among them, the Nb{sub 2}O{sub 5} catalyst is found to be the most effective one in this work. Compared to the wet ball milled MgH{sub 2} powder, the particle size and specific surface area of the MgH{sub 2} powder with catalysts are similar to the previous ones, while the grain size of the MgH{sub 2} with catalysts is much finer. In this case, two reasons for hydrogen sorption improvement are suggested: one is the reduction of the grain size. The other may be as pointed out in some literatures that formation of new oxidation could enhance the hydrogen sorption kinetics, which is also the reason why its hydrogen capacity is decreased compared to without catalysts. After further ball milling, the specific surface area of wet ball milled Mg

  20. Effect of Magnesium Fluoride on Hydrogenation Properties of Magnesium Hydride

    Directory of Open Access Journals (Sweden)

    Pragya Jain

    2015-11-01

    Full Text Available A cost effective catalyst is of great importance for consideration of MgH2 as potential hydrogen storage material. In this regard, we investigated the catalytic role of alkaline metal fluoride on the hydrogen storage behavior of MgH2. Samples were synthesized by admixing 5 mol % MgF2 into MgH2 powder using planetary ball mill. Hydrogenation measurements made at 335 °C showed that in comparison to only 70% absorption by pure MgH2, catalyzed material absorbed 92% of theoretical capacity in less than 20 min and desorbed completely in almost the same time. Sorption studies done at lower temperatures revealed that complete absorption at temperature as low as 145 °C is possible. This is due to uniform distribution of MgF2 nano particles within the MgH2 powder. X-ray diffraction patterns also showed the presence of stable MgF2 phase that does not decompose upon hydrogen absorption-desorption. Cyclic measurements done at 310 °C showed negligible loss in the overall storage capacity with cycling. These results reveal that the presence of the chemically inert and stable MgF2 phase is responsible for good reversible characteristic and improved kinetics.

  1. Identification of destabilized metal hydrides for hydrogen storage using first principles calculations.

    Science.gov (United States)

    Alapati, Sudhakar V; Johnson, J Karl; Sholl, David S

    2006-05-04

    Hydrides of period 2 and 3 elements are promising candidates for hydrogen storage but typically have heats of reaction that are too high to be of use for fuel cell vehicles. Recent experimental work has focused on destabilizing metal hydrides through alloying with other elements. A very large number of possible destabilized metal hydride reaction schemes exist. The thermodynamic data required to assess the enthalpies of these reactions, however, are not available in many cases. We have used first principles density functional theory calculations to predict the reaction enthalpies for more than 100 destabilization reactions that have not previously been reported. Many of these reactions are predicted not be useful for reversible hydrogen storage, having calculated reaction enthalpies that are either too high or too low. More importantly, our calculations identify five promising reaction schemes that merit experimental study: 3LiNH(2) + 2LiH + Si --> Li(5)N(3)Si + 4H(2), 4LiBH(4) + MgH(2) --> 4LiH + MgB(4) + 7H(2), 7LiBH(4) + MgH(2) --> 7LiH + MgB(7) + 11.5H(2), CaH(2) + 6LiBH(4) --> CaB(6) + 6LiH + 10H(2), and LiNH(2) + MgH(2) --> LiMgN + 2H(2).

  2. Dealloyed Ruthenium Film Catalysts for Hydrogen Generation from Chemical Hydrides

    Directory of Open Access Journals (Sweden)

    Ramis B. Serin

    2017-07-01

    Full Text Available Thin-film ruthenium (Ru and copper (Cu binary alloys have been prepared on a Teflon™ backing layer by cosputtering of the precious and nonprecious metals, respectively. Alloys were then selectively dealloyed by sulfuric acid as an etchant, and their hydrogen generation catalysts performances were evaluated. Sputtering time and power of Cu atoms have been varied in order to tailor the hydrogen generation performances. Similarly, dealloying time and the sulfuric acid concentration have also been altered to tune the morphologies of the resulted films. A maximum hydrogen generation rate of 35 mL min−1 was achieved when Cu sputtering power and time were 200 W and 60 min and while acid concentration and dealloying time were 18 M and 90 min, respectively. It has also been demonstrated that the Ru content in the alloy after dealloying gradually increased with the increasing the sputtering power of Cu. After 90 min dealloying, the Ru to Cu ratio increased to about 190 times that of bare alloy. This is the key issue for observing higher catalytic activity. Interestingly, we have also presented template-free nanoforest-like structure formation within the context of one-step alloying and dealloying used in this study. Last but not least, the long-time hydrogen generation performances of the catalysts system have also been evaluated along 3600 min. During the first 600 min, the catalytic activity was quite stable, while about 24% of the catalytic activity decayed after 3000 min, which still makes these systems available for the development of robust catalyst systems in the area of hydrogen generation.

  3. Improved electrochemical hydrogen storage properties of Mg-Y thin films as a function of substrate temperature

    Institute of Scientific and Technical Information of China (English)

    Yanyan Wang; Gongbiao Xin; Chongyun Wang; Huiyu Li; Wei Li; Jie Zheng; Xingguo Li

    2014-01-01

    Pd-capped Mg78 Y22 thin films have been prepared by direct current magnetron co-sputtering system at different substrate temperatures and their electrochemical hydrogen storage properties have been investigated. It is found that rising substrate temperature to 60◦C can coarsen the surface of thin film, thus facilitating the diffusion of hydrogen atoms and then enhancing its discharge capacity to ∼1725 mAh·g-1 . Simultaneously, the cyclic stability is effectively improved due to the increased adhesion force between film and substrate as a function of temperature. In addition, the specimen exhibits a very long and flat discharge plateau at about-0.67 V, at which nearly 60%of capacity is maintained. The property is favorable for the application in metal hydride/nickel secondary batteries. The results indicate that rising optimal substrate temperature has a beneficial effect on the electrochemical hydrogen storage of Mg-Y thin films.

  4. Technical and economic evaluation of hydrogen storage systems based on light metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Jepsen, Julian

    2014-07-01

    Novel developments regarding materials for solid-state hydrogen storage show promising prospects. These complex hydrides exhibit high mass-related storage capacities and thus great technical potential to store hydrogen in an efficient and safe way. However, a comprehensive evaluation of economic competitiveness is still lacking, especially in the case of the LiBH4 / MgH2 storage material. In this study, an assessment with respect to the economic feasibility of implementing complex hydrides as hydrogen storage materials is presented. The cost structure of hydrogen storage systems based on NaAlH4 and LiBH4 / MgH2 is discussed and compared with the conventional high pressure (700 bar) and liquid storage systems. Furthermore, the properties of LiBH4 / MgH2, so-called Li-RHC (Reactive Hydride Composite), are scientifically compared and evaluated on the lab and pilot plant scale. To enhance the reaction rate, the addition of TiCl3 is investigated and high energy ball milling is evaluated as processing technique. The effect of the additive in combination with the processing technique is described in detail. Finally, an optimum set of processing parameters and additive content are identified and can be applied for scaled-up production of the material based on simple models considering energy input during processing. Furthermore, thermodynamic, heat transfer and kinetic properties are experimentally determined by different techniques and analysed as a basis for modelling and designing scaled-up storage systems. The results are analysed and discussed with respect to the reaction mechanisms and reversibility of the system. Heat transfer properties are assessed with respect to the scale-up for larger hydrogen storage systems. Further improvements of the heat transfer were achieved by compacting the material. In this regard, the influence of the compaction pressure on the apparent density, thermal conductivity and sorption behaviour, was investigated in detail. Finally, scaled

  5. Hydrogenation of cyclohexene with LaNi5−xAlxHn metal hydrides suspended in cyclohexane or ethanol

    NARCIS (Netherlands)

    Snijder, E.D.; Versteeg, G.F.; Swaaij, W.P.M. van

    1993-01-01

    The hydrogenation of cyclohexene on the metal hydride forming alloys LaNi4.8Al0.2, LaNi4.9Al0.1 and LaNi5, all suspended in cyclohexane and LaNi5 suspended in ethanol, has been investigated. Two sources for hydrogen are recognized: hydrogen supplied by the gas phase and hydrogen which is available i

  6. Hydrogenation of cyclohexene with LaNi5-xAlxHn metal hydrides, suspended in cyclohexane or ethanol

    NARCIS (Netherlands)

    Snijder, E.D.; Versteeg, G.F.; Swaaij, van W.P.M.

    1993-01-01

    The hydrogenation of cyclohexene on the metal hydride forming alloys LaNi4.8Al0.2, LaNi4.9Al0.1 and LaNi5, all suspended in cyclohexane and LaNi5 suspended in ethanol, has been investigated. Two sources for hydrogen are recognized: hydrogen supplied by the gas phase and hydrogen which is available i

  7. Hydrogen Absorbing Material in Carbonaceous-Metal Hydride

    Directory of Open Access Journals (Sweden)

    Farid Mulana

    2006-06-01

    Full Text Available One of the most promising materials for storing hydrogen in solid state would be included in metal-carbon composites. In order to obtain nanocrystalline metal particles encapsulated by crystalline or amorphous carbon, mechanosynthesis of zirconium-carbonaceous composites and alkali metal-carbonaceous composites was performed. For zirconium-carbonaceous composites, only zirconium-carbon black composite absorbed more hydrogen than expected for a mere mixture with the same composition. The higher hydrogen capacity on the zirconium-carbon black composite would be due to some specific sites on the carbonaceous material created during the milling. Another effect of the composite formation was stabilization of zirconium, that is, the composites did not ignite in air. On alkali metal-carbonaceous composites, carbon black has superior effect in composite formation compared with graphite in which some cooperative effect was only detected on alkali metal-carbon black composite. The effect of the carbonaceous composite formation was resistance to air and anti-sticking characteristics to balls and the wall of the vial during the ball milling.

  8. Multiphysics phase field modeling of hydrogen diffusion and delta-hydride precipitation in alpha-zirconium

    Science.gov (United States)

    Jokisaari, Andrea M.

    Hydride precipitation in zirconium is a significant factor limiting the lifetime of nuclear fuel cladding, because hydride microstructures play a key role in the degradation of fuel cladding. However, the behavior of hydrogen in zirconium has typically been modeled using mean field approaches, which do not consider microstructural evolution. This thesis describes a quantitative microstructural evolution model for the alpha-zirconium/delta-hydride system and the associated numerical methods and algorithms that were developed. The multiphysics, phase field-based model incorporates CALPHAD free energy descriptions, linear elastic solid mechanics, and classical nucleation theory. A flexible simulation software implementing the model, Hyrax, is built on the Multiphysics Object Oriented Simulation Environment (MOOSE) finite element framework. Hyrax is open-source and freely available; moreover, the numerical methods and algorithms that have been developed are generalizable to other systems. The algorithms are described in detail, and verification studies for each are discussed. In addition, analyses of the sensitivity of the simulation results to the choice of numerical parameters are presented. For example, threshold values for the CALPHAD free energy algorithm and the use of mesh and time adaptivity when employing the nucleation algorithm are studied. Furthermore, preliminary insights into the nucleation behavior of delta-hydrides are described. These include a) the sensitivities of the nucleation rate to temperature, interfacial energy, composition and elastic energy, b) the spatial variation of the nucleation rate around a single precipitate, and c) the effect of interfacial energy and nucleation rate on the precipitate microstructure. Finally, several avenues for future work are discussed. Topics encompass the terminal solid solubility hysteresis of hydrogen in zirconium and the effects of the alpha/delta interfacial energy, as well as thermodiffusion, plasticity

  9. Triphosphine-Ligated Copper Hydrides for CO2 Hydrogenation: Structure, Reactivity, and Thermodynamic Studies.

    Science.gov (United States)

    Zall, Christopher M; Linehan, John C; Appel, Aaron M

    2016-08-10

    The copper(I) triphosphine complex LCu(MeCN)PF6 (L = 1,1,1-tris(diphenylphosphinomethyl)ethane), which we recently demonstrated is an active catalyst precursor for hydrogenation of CO2 to formate, reacts with H2 in the presence of a base to form a cationic dicopper hydride, [(LCu)2H]PF6. [(LCu)2H](+) is also an active precursor for catalytic CO2 hydrogenation, with equivalent activity to that of LCu(MeCN)(+), and therefore may be a relevant catalytic intermediate. The thermodynamic hydricity of [(LCu)2H](+) was determined to be 41.0 kcal/mol by measuring the equilibrium constant for this reaction using three different bases. [(LCu)2H](+) and the previously reported dimer (LCuH)2 can be synthesized by the reaction of LCu(MeCN)(+) with 0.5 and 1 equiv of KB(O(i)Pr)3H, respectively. The solid-state structure of [(LCu)2H](+) shows threefold symmetry about a linear Cu-H-Cu axis and significant steric strain imposed by bringing two LCu(+) units together around the small hydride ligand. [(LCu)2H](+) reacts stoichiometrically with CO2 to generate the formate complex LCuO2CH and the solvento complex LCu(MeCN)(+). The rate of the stoichiometric reaction between [(LCu)2H](+) and CO2 is dramatically increased in the presence of bases that coordinate strongly to the copper center, e.g. DBU and TMG. In the absence of CO2, the addition of a large excess of DBU to [(LCu)2H](+) results in an equilibrium that forms LCu(DBU)(+) and also presumably the mononuclear hydride LCuH, which is not directly observed. Due to the significantly enhanced CO2 reactivity of [(LCu)2H](+) under these catalytically relevant conditions, LCuH is proposed to be the catalytically active metal hydride.

  10. A kinetic study of the electrochemical hydrogenation of ethylene

    Energy Technology Data Exchange (ETDEWEB)

    Sedighi, S. [Department of Chemical Engineering and Centre for Catalysis Research and Innovation, University of Ottawa, Ottawa, Ontario K1N 6N5 (Canada); Gardner, C.L., E-mail: cgardner88@sympatico.c [Department of Chemical Engineering and Centre for Catalysis Research and Innovation, University of Ottawa, Ottawa, Ontario K1N 6N5 (Canada)

    2010-02-01

    In this study, we have examined the kinetics of the electrochemical hydrogenation of ethylene in a PEM reactor. While in itself this reaction is of little industrial interest, this reaction can be looked upon as a model reaction for many of the important hydrogenation processes including the refining of heavy oils and the hydrogenation of vegetable oils. To study the electrochemical hydrogenation of ethylene, several experimental techniques have been used including polarization measurements, measurement of the composition of the exit gases and potential step, transient measurements. The results show that the hydrogenation reaction proceeds rapidly and essentially to completion. By fitting the experimental transient data to the results from a zero-dimensional mathematical model of the process, a set of kinetic parameters for the reactions has been obtained that give generally good agreement with the experimental results. It seems probable that similar experimental techniques could be used to study the electrochemical hydrogenation of other unsaturated organic molecules of more industrial significance.

  11. Hybrid functional calculations of potential hydrogen storage material: Complex dimagnesium iron hydride

    KAUST Repository

    Ul Haq, Bakhtiar

    2014-06-01

    By employing the state of art first principles approaches, comprehensive investigations of a very promising hydrogen storage material, Mg 2FeH6 hydride, is presented. To expose its hydrogen storage capabilities, detailed structural, elastic, electronic, optical and dielectric aspects have been deeply analysed. The electronic band structure calculations demonstrate that Mg2FeH6 is semiconducting material. The obtained results of the optical bandgap (4.19 eV) also indicate that it is a transparent material for ultraviolet light, thus demonstrating its potential for optoelectronics application. The calculated elastic properties reveal that Mg2FeH6 is highly stiff and stable hydride. Finally, the calculated hydrogen (H2) storage capacity (5.47 wt.%) within a reasonable formation energy of -78 kJ mol-1, at room temperature, can be easily achievable, thus making Mg2FeH6 as potential material for practical H2 storage applications. Copyright © 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

  12. Investigation and characterization of ball-milled magnesium-based hydrides for hydrogen storage materials

    Science.gov (United States)

    Yang, Jing

    2011-12-01

    Three alloys are prepared through mechanical alloying and the hydrogen storage properties have been investigated systematically. In Mg-Ni and Mg-Ni-Fe alloys, the main binary alloy phase is Mg2Ni, while in Mg-Ni-Fe-Ti alloys, NiTi, FeTi are also found as the main binary phases beside Mg 2Ni. The hydrogen absorption capacities of the three alloys are 2.9wt%, 2.2wt% and 2.3wt% respectively. Absorption content increases with the increasing of milling time, which also increases the amorphous degree of the alloys. The amorphous degree increasing is unfavorable to improve hydrogen storage capacity. Longer milling time will contribute to a higher hydriding/dehydriding rate at a constant temperature. The alloys exhibit a different hydriding behavior when temperature was increased from 473K to 673K. The alloys particles became finer after long time milling, which led to a decrease in the different distance of the hydrogen atoms.

  13. Rapid hydrogen gas generation using reactive thermal decomposition of uranium hydride.

    Energy Technology Data Exchange (ETDEWEB)

    Kanouff, Michael P.; Van Blarigan, Peter; Robinson, David B.; Shugard, Andrew D.; Gharagozloo, Patricia E.; Buffleben, George M.; James, Scott Carlton; Mills, Bernice E.

    2011-09-01

    Oxygen gas injection has been studied as one method for rapidly generating hydrogen gas from a uranium hydride storage system. Small scale reactors, 2.9 g UH{sub 3}, were used to study the process experimentally. Complimentary numerical simulations were used to better characterize and understand the strongly coupled chemical and thermal transport processes controlling hydrogen gas liberation. The results indicate that UH{sub 3} and O{sub 2} are sufficiently reactive to enable a well designed system to release gram quantities of hydrogen in {approx} 2 seconds over a broad temperature range. The major system-design challenge appears to be heat management. In addition to the oxidation tests, H/D isotope exchange experiments were performed. The rate limiting step in the overall gas-to-particle exchange process was found to be hydrogen diffusion in the {approx}0.5 {mu}m hydride particles. The experiments generated a set of high quality experimental data; from which effective intra-particle diffusion coefficients can be inferred.

  14. Hydrogen Storage Characteristics of Metal Hydro-Borate and Transition Element-Added Magnesium Hydride

    Energy Technology Data Exchange (ETDEWEB)

    Song, Myoung Youp; Kwak, Young Jun [Chonbuk National University, Jeonju (Korea, Republic of); Park, Hye Ryoung [Chonnam National University, Gwangju (Korea, Republic of)

    2016-07-15

    A metal hydro-borate Zn(BH{sub 4}){sub 2} was prepared by milling ZnCl{sub 2} and NaBH{sub 4} in a planetary ball mill in an Ar atmosphere. This sample contained NaCl. 95 wt% MgH{sub 2}-2.5 wt% Zn(BH{sub 4}){sub 2}-2.5 wt% Ni samples [named MgH{sub 2}-2.5Zn(BH{sub 4}){sub 2}-2.5Ni] were then prepared by milling in a planetary ball mill in a hydrogen atmosphere. The hydrogen absorption and release properties of the prepared samples were investigated. In particular, variations in the initial hydriding and dehydriding rates with temperature were examined. MgH{sub 2}-2.5Zn(BH{sub 4}){sub 2}-2.5Ni dehydrided at the fourth cycle contained Mg, MgO, and small amounts of β-MgH2 and Mg2Ni. The sample after hydriding-dehydriding cycling had a slightly smaller average particle size and a larger BET specific surface area than the sample after milling. Increasing the temperature from 573 K to 623 K led to a decrease in the initial hydriding rate. The initial dehydriding rate increased as the temperature increased from 573 K to 643 K. At 573 K under 12 bar H{sub 2}, the sample absorbed 3.85 wt% H for 2.5 min, 4.60 wt% H for 5 min, 4.64 wt% H for 10 min, and 4.80 wt% H for 60 min. The MgH{sub 2}-2.5Zn(BH{sub 4}){sub 2}-2.5Ni had an effective hydrogen storage capacity (the quantity of hydrogen absorbed for 60 min) of near 5 wt% (4.96 wt% at 593 K).

  15. Development and investigation of novel nanostructures and complex hydrides for hydrogen storage

    Science.gov (United States)

    Niemann, Michael Ulrich

    2009-12-01

    Over the past few years, the need for a clean and renewable fuel has sharply risen. This is due to increasing fossil fuel costs and the desire to limit or eliminate harmful byproducts which are created during the burning of these fuels. Hydrogen is the most abundant element in the universe and can be used in either fuel cells or traditional internal combustion engines to produce energy with no harmful emissions. One of the main obstacles facing the implementation of a hydrogen economy is its storage. Classical methods of storage involve either high and unsafe pressures or liquid storage involving a large amount of energy. Two alternative hydrogen storage methods are investigated---physisorption, which is the weak chemical bonding to a material, as well as chemisorption, which is a strong chemical bond of hydrogen to a host material. Polyaniline, a conducting polymer, is investigated in both its bulk form as well as in nanostructured forms, more precisely nanofibers and nanospheres, to store hydrogen via physisorption. It is found the bulk form of polyaniline can store only approximately 0.5wt.% hydrogen, which is far short of the 6wt.% required for practical applications. Nanofibers and nanospheres, however, have been developed, which can store between 4wt.% and 10wt.% of hydrogen at room temperature with varying kinetics. A new complex metal hydride comprised of LiBH4, LiNH 2 and MgH2 has been developed to store hydrogen via chemisorption. While the parent compounds require high temperatures and suffer of slow kinetics for hydrogen sorption, the work performed as part of this dissertation shows that optimized processing conditions reduce the hydrogen release temperature from 250°C to approximately 150°C, while the addition of nano sized materials has been found to increase the kinetics of hydrogen sorption as well as further decrease the hydrogen release temperature, making this one of the first viable hydrogen storage materials available. This is the first time

  16. Hydrogen release reactions of Al-based complex hydrides enhanced by vibrational dynamics and valences of metal cations.

    Science.gov (United States)

    Sato, T; Ramirez-Cuesta, A J; Daemen, L; Cheng, Y-Q; Tomiyasu, K; Takagi, S; Orimo, S

    2016-09-27

    Hydrogen release from Al-based complex hydrides composed of metal cation(s) and [AlH4](-) was investigated using inelastic neutron scattering viewed from vibrational dynamics. The hydrogen release followed the softening of translational and [AlH4](-) librational modes, which was enhanced by vibrational dynamics and the valence(s) of the metal cation(s).

  17. Efficient Electrochemical Hydrogen Peroxide Generation in Water Project

    Data.gov (United States)

    National Aeronautics and Space Administration — An electrochemical cell is proposed for the efficient generation of 3% hydrogen peroxide (H2O2) in pure water using only power, oxygen and water. H2O2 is an...

  18. Analysis of Pressure Variations in a Low-Pressure Nickel-Hydrogen Battery– Part 2: Cells with Metal Hydride Storage

    Science.gov (United States)

    Purushothaman, B. K.; Wainright, J. S.

    2012-01-01

    A sub-atmospheric pressure nickel hydrogen (Ni-H2) battery with metal hydride for hydrogen storage is developed for implantable neuroprosthetic devices. Pressure variations during charge and discharge of the cell are analyzed at different states of charge and are found to follow the desorption curve of the pressure composition isotherm (PCI) of the metal hydride. The measured pressure agreed well with the calculated theoretical pressure based on the PCI and is used to predict the state of charge of the battery. Hydrogen equilibration with the metal hydride during charge/discharge cycling is fast when the pressure is in the range from 8 to 13 psia and slower in the range from 6 to 8 psia. The time constant for the slower hydrogen equilibration, 1.37h, is similar to the time constant for oxygen recombination and therefore pressure changes due to different mechanisms are difficult to estimate. The self-discharge rate of the cell with metal hydride is two times lower in comparison to the cell with gaseous hydrogen storage alone and is a result of the lower pressure in the cell when the metal hydride is used. PMID:22711974

  19. Analysis of Pressure Variations in a Low-Pressure Nickel-Hydrogen Battery- Part 2: Cells with Metal Hydride Storage.

    Science.gov (United States)

    Purushothaman, B K; Wainright, J S

    2012-05-15

    A sub-atmospheric pressure nickel hydrogen (Ni-H(2)) battery with metal hydride for hydrogen storage is developed for implantable neuroprosthetic devices. Pressure variations during charge and discharge of the cell are analyzed at different states of charge and are found to follow the desorption curve of the pressure composition isotherm (PCI) of the metal hydride. The measured pressure agreed well with the calculated theoretical pressure based on the PCI and is used to predict the state of charge of the battery. Hydrogen equilibration with the metal hydride during charge/discharge cycling is fast when the pressure is in the range from 8 to 13 psia and slower in the range from 6 to 8 psia. The time constant for the slower hydrogen equilibration, 1.37h, is similar to the time constant for oxygen recombination and therefore pressure changes due to different mechanisms are difficult to estimate. The self-discharge rate of the cell with metal hydride is two times lower in comparison to the cell with gaseous hydrogen storage alone and is a result of the lower pressure in the cell when the metal hydride is used.

  20. Hydrogen storage property of sandwiched magnesium hydride nanoparticle thin film

    Energy Technology Data Exchange (ETDEWEB)

    Barcelo, Steven; Rogers, Matthew; Grigoropoulos, Costas P.; Mao, Samuel S. [Lawrence Berkeley National Laboratory and Department of Mechanical Engineering, University of California at Berkeley, Berkeley, CA 94720 (United States)

    2010-07-15

    Hydrogen sorption property of magnesium (Mg) in the form of sandwiched Pd/Mg/Pd films is investigated. Pulsed laser deposition method was applied to deposit the samples consisting of films of nanoparticles. The enthalpy of formation of MgH{sub 2} was found to be -68 kJ/mol H{sub 2} for films with nanoparticle size on the order of 50 nm, which is smaller than the value for bulk MgH{sub 2} and may be explained by the concept of excess volume. (author)

  1. IMPROVEMENT OF ELECTROCHEMICAL PROCESSES IN HYDROGEN POWER ENGINEERING

    Directory of Open Access Journals (Sweden)

    Covaliova O.V.

    2011-04-01

    Full Text Available The possibility is studied of using the three-dimensional voluminous-porous electrodes made of the carbonic-fibrous materials and foamy metals, which surface is covered with Ni-Re alloy, for hydrogen electrochemical generation. Electrode surface modification makes it possible to obtain high reactive surface with low overvoltage of hydrogen evolution. The design is given of the developed compact electrochemical reactors for hydrogen power engineering. The method is described of oxygen-hydrogen mixture separation in the water electrolysis processes.

  2. Probing the chemistry of nickel/metal hydride battery cells using electrochemical impedance spectroscopy

    Science.gov (United States)

    Isaac, Bryan J.

    1994-01-01

    Electrochemical Impedance Spectroscopy (EIS) is a valuable tool for investigating the chemical and physical processes occurring at electrode surfaces. It offers information about electron transfer at interfaces, kinetics of reactions, and diffusion characteristics of the bulk phase between the electrodes. For battery cells, this technique offers another advantage in that it can be done without taking the battery apart. This non-destructive analysis technique can thus be used to gain a better understanding of the processes occurring within a battery cell. This also raises the possibility of improvements in battery design and identification or prediction of battery characteristics useful in industry and aerospace applications. EIS as a technique is powerful and capable of yielding significant information about the cell, but it also requires that the many parameters under investigation can be resolved. This implies an understanding of the processes occurring in a battery cell. Many battery types were surveyed in this work, but the main emphasis was on nickel/metal hydride batteries.

  3. Scattering influences in quantitative fission neutron radiography for the in situ analysis of hydrogen distribution in metal hydrides

    Science.gov (United States)

    Börries, S.; Metz, O.; Pranzas, P. K.; Bücherl, T.; Söllradl, S.; Dornheim, M.; Klassen, T.; Schreyer, A.

    2015-10-01

    In situ neutron radiography allows for the time-resolved study of hydrogen distribution in metal hydrides. However, for a precise quantitative investigation of a time-dependent hydrogen content within a host material, an exact knowledge of the corresponding attenuation coefficient is necessary. Additionally, the effect of scattering has to be considered as it is known to violate Beer's law, which is used to determine the amount of hydrogen from a measured intensity distribution. Within this study, we used a metal hydride inside two different hydrogen storage tanks as host systems, consisting of steel and aluminum. The neutron beam attenuation by hydrogen was investigated in these two different setups during the hydrogen absorption process. A linear correlation to the amount of absorbed hydrogen was found, allowing for a readily quantitative investigation. Further, an analysis of scattering contributions on the measured intensity distributions was performed and is described in detail.

  4. Scattering influences in quantitative fission neutron radiography for the in situ analysis of hydrogen distribution in metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Börries, S., E-mail: stefan.boerries@hzg.de [Helmholtz-Zentrum Geesthacht, Centre for Materials and Coastal Research, Max-Planck-Strasse 1, D-21502 Geesthacht (Germany); Metz, O.; Pranzas, P.K. [Helmholtz-Zentrum Geesthacht, Centre for Materials and Coastal Research, Max-Planck-Strasse 1, D-21502 Geesthacht (Germany); Bücherl, T. [ZTWB Radiochemie München (RCM), Technische Universität München (TUM), Walther-Meissner-Str. 3, D-85748 Garching (Germany); Söllradl, S. [Forschungs-Neutronenquelle Heinz Maier-Leibnitz (FRMII), Technische Universität München (TUM), Lichtenbergstr. 1, D-85748 Garching (Germany); Dornheim, M.; Klassen, T.; Schreyer, A. [Helmholtz-Zentrum Geesthacht, Centre for Materials and Coastal Research, Max-Planck-Strasse 1, D-21502 Geesthacht (Germany)

    2015-10-11

    In situ neutron radiography allows for the time-resolved study of hydrogen distribution in metal hydrides. However, for a precise quantitative investigation of a time-dependent hydrogen content within a host material, an exact knowledge of the corresponding attenuation coefficient is necessary. Additionally, the effect of scattering has to be considered as it is known to violate Beer's law, which is used to determine the amount of hydrogen from a measured intensity distribution. Within this study, we used a metal hydride inside two different hydrogen storage tanks as host systems, consisting of steel and aluminum. The neutron beam attenuation by hydrogen was investigated in these two different setups during the hydrogen absorption process. A linear correlation to the amount of absorbed hydrogen was found, allowing for a readily quantitative investigation. Further, an analysis of scattering contributions on the measured intensity distributions was performed and is described in detail.

  5. Studies of hydrogen absorption and desorption processes in advanced intermetallic hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Sato, Masashi

    2005-07-01

    This work is a part of the research program performed in the Department of Energy Systems, Institute for Energy Technology (Kjeller, Norway), which is focused on the development of the advanced hydrogen storage materials. The activities are aimed on studies of the mechanisms of hydrogen interactions with intermetallic alloys with focus on establishing an interrelation between the crystal structure, thermodynamics and kinetics of the processes in the metal-hydrogen systems, on the one hand, and hydrogen storage properties (capacity, rates of desorption, hysteresis). Many of the materials under investigation have potential to be applied in applications, whereas some already have been commercialised in the world market. A number of metals take up considerable amounts of hydrogen and form chemical compounds with H, metal hydrides. Unfortunately, binary hydrides are either very stable (e.g. for the rare earth metals [RE], Zr, Ti, Mg: metal R) or are formed at very high applied pressures of hydrogen gas (e.g. for the transition metals, Ni, Co, Fe, etc.: Metal T). However, hydrogenation process becomes easily reversible at very convenient from practical point of view conditions, around room temperature and at H2 pressures below 1 MPa for the two-component intermetallic alloys R{sub x}T{sub y}. This raised and maintains further interest to the intermetallic hydrides as solid H storage materials. Materials science research of this thesis is focused on studies of the reasons staying behind the beneficial effect of two non-transition elements M(i.e., In and Sn) contributing to the formation of the ternary intermetallic alloys R{sub x}T{sub y}M{sub 2}., on the hydrogen storage behaviours. Particular focus is on two aspects where the remarkable improvement of ordinary metal hydrides is achieved via introduction of In and Sn: a) Increase of the volume density of stored hydrogen in solid materials to the record high level. b) Improvement of the kinetics of hydrogen charge and

  6. Hydrogen storage properties of Na-Li-Mg-Al-H complex hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Tang Xia [United Technologies Research Center, 411 Silver Lane, East Hartford, CT 06108 (United States)], E-mail: tangx@utrc.utc.com; Opalka, Susanne M.; Laube, Bruce L. [United Technologies Research Center, 411 Silver Lane, East Hartford, CT 06108 (United States); Wu Fengjung; Strickler, Jamie R. [Albemarle Corporation, Gulf States Road, Baton Rouge, LA 70805 (United States); Anton, Donald L. [Savannah River National Laboratory, 227 Gateway Dr., Aiken, SC 29808 (United States)

    2007-10-31

    Lightweight complex hydrides have attracted attention for their high storage hydrogen capacity. NaAlH{sub 4} has been widely studied as a hydrogen storage material for its favorable reversible operating temperature and pressure range for automotive fuel cell applications. The increased understanding of NaAlH{sub 4} has led to an expanded search for high capacity materials in mixed alkali and akali/alkaline earth alanates. In this study, promising candidates in the Na-Li-Mg-Al-H system were evaluated using a combination of experimental chemistry, atomic modeling, and thermodynamic modeling. New materials were synthesized using solid state and solution based processing methods. Their hydrogen storage properties were measured experimentally, and the test results were compared with theoretical modeling assessments.

  7. Minimum Entropy Generation Theorem Investigation and Optimization of Metal Hydride Alloy Hydrogen Storage

    Directory of Open Access Journals (Sweden)

    Chi-Chang Wang

    2014-05-01

    Full Text Available The main purpose of this paper is to carry out numerical simulation of the hydrogen storage on exothermic reaction of metal hydride LaNi5 alloy container. In addition to accelerating the reaction speed of the internal metal hydride by internal control tube water-cooled mode, analyze via the application of second law of thermodynamics the principle of entropy generation. Use COMSOL Mutilphysics 4.3 a to engage in finite element method value simulation on two-dimensional axisymmetric model. Also on the premise that the internal control tube parameters the radius ri, the flow rate U meet the metal hydride saturation time, observe the reaction process of two parameters on the tank, entropy distribution and the results of the accumulated entropy. And try to find the internal tube parameter values of the minimum entropy, whose purpose is to be able to identify the reaction process and the reaction results of internal tank’s optimum energy conservation.

  8. Aging Effects on the Hydrogen Storage Characteristics of Li-Mg-B-N-H Complex Hydrides

    Science.gov (United States)

    Srinivasan, Sesha; Vickers, Eric; Mulharan, James; Darkazalli, Gazi; Goswami, Yogi; Stefanakos, Elias; FLPoly-CERC Collaboration

    2015-03-01

    The aging effects on the hydrogen storage characteristics and chemical formulations of the complex hydrides are discussed in this study. The aging effects due to atmospheric events such as oxygen and moisture coverage and self-decomposition are currently under investigation. The candidate material chosen for this study is Lithium/Magnesium based complex hydride LiBH4/LiNH2/MgH2. These materials were prepared using high energy ball milling under Ar/H2 atmosphere with different milling durations. The chemical, structural and microstructural characteristics of the synthesized and aged materials were compared and investigated using TGA/DSC, FTIR, XRD, BET and SEM analytical tools. Hydrogen storage properties such as hydrogen sorption kinetics, cycle life and pressure-composition isotherm (PCI) was examined via high pressure, high temperature Sievert's type apparatus. This current study will shed light to compare and contrast the above mentioned characteristics for the aged samples practically at the same experimental conditions. Furthermore, we have investigated the relationship between the aging effects with respect to the crystallite sizes of the candidate compounds and their nano-dopant variants. We acknowledge the grant from Florida Energy Systems Consortium and support from Florida Polytechnic University.

  9. Metal hydride hydrogen and heat storage systems as enabling technology for spacecraft applications

    Energy Technology Data Exchange (ETDEWEB)

    Reissner, Alexander, E-mail: reissner@fotec.at [FOTEC Forschungs- und Technologietransfer GmbH, Viktor Kaplan Straße 2, 2700 Wiener Neustadt (Austria); University of Applied Sciences Wiener Neustadt, Johannes Gutenberg-Straße 3, 2700 Wiener Neustadt (Austria); Pawelke, Roland H.; Hummel, Stefan; Cabelka, Dusan [FOTEC Forschungs- und Technologietransfer GmbH, Viktor Kaplan Straße 2, 2700 Wiener Neustadt (Austria); Gerger, Joachim [University of Applied Sciences Wiener Neustadt, Johannes Gutenberg-Straße 3, 2700 Wiener Neustadt (Austria); Farnes, Jarle, E-mail: Jarle.farnes@prototech.no [CMR Prototech AS, Fantoftvegen 38, PO Box 6034, 5892 Bergen (Norway); Vik, Arild; Wernhus, Ivar; Svendsen, Tjalve [CMR Prototech AS, Fantoftvegen 38, PO Box 6034, 5892 Bergen (Norway); Schautz, Max, E-mail: max.schautz@esa.int [European Space Agency, ESTEC – Keplerlaan 1, 2201 AZ Noordwijk Zh (Netherlands); Geneste, Xavier, E-mail: xavier.geneste@esa.int [European Space Agency, ESTEC – Keplerlaan 1, 2201 AZ Noordwijk Zh (Netherlands)

    2015-10-05

    Highlights: • A metal hydride tank concept for heat and hydrogen storage is presented. • The tank is part of a closed-loop reversible fuel cell system for space application. • For several engineering issues specific to the spacecraft application, solutions have been developed. • The effect of water contamination has been approximated for Ti-doped NaAlH{sub 4}. • A novel heat exchanger design has been realized by Selective Laser Melting. - Abstract: The next generation of telecommunication satellites will demand a platform payload performance in the range of 30+ kW within the next 10 years. At this high power output, a Regenerative Fuel Cell Systems (RFCS) offers an efficiency advantage in specific energy density over lithium ion batteries. However, a RFCS creates a substantial amount of heat (60–70 kJ per mol H{sub 2}) during fuel cell operation. This requires a thermal hardware that accounts for up to 50% of RFCS mass budget. Thus the initial advantage in specific energy density is reduced. A metal hydride tank for combined storage of heat and hydrogen in a RFCS may overcome this constraint. Being part of a consortium in an ongoing European Space Agency project, FOTEC is building a technology demonstrator for such a combined hydrogen and heat storage system.

  10. Characteristics of Hydrogen Storage Alloy Mg2Ni Produced by Hydriding Combustion Synthesis

    Institute of Scientific and Technical Information of China (English)

    Qian LI; Qin LIN; Lijun JIANG; Kou-chih CHOU; Feng ZHAN; Qiang ZHENG

    2004-01-01

    A high activity and large capacity of hydrogen storage alloy Mg2Ni by hydriding combustion synthesis was investigatedby means of pressure composition isotherms, X-ray diffraction and scanning electron microscopy. The results showedthat the maximum hydrogen absorption capacity of Mg2Ni is 3.25 mass fraction at 523 K, just after synthesis withoutany activation. The relationships between the equilibrium plateau pressure and the temperature for Mg2Ni were lgp(0.1 Mpa)=3026/T+5.814 (523 K≤ T ≤623 K) for hydriding and Igp (0.1 Mpa)=-3613/T+6.715 (523 K≤T ≤623 K) for dehydriding. The kinetic equation is [-ln(1 - α)]3/2 = kt and the apparent activation energy for thenucleation and growth-controlled hydrogen absorption and desorption were determined to be 64.3±2.31 kJ/(mol.H2)and 59.9±2.99 kJ/(moI.H2) respectively.

  11. Characteristics of multi-component MI-based hydrogen storage alloys and their hydride electrodes

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A series of multi-component MI-based hydrogen storage alloys with a cobalt atomic ratio of 0.40-0.75 w ere prepared. The electrochemical properties under different charge-discharge conditions and PCT characteristics measured by electrochemical method were investigated. The addition of other alloying elements for partial substitution of Co lowers the hydrogen equilibrium pressure and discharge capacity, but improves the cycling stability and makes the alloys keep nearly the same rate discharge capability and high-temperature discharge capability as those of the compared alloy.The reasons were discussed.

  12. Reversible hydrogen storage properties of Ti-doped lithium aluminium hydride

    Institute of Scientific and Technical Information of China (English)

    WANG; Tong-tao; WANG; Shu-mao; JIANG; Li-jun; LIU; Xiao-peng

    2005-01-01

    In this paper our work on lithium aluminium hydride doping with Ti(OBu)4by mechanical milling was showed. Its thermodynamic and kinetics were enhanced greatly and its reversible hydrogen storage capacity could reach 3. 0% (mass fraction). From the X-ray diffraction (XRD) patterns, we found that a lot of LiAlH4 had been decomposed to Li3AlH6 and Al. The catalyst Ti (OBu)4 couldn't be found after ball-milling, instead TiAl3 appeared. But the locations of Ti atoms are still not determined.

  13. Thermodynamically destabilized hydride formation in "bulk" Mg-AlTi multilayers for hydrogen storage.

    Science.gov (United States)

    Kalisvaart, Peter; Shalchi-Amirkhiz, Babak; Zahiri, Ramin; Zahiri, Beniamin; Tan, XueHai; Danaie, Mohsen; Botton, Gianluigi; Mitlin, David

    2013-10-21

    Thermodynamic destabilization of MgH2 formation through interfacial interactions in free-standing Mg-AlTi multilayers of overall "bulk" (0.5 μm) dimensions with a hydrogen capacity of up to 5.5 wt% is demonstrated. The interfacial energies of Mg-AlTi and Mg-Ti (examined as a baseline) are calculated to be 0.81 and 0.44 J m(-2). The enhanced interfacial energy of AlTi opens the possibility of creating ultrathin alloy interlayers that provide further thermodynamic improvements in metal hydrides.

  14. Hydrogen desorption properties of magnesium hydride catalyzed multiply with carbon and silicon

    Energy Technology Data Exchange (ETDEWEB)

    Klimkowicz, Alicja [AGH University of Science and Technology Faculty of Energy and Fuels, al. A. Mickiewicza 30, 30-059 Krakow (Poland); Shibaura Institute of Technology, Department of Engineering Science and Mechanics, 3-7-5 Toyosu, Koto-ku 135-8548, Tokyo (Japan); Takasaki, Akito, E-mail: takasaki@sic.shibaura-it.ac.jp [Shibaura Institute of Technology, Department of Engineering Science and Mechanics, 3-7-5 Toyosu, Koto-ku 135-8548, Tokyo (Japan); Gondek, Łukasz; Figiel, Henryk [AGH University of Science and Technology, Faculty of Physics and Applied Computer Science, al. A. Mickiewicza 30, 30-059 Krakow (Poland); Świerczek, Konrad [AGH University of Science and Technology Faculty of Energy and Fuels, al. A. Mickiewicza 30, 30-059 Krakow (Poland)

    2015-10-05

    Highlights: • Crystal structure of 2 mol MgH{sub 2} + (1 − X) mol C + X mol Si (for X = 0, 0.25, 0.5, 0.75 and 1). • Enhanced hydrogen desorption properties. • Lowered temperature of hydrogen desorption for MgH{sub 2} with the multiple addition of C and Si. • Distribution of Si and C on MgH{sub 2} particles after mechanical milling. - Abstract: Magnesium hydride (MgH{sub 2}) is considered as one of hydrogen storage materials. However, the application is limited because of slow hydrogen kinetics and high thermodynamic stability. In this study, MgH{sub 2} powders were mechanically milled with graphite (C) and/or silicon (Si) powders, and effect of multiple addition of C and Si on hydrogen desorption properties was investigated. The multiple addition caused a decrease of the hydrogen desorption (onset and peak) temperatures more than single addition, and the lowest activation energy for hydrogen desorption, 62 kJ/mol, was obtained from sample powders of (2 mol MgH{sub 2} + 0.5 mol C + 0.5 mol Si). The surface of the sample powders after mechanical milling revealed a good distribution of C on the MgH{sub 2} surface and a presence of finer Si particles.

  15. Hydrogen storage properties of carbon nanomaterials and carbon containing metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Maehlen, Jan Petter

    2003-07-01

    The topic of this thesis is structural investigations of carbon containing materials in respect to their hydrogen storage properties. This work was initially triggered by reports of extremely high hydrogen storage capacities of specific carbon nanostructures. It was decided to try to verify and understand the mechanisms in play in case of the existence of such high hydrogen densities in carbon. Two different routes towards the goal were employed; by studying selected hydrides with carbon as one of its constituents (mainly employing powder diffraction techniques in combination with hydrogen absorption and desorption measurements) and by carefully conducting hydrogen sorption experiments on what was believed to be the most ''promising'' carbon nanomaterial sample. In the latter case, a lot of effort was attributed to characterisations of different carbon nanomaterial containing samples with the aid of electron microscopy. Three different carbon-containing metal hydride systems, Y2C-H, YCoC-H and Y5SiC0.2-H, were examined. A relation between hydrogen occupation and the local arrangement of metal and carbon atoms surrounding the hydrogen sites was established. Several characteristic features of the compounds were noted in addition to solving the structure of the former unknown deuterideY5Si3C0.2D2.0 by the use of direct methods. Several carbon-nanomaterial containing samples were studied by means of transmission electron microscopy and powder diffraction, thus gaining knowledge concerning the structural aspects of nanomaterials. Based on these investigations, a specific sample containing a large amount of open-ended single-wall carbon nanotubes was chosen for subsequent hydrogen storage experiments. The latter experiments revealed moderate hydrogen storage capacities of the nanotubes not exceeding the values obtained for more conventional forms of carbon. These two different routes in investigating the hydrogen storage properties of carbon and

  16. Actuation of Pneumatic Artificial Muscle via Hydrogen Absorption/Desorption of Metal Hydride-LaNi5

    OpenAIRE

    Thanana Nuchkrua; Thananchai Leephakpreeda

    2015-01-01

    This paper presents experimental studies on mechanical actuations of a pneumatic artificial muscle (PAM), which is driven by hydrogen gas based metal hydride (MH). The dynamic performances of hydrogen absorption/desorption, taking place within a MH reactor, are controlled via implementing cooling/heating effects of a thermoelectric module (TEM). Hydrogen pressure is applied as a driving force to commanding work outputs of the PAM as desired mechanical actuations. Due to strong inherent nonlin...

  17. Electrochemical characterization of melt spun AB{sub 5} alloys for metal hydride batteries

    Energy Technology Data Exchange (ETDEWEB)

    Brateng, Randi

    2003-05-01

    This thesis is part of a larger research project where two metal hydride forming AB{sub 5} type alloys have been investigated. A slightly non-stoichiometric alloy with mischmetal on A-site and nickel, cobalt, manganese and aluminium on B-site has been characterized. The composition of this material, which will be referred to as Mm(NiCoMnA1){sub 5.15}, is close to the normal battery composition. The other alloy characterized is LaNi{sub 5} based, where nickel is partly substituted with tin. This material will later be referred to as La(NiSn){sub 5}. These materials were produced by melt spinning to vary the cooling rate during solidification. The main purpose of the study has been to characterize the electrochemical properties related to battery performance. The production as well as the metallurgical and structural characterization of the materials were performed in another part of the project. For Mm(NiCoMnA1){sub 5.15} the unit cell volume was dependent on the cooling rate before heat treatment, while the unit cell volume was almost independent of the cooling rate for La(NiSn){sub 5}. For both alloy compositions, the electrochemical properties seemed to change with varying cooling rate. The desorption equilibrium potential, the discharge capacity when discharging at a low current and the deterioration rate were found to be reduced with decreasing unit cell volume and increased with increasing unit cell volume, before heat treatment of Mm(NiCoMnA1){sub 5.15}. The self discharge rate was observed to be inversely proportional to the unit cell volume for this material. For not heat treated La(NiSn){sub 5}, produced at different cooling rates, the desorption equilibrium potential decreased when the self discharge rate and the discharge capacity increased after cycling for 300 cycles. The deterioration rate decreased when the desorption equilibrium potential was reduced for La(NiSn){sub 5}. The electrochemical parameters both before and after heat treatment of La

  18. Studies of hydrogen absorption and desorption processes in advanced intermetallic hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Sato, Masashi

    2005-07-01

    This work is a part of the research program performed in the Department of Energy Systems, Institute for Energy Technology (Kjeller, Norway), which is focused on the development of the advanced hydrogen storage materials. The activities are aimed on studies of the mechanisms of hydrogen interactions with intermetallic alloys with focus on establishing an interrelation between the crystal structure, thermodynamics and kinetics of the processes in the metal-hydrogen systems, on the one hand, and hydrogen storage properties (capacity, rates of desorption, hysteresis). Many of the materials under investigation have potential to be applied in applications, whereas some already have been commercialised in the world market. A number of metals take up considerable amounts of hydrogen and form chemical compounds with H, metal hydrides. Unfortunately, binary hydrides are either very stable (e.g. for the rare earth metals [RE], Zr, Ti, Mg: metal R) or are formed at very high applied pressures of hydrogen gas (e.g. for the transition metals, Ni, Co, Fe, etc.: Metal T). However, hydrogenation process becomes easily reversible at very convenient from practical point of view conditions, around room temperature and at H2 pressures below 1 MPa for the two-component intermetallic alloys R{sub x}T{sub y}. This raised and maintains further interest to the intermetallic hydrides as solid H storage materials. Materials science research of this thesis is focused on studies of the reasons staying behind the beneficial effect of two non-transition elements M(i.e., In and Sn) contributing to the formation of the ternary intermetallic alloys R{sub x}T{sub y}M{sub 2}., on the hydrogen storage behaviours. Particular focus is on two aspects where the remarkable improvement of ordinary metal hydrides is achieved via introduction of In and Sn: a) Increase of the volume density of stored hydrogen in solid materials to the record high level. b) Improvement of the kinetics of hydrogen charge and

  19. Kinetic Modification on Hydrogen Desorption of Lithium Hydride and Magnesium Amide System

    Directory of Open Access Journals (Sweden)

    Hiroki Miyaoka

    2015-06-01

    Full Text Available Various synthesis and rehydrogenation processes of lithium hydride (LiH and magnesium amide (Mg(NH22 system with 8:3 molar ratio are investigated to understand the kinetic factors and effectively utilize the essential hydrogen desorption properties. For the hydrogen desorption with a solid-solid reaction, it is expected that the kinetic properties become worse by the sintering and phase separation. In fact, it is experimentally found that the low crystalline size and the close contact of LiH and Mg(NH22 lead to the fast hydrogen desorption. To preserve the potential hydrogen desorption properties, thermochemical and mechanochemical rehydrogenation processes are investigated. Although the only thermochemical process results in slowing the reaction rate due to the crystallization, the ball-milling can recover the original hydrogen desorption properties. Furthermore, the mechanochemical process at 150 °C is useful as the rehydrogenation technique to preserve the suitable crystalline size and mixing state of the reactants. As a result, it is demonstrated that the 8LiH and 3Mg(NH22 system is recognized as the potential hydrogen storage material to desorb more than 5.5 mass% of H2 at 150 °C.

  20. Kinetic Modification on Hydrogen Desorption of Lithium Hydride and Magnesium Amide System.

    Science.gov (United States)

    Miyaoka, Hiroki; Wang, Yongming; Hino, Satoshi; Isobe, Shigehito; Tokoyoda, Kazuhiko; Ichikawa, Takayuki; Kojima, Yoshitsugu

    2015-06-29

    Various synthesis and rehydrogenation processes of lithium hydride (LiH) and magnesium amide (Mg(NH₂)₂) system with 8:3 molar ratio are investigated to understand the kinetic factors and effectively utilize the essential hydrogen desorption properties. For the hydrogen desorption with a solid-solid reaction, it is expected that the kinetic properties become worse by the sintering and phase separation. In fact, it is experimentally found that the low crystalline size and the close contact of LiH and Mg(NH₂)₂ lead to the fast hydrogen desorption. To preserve the potential hydrogen desorption properties, thermochemical and mechanochemical rehydrogenation processes are investigated. Although the only thermochemical process results in slowing the reaction rate due to the crystallization, the ball-milling can recover the original hydrogen desorption properties. Furthermore, the mechanochemical process at 150 °C is useful as the rehydrogenation technique to preserve the suitable crystalline size and mixing state of the reactants. As a result, it is demonstrated that the 8LiH and 3Mg(NH₂)₂ system is recognized as the potential hydrogen storage material to desorb more than 5.5 mass% of H₂ at 150 °C.

  1. Photoelectron Spectroscopy of Transition Metal Hydride Cluster Anions and Their Roles in Hydrogenation Reactions

    Science.gov (United States)

    Zhang, Xinxing; Bowen, Kit

    The interaction between transition metals and hydrogen has been an intriguing research topic for such applications as hydrogen storage and catalysis of hydrogenation and dehydrogenation. Special bonding features between TM and hydrogen are interesting not only because they are scarcely reported but also because they could help to discover and understand the nature of chemical bonding. Very recently, we discovered a PtZnH5- cluster which possessed an unprecedented planar pentagonal coordination between the H5- moiety and Pt, and exhibited special σ-aromaticity. The H5-kernel as a whole can be viewed as a η5-H5 ligand for Pt. As the second example, an H2 molecule was found to act as a ligand in the PdH3-cluster, in which two H atoms form a η2-H2 type of ligation to Pd. These transition metal hydride clusters were considered to be good hydrogen sources for hydrogenation. The reactions between PtHn- and CO2 were investigated. We observed formate in the final product H2Pt(HCO2)- .

  2. In-situ Hydrogen Sorption 2D-ACAR Facility for the Study of Metal Hydrides for Hydrogen Storage

    Science.gov (United States)

    Legerstee, W. J.; de Roode, J.; Anastasopol, A.; Falub, C. V.; Eijt, S. W. H.

    We developed a dedicated hydrogen sorption setup coupled to a positron 2D-ACAR (two-dimensional Angular Correlation of Annihilation Radiation) setup employing a 22Na-source, which will enable to collect 2D-ACAR momentum distributions in-situ as a function of temperature, hydrogen pressure and hydrogen content. In parallel, a dedicated glovebox was constructed for handling air-sensitive metal and metal hydride samples, with a special entrance for the 2D-ACAR sample insert. The 2D-ACAR setup was tested in first measurements on a Pd0.75Ag0.25 foil and on a ball-milled MgH2 powder in both the hydrogen loaded and desorbed states. The hydrogen loaded Pd0.75Ag0.25Hx sample was kept under a 1 bar hydrogen pressure to prevent partial desorption during measurements at room temperature. The collected 2D-ACAR distributions of Pd0.75Ag0.25 and Pd0.75Ag0.25Hx showed similar features as observed in previous studies. The broadening of the ACAR distributions observed for the Mg to MgH2 metal-insulator transition was compared in a quantitative manner to ab-initio calculations reported in the literature.

  3. High-Temperature Electrochemical Hydrogen Pumps and Separators

    Directory of Open Access Journals (Sweden)

    P. Pasierb

    2011-01-01

    Full Text Available In this work different methods of hydrogen purification were presented and discussed. Special emphasis was given to electrochemical hydrogen pumps and membranes. The general principle of operation of such devices was shown, and the basic criteria for materials selection were formulated. The experimental part shows the example results concerning the pumping efficiency, demonstrating the possibility of application of high-temperature protonic conductors for the construction of pump or membrane for hydrogen purification.

  4. First-Principles Modeling of Hydrogen Storage in Metal Hydride Systems

    Energy Technology Data Exchange (ETDEWEB)

    J. Karl Johnson

    2011-05-20

    The objective of this project is to complement experimental efforts of MHoCE partners by using state-of-the-art theory and modeling to study the structure, thermodynamics, and kinetics of hydrogen storage materials. Specific goals include prediction of the heats of formation and other thermodynamic properties of alloys from first principles methods, identification of new alloys that can be tested experimentally, calculation of surface and energetic properties of nanoparticles, and calculation of kinetics involved with hydrogenation and dehydrogenation processes. Discovery of new metal hydrides with enhanced properties compared with existing materials is a critical need for the Metal Hydride Center of Excellence. New materials discovery can be aided by the use of first principles (ab initio) computational modeling in two ways: (1) The properties, including mechanisms, of existing materials can be better elucidated through a combined modeling/experimental approach. (2) The thermodynamic properties of novel materials that have not been made can, in many cases, be quickly screened with ab initio methods. We have used state-of-the-art computational techniques to explore millions of possible reaction conditions consisting of different element spaces, compositions, and temperatures. We have identified potentially promising single- and multi-step reactions that can be explored experimentally.

  5. Li4FeH6: Iron-containing complex hydride with high gravimetric hydrogen density

    Directory of Open Access Journals (Sweden)

    Hiroyuki Saitoh

    2014-07-01

    Full Text Available Li4FeH6, which has the highest gravimetric hydrogen density of iron-containing complex hydrides reported so far, is synthesized by hydrogenation of a powder mixture of iron and LiH above 6.1 GPa at 900 °C. In situ synchrotron radiation X-ray diffraction measurements reveal that while kinetics require high temperature and thus high pressure for the synthesis, Li4FeH6 is expected to be thermodynamically stable slightly below room temperature at ambient pressure; further synthetic studies to suppress the kinetic effects may enable us to synthesize Li4FeH6 at moderate pressures. Li4FeH6 can be recovered at ambient conditions where Li4FeH6 is metastable.

  6. A high-efficiency power cycle in which hydrogen is compressed by absorption in metal hydrides.

    Science.gov (United States)

    Powell, J R; Salzano, F J; Yu, W S; Milau, J S

    1976-07-23

    A high-efficiency power cycle is proposed in which molecular hydrogen gas is used as a working fluid in a regenerative closed Brayton cycle. The hydrogen gas is compressed by an absorption-desorption cycle on metal hydride (FeTiH(x)) beds. Low-temperature solar or geothermal heat (temperature about 100 degrees C) is used for the compression process, and high-temperature fossil fuel or nuclear heat (temperature about 700 degrees C) supplies the expansion work in the turbine. Typically, about 90 percent of the high-temperature heat input is converted to electricity, while about 3 kilowatts of low-temperature heat is required per kilowatt of electrical output.

  7. Electrochemical hydride generation atomic fluorescence spectrometry for detection of tin in canned foods using polyaniline-modified lead cathode.

    Science.gov (United States)

    Jiang, Xianjuan; Gan, Wuer; Wan, Lingzhong; Deng, Yun; Yang, Qinghua; He, Youzhao

    2010-12-15

    An electrochemical hydride generation system with polyaniline-modified lead cathode was developed for tin determination by coupling with atomic fluorescence spectrometry. The tin fluorescence signal intensity was improved evidently as the polyaniline membrane could facilitate the transformation process from atomic tin to the SnH(4) and prevent the aggradation of Sn atom on Pb electrode surface. The effects of experimental parameters and interferences have been studied. The limit of detection (LOD) was 1.5 ng mL(-1) (3σ) and the relative standard deviation (RSD) was 3.3% for 11 consecutive measurements of 50 ng mL(-1) Sn(IV) standard solution.

  8. The microstructures and electrochemical performances of La0.6Gd0.2Mg0.2Ni3.0Co0.5-xAlx (x=0-0.5) hydrogen storage alloys as negative electrodes for nickel/metal hydride secondary batteries

    Science.gov (United States)

    Li, Rongfeng; Xu, Peizhen; Zhao, Yamin; Wan, Jing; Liu, Xiaofang; Yu, Ronghai

    2014-12-01

    La0.6Gd0.2Mg0.2Ni3.0Co0.5-xAlx (x = 0-0.5) hydrogen storage alloys were prepared by induction melting followed by annealing treatment at 1173 K for 8 h. The effects of substitution Al for Co on the microstructures and electrochemical performances were studied systematically. The structure analyses show that all alloys consist of multiphase structures such as (La, Mg)2Ni7 phase, (La, Mg) Ni3 phase and LaNi5 phase. The abundance of (La, Mg)2Ni7 phase decreases while the abundance of LaNi5 phase and (La, Mg)Ni3 phase increases directly as the Al content increasing. The electrochemical tests show that the maximum discharge capacity of alloy electrodes are almost unchanged when x ≤ 0.2 while the cyclic stability of the alloy electrode are improved significantly after proper amount of Al substitution for Co. The alloy electrode with x = 0.1 exhibits the better balance between discharge capacity and cycling life than any others. Moreover, at the discharge current density of 900 mA g-1, the high rate dischargeability (HRD) of the alloy electrodes decreases with increasing Al substitution and the relative analyses reveal that the charge transfer on alloy surface is more important than the hydrogen diffusion in alloy bulk for the kinetic properties of the alloy electrodes.

  9. Metal Hydride Nanoparticles with Ultrahigh Structural Stability and Hydrogen Storage Activity Derived from Microencapsulated Nanoconfinement.

    Science.gov (United States)

    Zhang, Jiguang; Zhu, Yunfeng; Lin, Huaijun; Liu, Yana; Zhang, Yao; Li, Shenyang; Ma, Zhongliang; Li, Liquan

    2017-06-01

    Metal hydrides (MHs) have recently been designed for hydrogen sensors, switchable mirrors, rechargeable batteries, and other energy-storage and conversion-related applications. The demands of MHs, particular fast hydrogen absorption/desorption kinetics, have brought their sizes to nanoscale. However, the nanostructured MHs generally suffer from surface passivation and low aggregation-resisting structural stability upon absorption/desorption. This study reports a novel strategy named microencapsulated nanoconfinement to realize local synthesis of nano-MHs, which possess ultrahigh structural stability and superior desorption kinetics. Monodispersed Mg2 NiH4 single crystal nanoparticles (NPs) are in situ encapsulated on the surface of graphene sheets (GS) through facile gas-solid reactions. This well-defined MgO coating layer with a thickness of ≈3 nm efficiently separates the NPs from each other to prevent aggregation during hydrogen absorption/desorption cycles, leading to excellent thermal and mechanical stability. More interestingly, the MgO layer shows superior gas-selective permeability to prevent further oxidation of Mg2 NiH4 meanwhile accessible for hydrogen absorption/desorption. As a result, an extremely low activation energy (31.2 kJ mol(-1) ) for the dehydrogenation reaction is achieved. This study provides alternative insights into designing nanosized MHs with both excellent hydrogen storage activity and thermal/mechanical stability exempting surface modification by agents. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Cathodic electrocatalyst layer for electrochemical generation of hydrogen peroxide

    Science.gov (United States)

    Rhodes, Christopher P. (Inventor); Tennakoon, Charles L. K. (Inventor); Singh, Waheguru Pal (Inventor); Anderson, Kelvin C. (Inventor)

    2011-01-01

    A cathodic gas diffusion electrode for the electrochemical production of aqueous hydrogen peroxide solutions. The cathodic gas diffusion electrode comprises an electrically conductive gas diffusion substrate and a cathodic electrocatalyst layer supported on the gas diffusion substrate. A novel cathodic electrocatalyst layer comprises a cathodic electrocatalyst, a substantially water-insoluble quaternary ammonium compound, a fluorocarbon polymer hydrophobic agent and binder, and a perfluoronated sulphonic acid polymer. An electrochemical cell using the novel cathodic electrocatalyst layer has been shown to produce an aqueous solution having between 8 and 14 weight percent hydrogen peroxide. Furthermore, such electrochemical cells have shown stable production of hydrogen peroxide solutions over 1000 hours of operation including numerous system shutdowns.

  11. Hydrogen-based electrochemical energy storage

    Science.gov (United States)

    Simpson, Lin Jay

    2013-08-06

    An energy storage device (100) providing high storage densities via hydrogen storage. The device (100) includes a counter electrode (110), a storage electrode (130), and an ion conducting membrane (120) positioned between the counter electrode (110) and the storage electrode (130). The counter electrode (110) is formed of one or more materials with an affinity for hydrogen and includes an exchange matrix for elements/materials selected from the non-noble materials that have an affinity for hydrogen. The storage electrode (130) is loaded with hydrogen such as atomic or mono-hydrogen that is adsorbed by a hydrogen storage material such that the hydrogen (132, 134) may be stored with low chemical bonding. The hydrogen storage material is typically formed of a lightweight material such as carbon or boron with a network of passage-ways or intercalants for storing and conducting mono-hydrogen, protons, or the like. The hydrogen storage material may store at least ten percent by weight hydrogen (132, 134) at ambient temperature and pressure.

  12. Single walled carbon nanotubes functionalized with hydrides as potential hydrogen storage media: A survey of intermolecular interactions

    Energy Technology Data Exchange (ETDEWEB)

    Surya, V.J.; Iyakutti, K. [School of Physics, Madurai Kamaraj University, Madurai, Tamil Nadu (India); Venkataramanan, N.S.; Mizuseki, H.; Kawazoe, Y. [Institute for Materials Research, Tohoku University, Katahira Aoba-ku, Sendai (Japan)

    2011-09-15

    In this paper, we have analyzed the intermolecular interactions between H{sub 2} and single walled carbon nanotube (SWCNT)-hydride complexes and project their capability as a practicable hydrogen storage medium (HSM). In this respect, we have investigated the type of interactions namely van der Waals, electrostatic, and orbital interactions to understand the molecular hydrogen binding affinity of various systems. We found that the charge transfer effects coupled with induced electrostatic interactions are responsible for synergetic action of SWCNT and hydrides on adsorption of H{sub 2} molecules at ambient conditions. Also we have calculated the thermodynamically usable capacity of hydrogen in all the systems. This study enables one to identify and design potential hydrogen storage materials. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  13. Monitoring and control of a hydrogen production and storage system consisting of water electrolysis and metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Perez-Herranz, V.; Perez-Page, M. [Departamento de Ingenieria Quimica y Nuclear. Universidad Politecnica de Valencia. Camino de Vera S/N, 46022 Valencia (Spain); Beneito, R. [Area de Energia. Departamento de Gestion e Innovacion. Instituto Tecnologico del Juguete (AIJU). Avda. Industria 23, 03440 Ibi, Alicante (Spain)

    2010-02-15

    Renewable energy sources such as wind turbines and solar photovoltaic are energy sources that cannot generate continuous electric power. The seasonal storage of solar or wind energy in the form of hydrogen can provide the basis for a completely renewable energy system. In this way, water electrolysis is a convenient method for converting electrical energy into a chemical form. The power required for hydrogen generation can be supplied through a photovoltaic array. Hydrogen can be stored as metal hydrides and can be converted back into electricity using a fuel cell. The elements of these systems, i.e. the photovoltaic array, electrolyzer, fuel cell and hydrogen storage system in the form of metal hydrides, need a control and monitoring system for optimal operation. This work has been performed within a Research and Development contract on Hydrogen Production granted by Solar Iniciativas Tecnologicas, S.L. (SITEC), to the Politechnic University of Valencia and to the AIJU, and deals with the development of a system to control and monitor the operation parameters of an electrolyzer and a metal hydride storage system that allow to get a continuous production of hydrogen. (author)

  14. Electrochemical Hydrogen Storage in a Highly Ordered Mesoporous Carbon

    Directory of Open Access Journals (Sweden)

    Dan eLiu

    2014-10-01

    Full Text Available A highly order mesoporous carbon has been synthesized through a strongly acidic, aqueous cooperative assembly route. The structure and morphology of the carbon material were investigated using TEM, SEM and nitrogen adsorption-desorption isotherms. The carbon was proven to be meso-structural and consisted of graphitic micro-domain with larger interlayer space. AC impedance and electrochemical measurements reveal that the synthesized highly ordered mesoporous carbon exhibits a promoted electrochemical hydrogen insertion process and improved capacitance and hydrogen storage stability. The meso-structure and enlarged interlayer distance within the highly ordered mesoporous carbon are suggested as possible causes for the enhancement in hydrogen storage. Both hydrogen capacity in the carbon and mass diffusion within the matrix were improved.

  15. Highly efficient bimetal synergetic catalysis by a multi-wall carbon nanotube supported palladium and nickel catalyst for the hydrogen storage of magnesium hydride.

    Science.gov (United States)

    Yuan, Jianguang; Zhu, Yunfeng; Li, Liquan

    2014-06-25

    A multi-wall carbon nanotube supported Pd and Ni catalyst efficiently catalyzes the hydrogen storage of magnesium hydride prepared by HCS + MM. Excellent hydrogen storage properties were obtained: hydrogen absorption - 6.44 wt% within 100 s at 373 K, hydrogen desorption - 6.41 wt% within 1800 s at 523 K and 6.70 wt% within 400 s at 573 K.

  16. High-Temperature Electrochemical Hydrogen Pumps and Separators

    OpenAIRE

    P. Pasierb; Rekas, M.

    2011-01-01

    In this work different methods of hydrogen purification were presented and discussed. Special emphasis was given to electrochemical hydrogen pumps and membranes. The general principle of operation of such devices was shown, and the basic criteria for materials selection were formulated. The experimental part shows the example results concerning the pumping efficiency, demonstrating the possibility of application of high-temperature protonic conductors for the construction of pump or membrane ...

  17. Atoms and Nanoparticles of Transition Metals as Catalysts for Hydrogen Desorption from Magnesium Hydride

    Directory of Open Access Journals (Sweden)

    N. Bazzanella

    2011-01-01

    Full Text Available The hydrogen desorption kinetics of composite materials made of magnesium hydride with transition metal additives (TM: Nb, Fe, and Zr was studied by several experimental techniques showing that (i a few TM at.% concentrations catalyse the H2 desorption process, (ii the H2 desorption kinetics results stabilized after a few H2 sorption cycles when TM atoms aggregate by forming nanoclusters; (iii the catalytic process occurs also at TM concentration as low as 0.06 at.% when TM atoms clustering is negligible, and (iv mixed Fe and Zr additives produce faster H2 desorption kinetics than single additive. The improved H2 desorption kinetics of the composite materials can be explained by assuming that the interfaces between the MgH2 matrix and the TM nanoclusters act as heterogeneous sites for the nucleation of the Mg phase in the MgH2 matrix and promote the formation of fast diffusion channels for H migrating atoms.

  18. Catalitic effect of Co on hydrogen desorption form nanostucturated magnesium hydride

    Directory of Open Access Journals (Sweden)

    Matović Ljiljana Lj.

    2008-01-01

    Full Text Available To study the influence of 3d transition metal addition on desorption kinetics of MgH2 ball milling of MgH2-Co blends was performed under Ar. Microstructural and morphological characterization, performed by XRD and SEM, show a huge correlation with thermal stability and hydrogen desorption properties investigated by DSC. A complex desorption behavior is correlated with the dispersion of the metal additive particles on hydride matrix. The activation energy for H2 desorption from MgH2-Co composite was calculated from both non-isothermal and isothermal methods to be 130 kJ/mol which means that mutually diffusion and nucleation and growth of new phase control the dehydration process.

  19. Discovery of Novel Complex Metal Hydrides for Hydrogen Storage through Molecular Modeling and Combinatorial Methods

    Energy Technology Data Exchange (ETDEWEB)

    Lesch, David A; Adriaan Sachtler, J.W. J.; Low, John J; Jensen, Craig M; Ozolins, Vidvuds; Siegel, Don; Harmon, Laurel

    2011-02-14

    UOP LLC, a Honeywell Company, Ford Motor Company, and Striatus, Inc., collaborated with Professor Craig Jensen of the University of Hawaii and Professor Vidvuds Ozolins of University of California, Los Angeles on a multi-year cost-shared program to discover novel complex metal hydrides for hydrogen storage. This innovative program combined sophisticated molecular modeling with high throughput combinatorial experiments to maximize the probability of identifying commercially relevant, economical hydrogen storage materials with broad application. A set of tools was developed to pursue the medium throughput (MT) and high throughput (HT) combinatorial exploratory investigation of novel complex metal hydrides for hydrogen storage. The assay programs consisted of monitoring hydrogen evolution as a function of temperature. This project also incorporated theoretical methods to help select candidate materials families for testing. The Virtual High Throughput Screening served as a virtual laboratory, calculating structures and their properties. First Principles calculations were applied to various systems to examine hydrogen storage reaction pathways and the associated thermodynamics. The experimental program began with the validation of the MT assay tool with NaAlH4/0.02 mole Ti, the state of the art hydrogen storage system given by decomposition of sodium alanate to sodium hydride, aluminum metal, and hydrogen. Once certified, a combinatorial 21-point study of the NaAlH4 LiAlH4Mg(AlH4)2 phase diagram was investigated with the MT assay. Stability proved to be a problem as many of the materials decomposed during synthesis, altering the expected assay results. This resulted in repeating the entire experiment with a mild milling approach, which only temporarily increased capacity. NaAlH4 was the best performer in both studies and no new mixed alanates were observed, a result consistent with the VHTS. Powder XRD suggested that the reverse reaction, the regeneration of the

  20. Discovery of Novel Complex Metal Hydrides for Hydrogen Storage through Molecular Modeling and Combinatorial Methods

    Energy Technology Data Exchange (ETDEWEB)

    Lesch, David A; Adriaan Sachtler, J.W. J.; Low, John J; Jensen, Craig M; Ozolins, Vidvuds; Siegel, Don; Harmon, Laurel

    2011-02-14

    UOP LLC, a Honeywell Company, Ford Motor Company, and Striatus, Inc., collaborated with Professor Craig Jensen of the University of Hawaii and Professor Vidvuds Ozolins of University of California, Los Angeles on a multi-year cost-shared program to discover novel complex metal hydrides for hydrogen storage. This innovative program combined sophisticated molecular modeling with high throughput combinatorial experiments to maximize the probability of identifying commercially relevant, economical hydrogen storage materials with broad application. A set of tools was developed to pursue the medium throughput (MT) and high throughput (HT) combinatorial exploratory investigation of novel complex metal hydrides for hydrogen storage. The assay programs consisted of monitoring hydrogen evolution as a function of temperature. This project also incorporated theoretical methods to help select candidate materials families for testing. The Virtual High Throughput Screening served as a virtual laboratory, calculating structures and their properties. First Principles calculations were applied to various systems to examine hydrogen storage reaction pathways and the associated thermodynamics. The experimental program began with the validation of the MT assay tool with NaAlH4/0.02 mole Ti, the state of the art hydrogen storage system given by decomposition of sodium alanate to sodium hydride, aluminum metal, and hydrogen. Once certified, a combinatorial 21-point study of the NaAlH4 LiAlH4Mg(AlH4)2 phase diagram was investigated with the MT assay. Stability proved to be a problem as many of the materials decomposed during synthesis, altering the expected assay results. This resulted in repeating the entire experiment with a mild milling approach, which only temporarily increased capacity. NaAlH4 was the best performer in both studies and no new mixed alanates were observed, a result consistent with the VHTS. Powder XRD suggested that the reverse reaction, the regeneration of the

  1. Structural and hydrogen storage capacity evolution of Mg2FeH6 hydride synthesized by reactive mechanical alloying

    Institute of Scientific and Technical Information of China (English)

    LI Song-lin(李松林); R.A.Varin

    2004-01-01

    Mg-based metal hydrides are promising as hydrogen storage materials for fuel cell application. In this work, Mg2 FeH6 complex hydride phase was synthesized by controlled reactive ball milling of 2Mg-Fe (atomic ratio)powder mixture in H2. Mg2 FeH6 is confirmed to be formed via the following three stages: formation of MgH2 via the reaction of Mg with H2, incubation stage and formation of Mg2 FeH6 by reaction of fully refined MgH2 and Fe.The incubation stage is characterized by no traces of Mg or hydride crystalline phase by XRD. On the other hand,Mg is observed uniformly distributed in the milled powder by SEM-EDS. Also, almost the same amount of H2 as the first stage is detected stored in the powders of the second stage by DSC and TGA.

  2. Selective Electrochemical Generation of Hydrogen Peroxide from Water Oxidation

    DEFF Research Database (Denmark)

    Viswanathan, Venkatasubramanian; Hansen, Heine Anton; Nørskov, Jens K.

    2015-01-01

    device concept that can utilize sunlight to split water into hydrogen and hydrogen peroxide. The hydrogen peroxide can oxidize organics while the hydrogen bubbles out. In enabling this device, we require an electrocatalyst that can oxidize water while suppressing the thermodynamically favored oxygen...... evolution and form hydrogen peroxide. Using density functional theory calculations, we show that the free energy of adsorbed OH* can be used to determine selectivity trends between the 2e(-) water oxidation to H2O2 and the 4e(-) oxidation to O2. We show that materials which bind oxygen intermediates...... sufficiently weakly, such as SnO2, can activate hydrogen peroxide evolution. We present a rational design principle for the selectivity in electrochemical water oxidation and identify new material candidates that could perform H2O2 evolution selectively....

  3. Comparison of Hydrogen Elimination from Molecular Zinc and Magnesium Hydride Clusters

    NARCIS (Netherlands)

    Intemann, J.; Sirsch, Peter; Harder, Sjoerd

    2014-01-01

    In analogy to the previously reported tetranuclear magnesium hydride cluster with a bridged dianionic bis-beta-diketiminate ligand, a related zinc hydride cluster has been prepared. The crystal structures of these magnesium and zinc hydride complexes are similar: the metal atoms are situated at the

  4. Comparison of Hydrogen Elimination from Molecular Zinc and Magnesium Hydride Clusters

    NARCIS (Netherlands)

    Intemann, J.; Sirsch, Peter; Harder, Sjoerd

    2014-01-01

    In analogy to the previously reported tetranuclear magnesium hydride cluster with a bridged dianionic bis-beta-diketiminate ligand, a related zinc hydride cluster has been prepared. The crystal structures of these magnesium and zinc hydride complexes are similar: the metal atoms are situated at the

  5. Bio-inspired transition metal-organic hydride conjugates for catalysis of transfer hydrogenation: experiment and theory.

    Science.gov (United States)

    McSkimming, Alex; Chan, Bun; Bhadbhade, Mohan M; Ball, Graham E; Colbran, Stephen B

    2015-02-09

    Taking inspiration from yeast alcohol dehydrogenase (yADH), a benzimidazolium (BI(+) ) organic hydride-acceptor domain has been coupled with a 1,10-phenanthroline (phen) metal-binding domain to afford a novel multifunctional ligand (L(BI+) ) with hydride-carrier capacity (L(BI+) +H(-) ⇌L(BI) H). Complexes of the type [Cp*M(L(BI) )Cl][PF6 ]2 (M=Rh, Ir) have been made and fully characterised by cyclic voltammetry, UV/Vis spectroelectrochemistry, and, for the Ir(III) congener, X-ray crystallography. [Cp*Rh(L(BI) )Cl][PF6 ]2 catalyses the transfer hydrogenation of imines by formate ion in very goods yield under conditions where the corresponding [Cp*Ir(L(BI) )Cl][PF6 ] and [Cp*M(phen)Cl][PF6 ] (M=Rh, Ir) complexes are almost inert as catalysts. Possible alternatives for the catalysis pathway are canvassed, and the free energies of intermediates and transition states determined by DFT calculations. The DFT study supports a mechanism involving formate-driven RhH formation (90 kJ mol(-1) free-energy barrier), transfer of hydride between the Rh and BI(+) centres to generate a tethered benzimidazoline (BIH) hydride donor, binding of imine substrate at Rh, back-transfer of hydride from the BIH organic hydride donor to the Rh-activated imine substrate (89 kJ mol(-1) barrier), and exergonic protonation of the metal-bound amide by formic acid with release of amine product to close the catalytic cycle. Parallels with the mechanism of biological hydride transfer in yADH are discussed.

  6. In operando visualization of hydride-graphite composites during cyclic hydrogenation by high-resolution neutron imaging

    Science.gov (United States)

    Pohlmann, Carsten; Herbrig, Kai; Gondek, Łukasz; Kardjilov, Nikolay; Hilger, André; Figiel, Henryk; Banhart, John; Kieback, Bernd; Manke, Ingo; Röntzsch, Lars

    2015-03-01

    Hydrogen solid-state storage in metal hydrides has attracted remarkable attention within the past decades due to their high volumetric storage densities at low operating pressures. In particular, recently emerged hydride-graphite composites (HGC) can enable a safe, reliable and very compact hydrogen storage solution for various applications. In this regard, only little is known about the activation behavior of such HGC, their cycle stability and degradation effects. Because of the high sensitivity to hydrogen, neutron imaging offers a distinctive approach to examine in operando reaction fronts, swelling effects and microstructural changes of hydrogen absorbing materials with high spatial and temporal resolution. In this contribution, a comprehensive analysis of various phenomena during activation and cycling of HGC based on a Ti-Mn hydrogen absorbing alloy and expanded natural graphite is reported for the first time. A neutron radiography and tomography set-up with a spatial resolution down to 7 μm was utilized allowing highest detection precision. During initial hydrogenation, regions with enhanced reactivity are observed which contradicts a theoretically expected homogeneous reactivity inside the HGC. These active regions grow with the number of hydrogenation-dehydrogenation cycles until the whole HGC volume uniformly participates in the hydrogen sorption reaction. With regard to long-term hydrogenation-dehydrogenation cycling, inhomogeneous swelling effects were observed from which essential conclusions for technical HGC-based tank systems can be derived.

  7. Electrochemical Hydrogen Evolution: Sabatier's Principle and the Volcano Plot

    Science.gov (United States)

    Laursen, Anders B.; Varela, Ana Sofia; Dionigi, Fabio; Fanchiu, Hank; Miller, Chandler; Trinhammer, Ole L.; Rossmeisl, Jan; Dahl, Soren

    2012-01-01

    The electrochemical hydrogen evolution reaction (HER) is growing in significance as society begins to rely more on renewable energy sources such as wind and solar power. Thus, research on designing new, inexpensive, and abundant HER catalysts is important. Here, we describe how a simple experiment combined with results from density functional…

  8. Electrochemical Hydrogen Evolution: Sabatier's Principle and the Volcano Plot

    Science.gov (United States)

    Laursen, Anders B.; Varela, Ana Sofia; Dionigi, Fabio; Fanchiu, Hank; Miller, Chandler; Trinhammer, Ole L.; Rossmeisl, Jan; Dahl, Soren

    2012-01-01

    The electrochemical hydrogen evolution reaction (HER) is growing in significance as society begins to rely more on renewable energy sources such as wind and solar power. Thus, research on designing new, inexpensive, and abundant HER catalysts is important. Here, we describe how a simple experiment combined with results from density functional…

  9. Optimization and comprehensive characterization of metal hydride based hydrogen storage systems using in-situ Neutron Radiography

    Science.gov (United States)

    Börries, S.; Metz, O.; Pranzas, P. K.; Bellosta von Colbe, J. M.; Bücherl, T.; Dornheim, M.; Klassen, T.; Schreyer, A.

    2016-10-01

    For the storage of hydrogen, complex metal hydrides are considered as highly promising with respect to capacity, reversibility and safety. The optimization of corresponding storage tanks demands a precise and time-resolved investigation of the hydrogen distribution in scaled-up metal hydride beds. In this study it is shown that in situ fission Neutron Radiography provides unique insights into the spatial distribution of hydrogen even for scaled-up compacts and therewith enables a direct study of hydrogen storage tanks. A technique is introduced for the precise quantification of both time-resolved data and a priori material distribution, allowing inter alia for an optimization of compacts manufacturing process. For the first time, several macroscopic fields are combined which elucidates the great potential of Neutron Imaging for investigations of metal hydrides by going further than solely 'imaging' the system: A combination of in-situ Neutron Radiography, IR-Thermography and thermodynamic quantities can reveal the interdependency of different driving forces for a scaled-up sodium alanate pellet by means of a multi-correlation analysis. A decisive and time-resolved, complex influence of material packing density is derived. The results of this study enable a variety of new investigation possibilities that provide essential information on the optimization of future hydrogen storage tanks.

  10. Applications of hydrogen peroxide in electrochemical technology

    Energy Technology Data Exchange (ETDEWEB)

    Alvarez Gallegos, Alberto Armando

    1998-12-01

    It is demonstrated that hydrogen peroxide can be produced with a current efficiency of 40-70% by the cathodic reduction of oxygen at a reticulated vitreous carbon electrode in a divided flow-cell using catholytes consisting of aqueous chloride or sulphate media, pH >>{sub 2}. The supporting electrolyte does not influence either the current efficiency for H{sub 2}O{sub 2} or its rate of production. The current efficiency for H{sub 2}O{sub 2} is not a strong function of the potential and this suggests that 2e- and 4e- reduction of oxygen occurs in parallel at different sites on the carbon surface. Voltammetry experiments showed that (a) the I-E response for oxygen reduction at pH >>{sub 2} is a function of the electrode surface and/or the supporting electrolyte; (b) both H{sub 2} evolution and oxygen reduction are retarded on carbon with increasing ionic strength; (c) the presence of ferrous ions lead to the homogeneous decomposition of H{sub 2}O{sub 2} away from the cathode surface but their effectiveness as a catalyst for this decomposition depends on their speciation in solution which changes during an electrolysis. The use of a three-dimensional electrode fabricated from reticulated vitreous carbon allows Fenton`s reagent to be electroproduced at a practical rate which makes possible the removal of organics in slightly acidic aqueous media. A wide range of highly toxic organic molecules (phenol, catechol, hydroquinone, p-benzoquinone, oxalic acid, aniline, cresol and amaranth) have been oxidised in mild conditions and a significant fraction of the organic carbon is evolved as CO{sub 2}. In all cases studied the initial chemical oxygen demand (COD) was depleted to levels higher than 85%, indicating a complete mineralisation of the organic pollutants. The life-time of the reticulated vitreous carbon cathode was demonstrated to be over 1000 hours during two and a half years of experiments. During this time the cathode performance was very good, leading to

  11. Microstructure of alloy MlNi3.75 Co0.75 Mn0.3 Al0.2(Ml-La-rich mischmetal)during electrochemical hydriding-dehydriding process

    Institute of Scientific and Technical Information of China (English)

    YUAN Zhi-qing; L(U) Guang-lie; GU Jian-ming; SHENG Xiao-fei

    2005-01-01

    Evolution of microstructures of alloy MlNi3.75 Co0.75 Mn0.3Al0.2 (Ml-La-rich mischmetal) during the electrochemical hydriding-dehydriding process was studied by using in-situ X-ray diffraction method.It is indicated that both the crystallite sizes of α phase (solid solution phase) andβ phase (hydride phase) decrease with the hydrogen content increasing during this process.β phase is found to be composed of the plate-like and the needle-like crystallites,while the crystallite size of the former changes more rapidly than that of the later during the hydridingdehydriding process.It's also clearly found that strains along (110) plane and (001) plane of α phase and β phase are higher in the α+β region than those in the corresponding single phase region.Based on the microstructural studies,mechanism for the hydride growth has also been proposed.

  12. Ti–V–Mn based metal hydrides for hydrogen compression applications

    Energy Technology Data Exchange (ETDEWEB)

    Pickering, Lydia, E-mail: lydia.pickering@btinternet.com; Reed, Daniel; Bevan, Alexander I.; Book, David, E-mail: d.book@bham.ac.uk

    2015-10-05

    Highlights: • Ti–V–Mn based alloys were investigated as V was substituted for Nb, Cr, Mo and Ta. • The produced alloys were found to possess C14 Laves, BCC and FCC phases. • <0.2 Nb substituted for V led to small hysteresis and high dissociation pressures. • Ti{sub 0.5}–V{sub 0.45}–Nb{sub 0.05}–Mn is a suitable alloy to be used in a metal hydride compressor. - Abstract: Ti–V–Mn based alloys, consisting mainly of the hexagonal C14 Laves and BCC phases, with nominal compositions of Ti{sub 0.5}V{sub 0.4}TM{sub 0.1}Mn, where TM = Nb, Cr, Mo, Ta and Ti{sub 0.5}V{sub 0.5−x}Nb{sub x}Mn, where x = 0.05 and 0.2, were synthesised by arc melting. It was found that small amounts of Nb substituted for V (x = 0.05 and 0.1) resulted in smaller hysteresis between absorption and desorption as well as higher hydrogen dissociation pressures, compared to Ti{sub 0.5}V{sub 0.5}Mn. These findings show that Ti{sub 0.5}–V{sub 0.45}–Nb{sub 0.05}–Mn is a suitable alloy to be used in a metal hydride compressor to deliver a pressure of 650 bar in the temperature range 303–473 K.

  13. Design of Hydrogen Storage Alloys/Nanoporous Metals Hybrid Electrodes for Nickel-Metal Hydride Batteries

    Science.gov (United States)

    Li, M. M.; Yang, C. C.; Wang, C. C.; Wen, Z.; Zhu, Y. F.; Zhao, M.; Li, J. C.; Zheng, W. T.; Lian, J. S.; Jiang, Q.

    2016-06-01

    Nickel metal hydride (Ni-MH) batteries have demonstrated key technology advantages for applications in new-energy vehicles, which play an important role in reducing greenhouse gas emissions and the world’s dependence on fossil fuels. However, the poor high-rate dischargeability of the negative electrode materials—hydrogen storage alloys (HSAs) limits applications of Ni-MH batteries in high-power fields due to large polarization. Here we design a hybrid electrode by integrating HSAs with a current collector of three-dimensional bicontinuous nanoporous Ni. The electrode shows enhanced high-rate dischargeability with the capacity retention rate reaching 44.6% at a discharge current density of 3000 mA g-1, which is 2.4 times that of bare HSAs (18.8%). Such a unique hybrid architecture not only enhances charge transfer between nanoporous Ni and HSAs, but also facilitates rapid diffusion of hydrogen atoms in HSAs. The developed HSAs/nanoporous metals hybrid structures exhibit great potential to be candidates as electrodes in high-performance Ni-MH batteries towards applications in new-energy vehicles.

  14. Design of Hydrogen Storage Alloys/Nanoporous Metals Hybrid Electrodes for Nickel-Metal Hydride Batteries

    Science.gov (United States)

    Li, M. M.; Yang, C. C.; Wang, C. C.; Wen, Z.; Zhu, Y. F.; Zhao, M.; Li, J. C.; Zheng, W. T.; Lian, J. S.; Jiang, Q.

    2016-01-01

    Nickel metal hydride (Ni-MH) batteries have demonstrated key technology advantages for applications in new-energy vehicles, which play an important role in reducing greenhouse gas emissions and the world’s dependence on fossil fuels. However, the poor high-rate dischargeability of the negative electrode materials—hydrogen storage alloys (HSAs) limits applications of Ni-MH batteries in high-power fields due to large polarization. Here we design a hybrid electrode by integrating HSAs with a current collector of three-dimensional bicontinuous nanoporous Ni. The electrode shows enhanced high-rate dischargeability with the capacity retention rate reaching 44.6% at a discharge current density of 3000 mA g−1, which is 2.4 times that of bare HSAs (18.8%). Such a unique hybrid architecture not only enhances charge transfer between nanoporous Ni and HSAs, but also facilitates rapid diffusion of hydrogen atoms in HSAs. The developed HSAs/nanoporous metals hybrid structures exhibit great potential to be candidates as electrodes in high-performance Ni-MH batteries towards applications in new-energy vehicles. PMID:27270184

  15. Intermolecular hydrogen bonding between neutral transition metal hydrides (eta(5)-C5H5)M(CO)3H (M = Mo, W) and bases.

    Science.gov (United States)

    Belkova, Natalia V; Gutsul, Evgenii I; Filippov, Oleg A; Levina, Vladislava A; Valyaev, Dmitriy A; Epstein, Lina M; Lledos, Agusti; Shubina, Elena S

    2006-03-22

    The interaction of CpM(CO)3H (M = Mo, W) hydrides as proton donors with different bases (B = pyridine, (n-Oc)3PO, ((CH3)2N)3PO, H3BNEt3) was studied by variable temperature IR spectroscopy and theoretically by DFT/B3LYP calculations. The data obtained show for the first time the formation of intermolecular hydrogen bonds between the neutral transition metal hydrides and bases in solutions of low polarity. These M-H...B hydrogen bonds are shown to precede the hydrides' deprotonation.

  16. Hydride structures in Ti-aluminides subjected to high temperature and hydrogen pressure charging conditions

    Science.gov (United States)

    Legzdina, D.; Robertson, I. M.; Birnbaum, H. K.

    1991-01-01

    The distribution and chemistry of hydrides produced in single and dual phase alloys with a composition near TiAl have been investigated by using a combination of TEM and X-ray diffraction techniques. The alloys were exposed at 650 C to 13.8 MPa of gaseous H2 for 100 h. In the single-phase gamma alloy, large hydrides preferentially nucleated on the grain boundaries and matrix dislocations and a population of small hydrides was distributed throughout the matrix. X-ray and electron diffraction patterns from these hydrides indicated that they have an fcc structure with a lattice parameter of 0.45 nm. EDAX analysis of the hydrides showed that they were enriched in Ti. The hydrides were mostly removed by vacuum annealing at 800 C for 24 h. On dissolution of the hydrides, the chemistry of hydride-free regions of the grain boundary returned to the matrix composition, suggesting that Ti segregation accompanied the hydride formation rather than Ti enrichment causing the formation of the hydride.

  17. Electrochemical hydride generation atomic fluorescence spectrometry for detection of tin in canned foods using polyaniline-modified lead cathode

    Energy Technology Data Exchange (ETDEWEB)

    Jiang Xianjuan [Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026 (China); Gan Wuer, E-mail: wgan@ustc.edu.cn [Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026 (China); Wan Lingzhong; Deng Yun; Yang Qinghua; He Youzhao [Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026 (China)

    2010-12-15

    An electrochemical hydride generation system with polyaniline-modified lead cathode was developed for tin determination by coupling with atomic fluorescence spectrometry. The tin fluorescence signal intensity was improved evidently as the polyaniline membrane could facilitate the transformation process from atomic tin to the SnH{sub 4} and prevent the aggradation of Sn atom on Pb electrode surface. The effects of experimental parameters and interferences have been studied. The limit of detection (LOD) was 1.5 ng mL{sup -1} (3{sigma}) and the relative standard deviation (RSD) was 3.3% for 11 consecutive measurements of 50 ng mL{sup -1} Sn(IV) standard solution.

  18. Self-assembled air-stable magnesium hydride embedded in 3-D activated carbon for reversible hydrogen storage.

    Science.gov (United States)

    Shinde, S S; Kim, Dong-Hyung; Yu, Jin-Young; Lee, Jung-Ho

    2017-06-01

    The rational design of stable, inexpensive catalysts with excellent hydrogen dynamics and sorption characteristics under realistic environments for reversible hydrogen storage remains a great challenge. Here, we present a simple and scalable strategy to fabricate a monodispersed, air-stable, magnesium hydride embedded in three-dimensional activated carbon with periodic synchronization of transition metals (MHCH). The high surface area, homogeneous distribution of MgH2 nanoparticles, excellent thermal stability, high energy density, steric confinement by carbon, and robust architecture of the catalyst resulted in a noticeable enhancement of the hydrogen storage performance. The resulting MHCH-5 exhibited outstanding hydrogen storage performance, better than that of most reported Mg-based hydrides, with a high storage density of 6.63 wt% H2, a rapid kinetics loading in hydrogenation compared to that of commercial MgH2. The origin of the intrinsic hydrogen thermodynamics was elucidated via solid state (1)H NMR. This work presents a readily scaled-up strategy towards the design of realistic catalysts with superior functionality and stability for applications in reversible hydrogen storage, lithium ion batteries, and fuel cells.

  19. Hydride, hydrogen, proton, and electron affinities of imines and their reaction intermediates in acetonitrile and construction of thermodynamic characteristic graphs (TCGs) of imines as a "molecule ID card".

    Science.gov (United States)

    Zhu, Xiao-Qing; Liu, Qiao-Yun; Chen, Qiang; Mei, Lian-Rui

    2010-02-01

    A series of 61 imines with various typical structures were synthesized, and the thermodynamic affinities (defined as enthalpy changes or redox potentials in this work) of the imines to abstract hydride anions, hydrogen atoms, and electrons, the thermodynamic affinities of the radical anions of the imines to abstract hydrogen atoms and protons, and the thermodynamic affinities of the hydrogen adducts of the imines to abstract electrons in acetonitrile were determined by using titration calorimetry and electrochemical methods. The pure heterolytic and homolytic dissociation energies of the C=N pi-bond in the imines were estimated. The polarity of the C=N double bond in the imines was examined using a linear free-energy relationship. The idea of a thermodynamic characteristic graph (TCG) of imines as an efficient "Molecule ID Card" was introduced. The TCG can be used to quantitatively diagnose and predict the characteristic chemical properties of imines and their various reaction intermediates as well as the reduction mechanism of the imines. The information disclosed in this work could not only supply a gap of thermodynamics for the chemistry of imines but also strongly promote the fast development of the applications of imines.

  20. Desorption of hydrogen from light metal hydrides: concerted electronic rearrangement and role of H···H interactions.

    Science.gov (United States)

    Wolstenholme, David J; Roy, Matthew M D; Thomas, Michael E; McGrady, G Sean

    2014-04-14

    A theoretical study of the desorption of hydrogen from rhombic Group 1 metal hydride dimers reveals a concerted reorganisation of the electron density for the M-H and H-H moieties as the reaction coordinate is traversed and a closed-shell H···H interaction evolves into a covalent H2 bond. The central role played by homopolar dihydrogen bonding in this process is revealed and analysed.

  1. Electrochemical properties of TiV-based hydrogen storage alloys

    Institute of Scientific and Technical Information of China (English)

    朱云峰; 李锐; 高明霞; 刘永锋; 潘洪革; 王启东

    2003-01-01

    The electrochemical properties of the super-stoichiometric TiV-based hydrogen storage electrode alloys(Ti0.8Zr0.2)(V0.533Mn0.107Cr0.16Ni0.2)x(x=2, 3, 4, 5, 6) were studied. It is found by XRD analysis that all the al-loys mainly consist of a C14 Laves phase with hexagonal structure and a V-based solid solution phase with BCCstructure. The lattice parameters and the unit cell volumes of the two phases decrease with increasing x. The cyclelife, the linear polarization, the anode polarization and the electrochemical impedance spectra of the alloy electrodeswere investigated systematically. The overall electrochemical properties of the alloy electrode are found improvedgreatly as the result of super-stoichiometry and get to the best when x= 5.

  2. Electrochemical performance and capacity degradation mechanism of single-phase La-Mg-Ni-based hydrogen storage alloys

    Science.gov (United States)

    Liu, Jingjing; Li, Yuan; Han, Da; Yang, Shuqin; Chen, Xiaocui; Zhang, Lu; Han, Shumin

    2015-12-01

    La-Mg-Ni-based hydrogen storage alloys are a promising candidate for the negative electrode materials of nickel metal hydride batteries. However, their fast capacity degradation hinders them from more extensive application. In this study, the electrochemical performance and capacity degradation mechanism of single-phase La2MgNi9, La3MgNi14 and La4MgNi19 alloys are studied from the perspective of their constituent subunits. It is found that the rate capability and cycling stability of the alloy electrodes increase with higher [LaNi5]/[LaMgNi4] subunit ratio, while the discharge capacity shows a reverse trend. Degradation study shows that the inter-molecular strains in the alloys are the main reason that leads to the fast capacity degradation of La-Mg-Ni-based alloys. The strains are caused by the difference in the expansion/contraction properties between [LaNi5] and [LaMgNi4] subunits during charge/discharge which is mainly observed in the H-dissolved solid solution instead of hydride. It is also found that the strains can be relieved by adjusting [LaNi5]/[LaMgNi4] subunit ratio of the alloys, thus achieving less pulverization and oxidation, and better cycling stability. We expect our findings can inspire new thoughts on improving the electrochemical performance of La-Mg-Ni-based alloys by tuning their superlattice structures.

  3. Metal Hydride Compression

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Terry A. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Bowman, Robert [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Smith, Barton [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Anovitz, Lawrence [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Jensen, Craig [Hawaii Hydrogen Carriers LLC, Honolulu, HI (United States)

    2017-07-01

    Conventional hydrogen compressors often contribute over half of the cost of hydrogen stations, have poor reliability, and have insufficient flow rates for a mature FCEV market. Fatigue associated with their moving parts including cracking of diaphragms and failure of seal leads to failure in conventional compressors, which is exacerbated by the repeated starts and stops expected at fueling stations. Furthermore, the conventional lubrication of these compressors with oil is generally unacceptable at fueling stations due to potential fuel contamination. Metal hydride (MH) technology offers a very good alternative to both conventional (mechanical) and newly developed (electrochemical, ionic liquid pistons) methods of hydrogen compression. Advantages of MH compression include simplicity in design and operation, absence of moving parts, compactness, safety and reliability, and the possibility to utilize waste industrial heat to power the compressor. Beyond conventional H2 supplies of pipelines or tanker trucks, another attractive scenario is the on-site generating, pressuring and delivering pure H2 at pressure (≥ 875 bar) for refueling vehicles at electrolysis, wind, or solar generating production facilities in distributed locations that are too remote or widely distributed for cost effective bulk transport. MH hydrogen compression utilizes a reversible heat-driven interaction of a hydride-forming metal alloy with hydrogen gas to form the MH phase and is a promising process for hydrogen energy applications [1,2]. To deliver hydrogen continuously, each stage of the compressor must consist of multiple MH beds with synchronized hydrogenation & dehydrogenation cycles. Multistage pressurization allows achievement of greater compression ratios using reduced temperature swings compared to single stage compressors. The objectives of this project are to investigate and demonstrate on a laboratory scale a two-stage MH hydrogen (H2) gas compressor with a

  4. Synthesis of ruthenium hydride

    Science.gov (United States)

    Kuzovnikov, M. A.; Tkacz, M.

    2016-02-01

    Ruthenium hydride was synthesized at a hydrogen pressure of about 14 GPa in a diamond-anvil cell. Energy-dispersive x-ray diffraction was used to monitor the ruthenium crystal structure as a function of hydrogen pressure up to 30 GPa. The hydride formation was accompanied by phase transition from the original hcp structure of the pristine metal to the fcc structure. Our results confirmed the theoretical prediction of ruthenium hydride formation under hydrogen pressure. The standard Gibbs free energy of the ruthenium hydride formation reaction was calculated assuming the pressure of decomposition as the equilibrium pressure.

  5. Effect of Cold Rolling on the Hydrogen Desorption Behavior of Binary Metal Hydride Powders under Microwave Irradiation

    Directory of Open Access Journals (Sweden)

    Ivaldete da Silva Dupim

    2015-10-01

    Full Text Available In this paper we report that cold rolling could drastically improve hydrogen desorption kinetics under microwave irradiation. Samples of metal hydride powders (TiH2, ZrH2, and MgH2 in as-received conditions and after cold rolling were microwave irradiated in a vacuum using a simple experimental setup. After irradiation, the samples were characterized by X-ray diffraction in other to evaluate the effectiveness of microwave heating. The diffraction patterns indicated that only MgH2 could be fully decomposed (dehydrided in the as received state. TiH2 was only partially decomposed while no decomposition was observed for ZrH2. However, cold rolling the hydride powders prior to microwave heating led to a significant improvement of hydride decomposition, resulting in the complete dehydriding of TiH2 and extensive dehydriding of ZrH2. These results clearly indicated the positive effects of cold rolling on the microwave assisted desorption of the investigated binary hydrides.

  6. Hydride-induced amplification of performance and binding enthalpies in chromium hydrazide gels for Kubas-type hydrogen storage.

    Science.gov (United States)

    Hamaed, Ahmad; Hoang, Tuan K A; Moula, Golam; Aroca, Ricardo; Trudeau, Michel L; Antonelli, David M

    2011-10-05

    Hydrogen is the ideal fuel because it contains the most energy per gram of any chemical substance and forms water as the only byproduct of consumption. However, storage still remains a formidable challenge because of the thermodynamic and kinetic issues encountered when binding hydrogen to a carrier. In this study, we demonstrate how the principal binding sites in a new class of hydrogen storage materials based on the Kubas interaction can be tuned by variation of the coordination sphere about the metal to dramatically increase the binding enthalpies and performance, while also avoiding the shortcomings of hydrides and physisorpion materials, which have dominated most research to date. This was accomplished through hydrogenation of chromium alkyl hydrazide gels, synthesized from bis(trimethylsilylmethyl) chromium and hydrazine, to form materials with low-coordinate Cr hydride centers as the principal H(2) binding sites, thus exploiting the fact that metal hydrides form stronger Kubas interactions than the corresponding metal alkyls. This led to up to a 6-fold increase in storage capacity at room temperature. The material with the highest capacity has an excess reversible storage of 3.23 wt % at 298 K and 170 bar without saturation, corresponding to 40.8 kg H(2)/m(3), comparable to the 2015 DOE system goal for volumetric density (40 kg/m(3)) at a safe operating pressure. These materials possess linear isotherms and enthalpies that rise on coverage, retain up to 100% of their adsorption capacities on warming from 77 to 298 K, and have no kinetic barrier to adsorption or desorption. In a practical system, these materials would use pressure instead of temperature as a toggle and can thus be used in compressed gas tanks, currently employed in the majority of hydrogen test vehicles, to dramatically increase the amount of hydrogen stored, and therefore range of any vehicle.

  7. A review of recent advances on the effects of microstructural refinement and nano-catalytic additives on the hydrogen storage properties of metal and complex hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Varin, R. A.; Zbroniec, L. [University of Waterloo, Department of Mechanical and Mechatronics Engineering, Waterloo, Ontario (Canada); Polanski, M.; Bystrzycki, J. [Faculty of Advanced Technology and Chemistry, Military University of Technology, Warsaw (Poland)

    2011-07-01

    The recent advances on the effects of microstructural refinement and various nano-catalytic additives on the hydrogen storage properties of metal and complex hydrides obtained in the last few years in the allied laboratories at the University of Waterloo (Canada) and Military University of Technology (Warsaw, Poland) are critically reviewed in this paper. The research results indicate that microstructural refinement (particle and grain size) induced by ball milling influences quite modestly the hydrogen storage properties of simple metal and complex metal hydrides. On the other hand, the addition of nanometric elemental metals acting as potent catalysts and/or metal halide catalytic precursors brings about profound improvements in the hydrogen absorption/desorption kinetics for simple metal and complex metal hydrides alike. In general, catalytic precursors react with the hydride matrix forming a metal salt and free nanometric or amorphous elemental metals/intermetallics which, in turn, act catalytically. However, these catalysts change only kinetic properties i.e. the hydrogen absorption/desorption rate but they do not change thermodynamics (e.g., enthalpy change of hydrogen sorption reactions). It is shown that a complex metal hydride, LiAlH{sub 4}, after high energy ball milling with a nanometric Ni metal catalyst and/or MnCl{sub 2} catalytic precursor, is able to desorb relatively large quantities of hydrogen at room temperature, 40 and 80 {sup o}C. This kind of behavior is very encouraging for the future development of solid state hydrogen systems. (authors)

  8. A Review of Recent Advances on the Effects of Microstructural Refinement and Nano-Catalytic Additives on the Hydrogen Storage Properties of Metal and Complex Hydrides

    Directory of Open Access Journals (Sweden)

    Jerzy Bystrzycki

    2010-12-01

    Full Text Available The recent advances on the effects of microstructural refinement and various nano-catalytic additives on the hydrogen storage properties of metal and complex hydrides obtained in the last few years in the allied laboratories at the University of Waterloo (Canada and Military University of Technology (Warsaw, Poland are critically reviewed in this paper. The research results indicate that microstructural refinement (particle and grain size induced by ball milling influences quite modestly the hydrogen storage properties of simple metal and complex metal hydrides. On the other hand, the addition of nanometric elemental metals acting as potent catalysts and/or metal halide catalytic precursors brings about profound improvements in the hydrogen absorption/desorption kinetics for simple metal and complex metal hydrides alike. In general, catalytic precursors react with the hydride matrix forming a metal salt and free nanometric or amorphous elemental metals/intermetallics which, in turn, act catalytically. However, these catalysts change only kinetic properties i.e. the hydrogen absorption/desorption rate but they do not change thermodynamics (e.g., enthalpy change of hydrogen sorption reactions. It is shown that a complex metal hydride, LiAlH4, after high energy ball milling with a nanometric Ni metal catalyst and/or MnCl2 catalytic precursor, is able to desorb relatively large quantities of hydrogen at RT, 40 and 80 °C. This kind of behavior is very encouraging for the future development of solid state hydrogen systems.

  9. Advanced Hydride Laboratory

    Energy Technology Data Exchange (ETDEWEB)

    Motyka, T.

    1989-01-01

    Metal hydrides have been used at the Savannah River Tritium Facilities since 1984. However, the most extensive application of metal hydride technology at the Savannah River Site is being planned for the Replacement Tritium Facility, a $140 million facility schedules for completion in 1990 and startup in 1991. In the new facility, metal hydride technology will be used to store, separate, isotopically purify, pump, and compress hydrogen isotopes. In support of the Replacement Tritium Facility, a $3.2 million, cold,'' process demonstration facility, the Advanced Hydride Laboratory began operation in November of 1987. The purpose of the Advanced Hydride Laboratory is to demonstrate the Replacement Tritium Facility's metal hydride technology by integrating the various unit operations into an overall process. This paper will describe the Advanced Hydride Laboratory, its role and its impact on the application of metal hydride technology to tritium handling.

  10. Advanced Hydride Laboratory

    Energy Technology Data Exchange (ETDEWEB)

    Motyka, T.

    1989-12-31

    Metal hydrides have been used at the Savannah River Tritium Facilities since 1984. However, the most extensive application of metal hydride technology at the Savannah River Site is being planned for the Replacement Tritium Facility, a $140 million facility schedules for completion in 1990 and startup in 1991. In the new facility, metal hydride technology will be used to store, separate, isotopically purify, pump, and compress hydrogen isotopes. In support of the Replacement Tritium Facility, a $3.2 million, ``cold,`` process demonstration facility, the Advanced Hydride Laboratory began operation in November of 1987. The purpose of the Advanced Hydride Laboratory is to demonstrate the Replacement Tritium Facility`s metal hydride technology by integrating the various unit operations into an overall process. This paper will describe the Advanced Hydride Laboratory, its role and its impact on the application of metal hydride technology to tritium handling.

  11. Hydrogen storage properties of Mg-Ni-Fe composites prepared by hydriding combustion synthesis and mechanical milling

    Energy Technology Data Exchange (ETDEWEB)

    Zhu Yunfeng, E-mail: yfzhu@njut.edu.cn [College of Materials Science and Engineering, Nanjing University of Technology, Nanjing 210009 (China); Yang Yang; Wei Lingjun; Zhao Zelun; Li Liquan [College of Materials Science and Engineering, Nanjing University of Technology, Nanjing 210009 (China)

    2012-04-15

    Highlights: Black-Right-Pointing-Pointer Mg-Ni-Fe composite was prepared by the process of HCS + MM. Black-Right-Pointing-Pointer Fe is favorable to grain and particle refinement of the composite. Black-Right-Pointing-Pointer Mg-Ni-Fe composite exhibits superior hydrogen storage properties. Black-Right-Pointing-Pointer Mg{sub 2}Ni and Fe have synergistic catalysis on hydrogen storage properties. - Abstract: We reported the structures and superior hydrogen storage properties of the composites Mg{sub 90}Ni{sub 10-x}Fe{sub x} (x = 0, 2, 4, 6 and 8) prepared by the process of HCS + MM, i.e., the hydriding combustion synthesis followed by mechanical milling. By means of X-ray diffraction (XRD), scanning electron microscopy (SEM) with an energy dispersive X-ray spectrometer (EDX) and gas reaction controller (GRC), the crystal structures, surface morphologies and hydriding/dehydriding properties of the composites were studied in detail. The Mg{sub 90}Ni{sub 10-x}Fe{sub x} (x = 2, 4, 6 and 8) composites consist of MgH{sub 2}, Mg, Mg{sub 2}NiH{sub 4}, Mg{sub 2}NiH{sub 0.3} and Fe phases, while Mg{sub 90}Ni{sub 10} is composed of MgH{sub 2}, Mg, Mg{sub 2}NiH{sub 4} and Mg{sub 2}NiH{sub 0.3}. It is found that Mg{sub 90}Ni{sub 2}Fe{sub 8} has the best hydriding properties, requiring only 30 s to absorb 97% of its saturated hydrogen capacity of 4.80 wt.% at 373 K. The best dehydriding result is obtained with Mg{sub 90}Ni{sub 8}Fe{sub 2}, which desorbs 2.02 and 4.40 wt.% hydrogen at 493 and 523 K, respectively. The microstructures of the composites prepared by HCS + MM have remarkable influences on the enhanced hydriding/dehydriding properties. In addition, the catalytic effects of Mg{sub 2}Ni and Fe phases during hydriding/dehydriding were discussed in this study.

  12. Electrochemical Properties of LaNiSIZE=2>(sub 5-x)GeSIZE=2>(sub x) Alloys in Ni-MH Batteries

    Science.gov (United States)

    Bowman, R. C., Jr.; Witham, C.

    1997-01-01

    Electrochemical studies were performed on LaNiSIZE=2>(sub 5-x)GeSIZE=2>(sub x) metal hydride alloys with 0 <= x <= 0.5. We carried out single-electrode studies to understand the effects of the Ge substituent on the hydrogen absorption characteristics, the electrochemical capacity, and the electrochemical kinetics of hydrogen absorption and desorption.

  13. Oxidation of alcohols by hydrogen peroxide, catalyzed by methyltrioxorhenium (MTO): A hydride abstraction

    Energy Technology Data Exchange (ETDEWEB)

    Zauche, T.H.; Espenson, J.H. [Ames Lab., IA (United States)]|[Iowa State Univ., Ames, IA (United States). Dept. of Chemistry

    1998-12-28

    Primary and secondary alcohols are oxidized using hydrogen peroxide as an oxygen donor and methyltrioxorhenium (MTO) as a catalyst. The methylrhenium di-peroxide, CH{sub 3}Re(O)({eta}{sub 2}-O{sub 2}){sub 2}(H{sub 2}O), was the dominant and reactive form of the catalyst. Representative rate constants k/L/mol s are 1.02 {times} 10{sup {minus}4} for 4-Me-{alpha}-methylbenzyl alcohol and 4.9 {times} 10{sup {minus}5} for 4-Cl-{alpha}-methylbenzyl alcohol. There was a kinetic isotope effect of 3.2 for the {alpha} C-H bond. When sec-phenethyl alcohol was labeled with {sup 18}O, 80% of the oxygen was retained in the ketone. Tests for the possible intervention of a free radical intermediate were carried out; the evidence was entirely negative. A mechanism featuring hydride abstraction is proposed, the first time for the H{sub 2}O{sub 2}/MTO system. Also, a cocatalytic set of reaction conditions has been developed on the synthetic scale, using bromide and MTO as cocatalysts, which cuts the reaction time from hours to minutes.

  14. Well-Defined Molecular Magnesium Hydride Clusters : Relationship between Size and Hydrogen-Elimination Temperature

    NARCIS (Netherlands)

    Intemann, Julia; Spielmann, Jan; Sirsch, Peter; Harder, Sjoerd

    A new tetranuclear magnesium hydride cluster, [{NN-(MgH)2}2], which was based on a NN-coupled bis--diketiminate ligand (NN2-), was obtained from the reaction of [{NN-(MgnBu)2}2] with PhSiH3. Its crystal structure reveals an almost-tetrahedral arrangement of Mg atoms and two different sets of hydride

  15. Reversible storage of the hydrogen by nano structured magnesium hydride; Stockage reversible de l'hydrogene sous forme d'hydrure de magnesium nano-structure

    Energy Technology Data Exchange (ETDEWEB)

    Rango, P. de; Chaise, A.; Fruchart, D.; Miraglia, S. [Institut Neel et CRETA, CNRS - UJF, 38 - Grenoble (France); Marty, P. [LEGI - INPG, 38 - Grenoble (France)

    2007-07-01

    The magnesium hydride MgH{sub 2} is an excellent hydrogen storage element: low cost, abundant, high mass storage capacity up to 7,6% by weight. Meanwhile it presents slow absorption-desorption kinetics and too high thermodynamical stability. Many studies have been realized to improve these kinetics by co-milling with a transition metal. The author presents the metal transition mechanism of this process and the transfer of the production in the industry. (A.L.B.)

  16. Thermodynamic and structural study of the Zr-Ni-Cr ternary system (Zr<50 at%) and of its equilibria with hydrogen: electrochemical application; Etude thermodynamique et structurale du systeme ternaire Zr-Ni-Cr (Zr<50at%) et de ses equilibres avec l`hydrogene: application electrochimique

    Energy Technology Data Exchange (ETDEWEB)

    Joubert, J.M.

    1995-07-12

    In the frame of the research on intermetallic compounds for nickel-hydride battery application, attention is focused on AB{sub 2} alloys so called Laves phases. ZrCr{sub 2}, for example, exhibits a large hydrogen capacity but a too low hydride formation equilibrium pressure for practical application. Moreover, the electrolyte (concentrated potassium hydroxide) involves surface passivation through blocking electrochemical mechanisms. First, the study is devoted to the adjustment of the hydride thermodynamic properties regarded to electrochemical application. This was achieved on ZrCr{sub 2} by substitution of chromium by nickel. In a second part surface properties are modified by the precipitation of secondary phases in equilibrium with the Laves phase. The Zr-Ni-Cr phase diagram has been determined at 1000 deg C in the ZrCr{sub 2}-ZrNi-Ni-Cr region and has revealed large solubility of nickel in C14 and C15 Laves phases as well as equilibrium of these phases with three Zr-Ni intermetallic compounds. The knowledge of this diagram has allowed the synthesis of biphasic alloys where the Laves phase of constant composition is in equilibrium with a secondary phase at variable rate. The study of hydrogenation properties of Laves phases has shown the possibility of adjusting the equilibrium pressure of its hydrides to electrochemical application keeping high hydrogen capacity. The hydrogenation properties of secondary phases were also characterized. Finally, it appeared that secondary phases precipitation with increasing rate in the Laves phase matrix produces a spectacular increase of electrochemical capacities. Such an effect of hydrogen by the modification of the surface in contact with electrolyte and by the diffusion of hydrogen from electrolyte to the Laves through the secondary phase when present. (author)

  17. Effect of lanthanum hydride on microstructures and hydrogen storage performances of 2LiNH2-MgH2 system

    Institute of Scientific and Technical Information of China (English)

    朱惜林; 韩树民; 赵鑫; 李媛; 刘宝忠

    2014-01-01

    Hydrogen storage properties of 2LiNH2-MgH2 system were improved by adding lanthanum hydride (LaH3), and the role of LaH3 in hydrogen sorption process of Li-Mg-N-H system was investigated. Temperature programmed sorption results showed that the addition of lanthanum hydride reduced the dehydriding/hydriding onset temperature of 2LiNH2-MgH2 system by at least 15 K. Moreover, A 0.053 wt.%/min average rate was determined for the hydrogen desorption of 2LiNH2-MgH2-0.05LaH3 composite, while it was only 0.035 wt.%/min for 2LiNH2-MgH2 system. Hydrogen absorption capacity increased from 1.62 wt.% to 2.12 wt.% within 200 min by adding LaH3 into 2LiNH2-MgH2 system at 383 K. In the dehydrogenation of 2LiNH2-MgH2-0.05LaH3 composite, LaH2 transferred to LaN phase, which reversed to LaH2 in the following hydrogen adsorption process. The reversible reaction of LaH2 ef-fectively promoted the hydrogen sorption of Li-Mg-N-H system. Moreover, the homogenous distribution of fine La hydride was fa-vorable to improving effect of lanthanum hydride.

  18. Structural and kinetic studies of metal hydride hydrogen storage materials using thin film deposition and characterization techniques

    Science.gov (United States)

    Kelly, Stephen Thomas

    Hydrogen makes an attractive energy carrier for many reasons. It is an abundant chemical fuel that can be produced from a wide variety of sources and stored for very long periods of time. When used in a fuel cell, hydrogen emits only water at the point of use, making it very attractive for mobile applications such as in an automobile. Metal hydrides are promising candidates for on-board reversible hydrogen storage in mobile applications due to their very high volumetric storage capacities---in most cases exceeding even that of liquid hydrogen. The United States Department of Energy (DOE) has set fuel system targets for an automotive hydrogen storage system, but as of yet no single material meets all the requirements. In particular, slow reaction kinetics and/or inappropriate thermodynamics plague many metal hydride hydrogen storage materials. In order to engineer a practical material that meets the DOE targets, we need a detailed understanding of the kinetic and thermodynamic properties of these materials during the phase change. In this work I employed sputter deposited thin films as a platform to study materials with highly controlled chemistry, microstructure and catalyst placement using thin film characterization techniques such as in situ x-ray diffraction (XRD) and neutron reflectivity. I observed kinetic limitations in the destabilized Mg2Si system due to the slow diffusion of the host Mg and Si atoms while forming separate MgH2 and Si phases. Conversely, I observed that the presence of Al in the Mg/Al system inhibits hydrogen diffusion while the host Mg and Al atoms interdiffuse readily, allowing the material to fall into a kinetic and/or thermodynamic trap by forming intermetallic compounds such as Mg17Al 12. By using in situ XRD to analyze epitaxial Mg films grown on (001) oriented Al2O3 substrates I observed hydride growth consistent with a model of a planar hydride layer growing into an existing metal layer. Subsequent film cycling changes the hydrogen

  19. Structure and electrochemical properties of La-Mg-Ni system hydrogen storage alloys with different Co contents

    Institute of Scientific and Technical Information of China (English)

    WANG Jian-hui; ZHONG Kai; DING Hui; LI Rui; GAO Ming-xia; PAN Hong-ge

    2005-01-01

    The structure and electrochemical properties of the La0.7Mg0.3Ni3.4-xMn0.1Cox (x=0-1.05) hydrogen storage alloys were investigated. The crystal structure and the lattice parameters of the alloys were analyzed by X-ray diffractometry and Rietveld method. Electrochemical properties of the alloys including p-c-t curves, discharge capacity, discharge capacity retention were studied. The results show that (La, Mg)Ni3 and LaNi5 are the main phases of all the alloys. The plateau pressure for hydrogen absorption/desorption decreases and the hydrogen storage capacity firstly increases and subsequently decreases with increasing Co content. The values of the maximum discharge capacity of the alloy electrodes remain in range of 395.3-403.1mA·h/g in spite of the change of Co content. The cycling stability of the alloy electrodes is greatly improved with increasing Co content, which is attributed to the suppression of the cell volume expansion during hydriding, leading the pulverization of the alloy particles lowered and the oxidation/corrosion of the active elements reduced.

  20. Selective Electrochemical Generation of Hydrogen Peroxide from Water Oxidation.

    Science.gov (United States)

    Viswanathan, Venkatasubramanian; Hansen, Heine A; Nørskov, Jens K

    2015-11-01

    Water is a life-giving source, fundamental to human existence, yet over a billion people lack access to clean drinking water. The present techniques for water treatment such as piped, treated water rely on time and resource intensive centralized solutions. In this work, we propose a decentralized device concept that can utilize sunlight to split water into hydrogen and hydrogen peroxide. The hydrogen peroxide can oxidize organics while the hydrogen bubbles out. In enabling this device, we require an electrocatalyst that can oxidize water while suppressing the thermodynamically favored oxygen evolution and form hydrogen peroxide. Using density functional theory calculations, we show that the free energy of adsorbed OH* can be used to determine selectivity trends between the 2e(-) water oxidation to H2O2 and the 4e(-) oxidation to O2. We show that materials which bind oxygen intermediates sufficiently weakly, such as SnO2, can activate hydrogen peroxide evolution. We present a rational design principle for the selectivity in electrochemical water oxidation and identify new material candidates that could perform H2O2 evolution selectively.

  1. Mechanistic aspects of dinitrogen cleavage and hydrogenation to produce ammonia in catalysis and organometallic chemistry: relevance of metal hydride bonds and dihydrogen.

    Science.gov (United States)

    Jia, Hong-Peng; Quadrelli, Elsje Alessandra

    2014-01-21

    Dinitrogen cleavage and hydrogenation by transition-metal centers to produce ammonia is central in industry and in Nature. After an introductory section on the thermodynamic and kinetic challenges linked to N2 splitting, this tutorial review discusses three major classes of transition-metal systems (homogeneous, heterogeneous and biological) capable of achieving dissociation and hydrogenation of dinitrogen. Molecular complexes, solid-state Haber-Bosch catalytic systems, silica-supported tantalum hydrides and nitrogenase will be discussed. Emphasis is focused on the reaction mechanisms operating in the process of dissociation and hydrogenation of dinitrogen, and in particular on the key role played by metal hydride bonds and by dihydrogen in such reactions.

  2. Metal Hydrides for Rechargeable Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Valoeen, Lars Ole

    2000-03-01

    Rechargeable battery systems are paramount in the power supply of modern electronic and electromechanical equipment. For the time being, the most promising secondary battery systems for the future are the lithium-ion and the nickel metal hydride (NiMH) batteries. In this thesis, metal hydrides and their properties are described with the aim of characterizing and improving those. The thesis has a special focus on the AB{sub 5} type hydrogen storage alloys, where A is a rare earth metal like lanthanum, or more commonly misch metal, which is a mixture of rare earth metals, mainly lanthanum, cerium, neodymium and praseodymium. B is a transition metal, mainly nickel, commonly with additions of aluminium, cobalt, and manganese. The misch metal composition was found to be very important for the geometry of the unit cell in AB{sub 5} type alloys, and consequently the equilibrium pressure of hydrogen in these types of alloys. The A site substitution of lanthanum by misch metal did not decrease the surface catalytic properties of AB{sub 5} type alloys. B-site substitution of nickel with other transition elements, however, substantially reduced the catalytic activity of the alloy. If the internal pressure within the electrochemical test cell was increased using inert argon gas, a considerable increase in the high rate charge/discharge performance of LaNi{sub 5} was observed. An increased internal pressure would enable the utilisation of alloys with a high hydrogen equivalent pressure in batteries. Such alloys often have favourable kinetics and high hydrogen diffusion rates and thus have a potential for improving the high current discharge rates in metal hydride batteries. The kinetic properties of metal hydride electrodes were found to improve throughout their lifetime. The activation properties were found highly dependent on the charge/discharge current. Fewer charge/discharge cycles were needed to activate the electrodes if a small current was used instead of a higher

  3. Metal Hydrides for Rechargeable Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Valoeen, Lars Ole

    2000-03-01

    Rechargeable battery systems are paramount in the power supply of modern electronic and electromechanical equipment. For the time being, the most promising secondary battery systems for the future are the lithium-ion and the nickel metal hydride (NiMH) batteries. In this thesis, metal hydrides and their properties are described with the aim of characterizing and improving those. The thesis has a special focus on the AB{sub 5} type hydrogen storage alloys, where A is a rare earth metal like lanthanum, or more commonly misch metal, which is a mixture of rare earth metals, mainly lanthanum, cerium, neodymium and praseodymium. B is a transition metal, mainly nickel, commonly with additions of aluminium, cobalt, and manganese. The misch metal composition was found to be very important for the geometry of the unit cell in AB{sub 5} type alloys, and consequently the equilibrium pressure of hydrogen in these types of alloys. The A site substitution of lanthanum by misch metal did not decrease the surface catalytic properties of AB{sub 5} type alloys. B-site substitution of nickel with other transition elements, however, substantially reduced the catalytic activity of the alloy. If the internal pressure within the electrochemical test cell was increased using inert argon gas, a considerable increase in the high rate charge/discharge performance of LaNi{sub 5} was observed. An increased internal pressure would enable the utilisation of alloys with a high hydrogen equivalent pressure in batteries. Such alloys often have favourable kinetics and high hydrogen diffusion rates and thus have a potential for improving the high current discharge rates in metal hydride batteries. The kinetic properties of metal hydride electrodes were found to improve throughout their lifetime. The activation properties were found highly dependent on the charge/discharge current. Fewer charge/discharge cycles were needed to activate the electrodes if a small current was used instead of a higher

  4. Catalytic Hydrogenation Activity and Electronic Structure Determination of Bis(arylimidazol-2-ylidene)pyridine Cobalt Alkyl and Hydride Complexes

    Science.gov (United States)

    Yu, Renyuan Pony; Darmon, Jonathan M.; Milsmann, Carsten; Margulieux, Grant W.; E. Stieber, S. Chantal; DeBeer, Serena

    2013-01-01

    The bis(arylimidazol-2-ylidene)pyridine cobalt methyl complex, (iPrCNC)CoCH3, was evaluated for the catalytic hydrogenation of alkenes. At 22 °C and 4 atm of H2 pressure, (iPrCNC)CoCH3 is an effective pre-catalyst for the hydrogenation of sterically hindered, unactivated alkenes such as trans-methylstilbene, 1-methyl-1-cyclohexene and 2,3-dimethyl-2-butene, representing one of the most active cobalt hydrogenation catalysts reported to date. Preparation of the cobalt hydride complex, (iPrCNC)CoH was accomplished by hydrogenation of (iPrCNC)CoCH3. Over the course of 3 hours at 22 °C, migration of the metal-hydride to the 4-position of the pyridine ring yielded (4-H2-iPrCNC)CoN2. Similar alkyl migration was observed upon treatment of (iPrCNC)CoH with 1,1-diphenylethylene. This reactivity raised the question as to whether this class of chelate is redoxactive, engaging in radical chemistry with the cobalt center. A combination of structural, spectroscopic and computational studies was conducted and provided definitive evidence for bis(arylimidazol-2-ylidene)pyridine radicals in reduced cobalt chemistry. Spin density calculations established that the radicals were localized on the pyridine ring, accounting for the observed reactivity and suggest a wide family of pyridine-based pincers may also be redox active. PMID:23968297

  5. Reversible hydrogen storage in nano-structured magnesium hydride; Stockage reversible de l'hydrogene sous forme d'hydrure de magnesium nano-structure

    Energy Technology Data Exchange (ETDEWEB)

    Rango, P. de; Chaise, A.; Fruchart, D.; Miraglia, S. [Grenoble-1 Univ. Joseph-Fourier, Institut Neel / CRETA, CNRS, 38 (France); Marty, P. [Institut National Polytechnique (INPG-LEGI), 38 - Grenoble (France)

    2007-07-01

    Magnesium hydride MgH{sub 2} is an excellent potential material for hydrogen storage: abundant and cheap, it presents a high gravimetric density (7.6% in mass of hydrogen). Nevertheless, it presents both very slow absorption/desorption kinetics and a too important thermodynamic stability leading to absorption/desorption temperatures of about 300 C. A lot of studies have been carried out to improve the reaction kinetics by co-grinding with a transition metal. The aim of this work is to explain particularly the role of the transition metal. Experimental results are presented and analyzed. (O.M.)

  6. Neutral transition metal hydrides as acids in hydrogen bonding and proton transfer: media polarity and specific solvation effects.

    Science.gov (United States)

    Levina, Vladislava A; Filippov, Oleg A; Gutsul, Evgenii I; Belkova, Natalia V; Epstein, Lina M; Lledos, Agusti; Shubina, Elena S

    2010-08-18

    Structural, spectroscopic, and electronic features of weak hydrogen-bonded complexes of CpM(CO)(3)H (M = Mo (1a), W (1b)) hydrides with organic bases (phosphine oxides R(3)PO (R = n-C(8)H(17), NMe(2)), amines NMe(3), NEt(3), and pyridine) are determined experimentally (variable temperature IR) and computationally (DFT/M05). The intermediacy of these complexes in reversible proton transfer is shown, and the thermodynamic parameters (DeltaH degrees , DeltaS degrees ) of each reaction step are determined in hexane. Assignment of the product ion pair structure is made with the help of the frequency calculations. The solvent effects were studied experimentally using IR spectroscopy in CH(2)Cl(2), THF, and CH(3)CN and computationally using conductor-like polarizable continuum model (CPCM) calculations. This complementary approach reveals the particular importance of specific solvation for the hydrogen-bond formation step. The strength of the hydrogen bond between hydrides 1 and the model bases is similar to that of the M-H...X hydrogen bond between 1 and THF (X = O) or CH(3)CN (X = N) or between CH(2)Cl(2) and the same bases. The latter competitive weak interactions lower the activities of both the hydrides and the bases in the proton transfer reaction. In this way, these secondary effects shift the proton transfer equilibrium and lead to the counterintuitive hampering of proton transfer upon solvent change from hexane to moderately polar CH(2)Cl(2) or THF.

  7. Effect of hydrogen atoms on the structures of trinuclear metal carbonyl clusters: trinuclear manganese carbonyl hydrides.

    Science.gov (United States)

    Liu, Xian-mei; Wang, Chao-yang; Li, Qian-shu; Xie, Yaoming; King, R Bruce; Schaefer, Henry F

    2009-05-18

    The structures of the trinuclear manganese carbonyl hydrides H(3)Mn(3)(CO)(n) (n = 12, 11, 10, 9) have been investigated by density functional theory (DFT). Optimization of H(3)Mn(3)(CO)(12) gives the experimentally known structure in which all carbonyl groups are terminal and each edge of a central Mn(3) equilateral triangle is bridged by a single hydrogen atom. This structure establishes the canonical distance 3.11 A for the Mn-Mn single bond satisfying the 18-electron rule. The central triangular (mu-H)(3)Mn(3) unit is retained in the lowest energy structure of H(3)Mn(3)(CO)(11), which may thus be derived from the H(3)Mn(3)(CO)(12) structure by removal of a carbonyl group with concurrent conversion of one of the remaining carbonyl groups into a semibridging carbonyl group to fill the resulting hole. The potential energy surface of H(3)Mn(3)(CO)(10) is relatively complicated with six singlet and five triplet structures. One of the lower energy H(3)Mn(3)(CO)(10) structures has one of the hydrogen atoms bridging the entire Mn(3) triangle and the other two hydrogen atoms bridging Mn-Mn edges. This H(3)Mn(3)(CO)(10) structure achieves the favored 18-electron configuration with a very short MnMn triple bond of 2.36 A. The other low energy H(3)Mn(3)(CO)(10) structure retains the (mu-H)(3)Mn(3) core of H(3)Mn(3)(CO)(12) but has a unique six-electron donor eta(2)-mu(3) carbonyl group bridging the entire Mn(3) triangle similar to the unique carbonyl group in the known compound Cp(3)Nb(3)(CO)(6)(eta(2)-mu(3)-CO). For H(3)Mn(3)(CO)(9) a structure with a central (mu(3)-H)(2)Mn(3) trigonal bipyramid lies >20 kcal/mol below any of the other structures. Triplet structures were found for the unsaturated H(3)Mn(3)(CO)(n) (n = 11, 10, 9) systems but at significantly higher energies than the lowest lying singlet structures.

  8. Lithium-lithium hydride process for the production of hydrogen: comparison of two concepts for 950 and 1300 deg C HTR helium outlet temperature

    Energy Technology Data Exchange (ETDEWEB)

    Oertel, M.; Weirich, W.; Kuegler, B.; Luecke, L.; Pietsch, M.; Winkelmann, U.

    1987-01-01

    The lithium-lithium hydride process serves to generate hydrogen from water efficiently, using the high temperature heat of a nuclear reactor. Thermodynamic analyses show that hydrogen can be produced with an overall thermal efficiency of 48% at conventional HTR outlet temperatures of 950/sup 0/C. Assuming helium heat of 1300/sup 0/C, 56% overall thermal efficiency can be achieved.

  9. Thermodynamic System Studies for a Natural Gas Combined Cycle (NGCC) Plant with CO2 Capture and Hydrogen Storage with Metal Hydrides

    NARCIS (Netherlands)

    Thallam Thattai, A.; Wittebrood, B.J.; Woudstra, T.; Geerlings, J.J.C.; Aravind, P.V.

    2014-01-01

    Flexibility in natural gas combined cycle power plants (NGCC) with pre-combustion CO2 capture could be introduced with co-production of hydrogen and subsequent hydrogen storage with metal hydrides (MH). The current work presents a thermodynamic analysis and comparison between steady state ASPEN Plus

  10. Thermodynamic System Studies for a Natural Gas Combined Cycle (NGCC) Plant with CO2 Capture and Hydrogen Storage with Metal Hydrides

    NARCIS (Netherlands)

    Thallam Thattai, A.; Wittebrood, B.J.; Woudstra, T.; Geerlings, J.J.C.; Aravind, P.V.

    2014-01-01

    Flexibility in natural gas combined cycle power plants (NGCC) with pre-combustion CO2 capture could be introduced with co-production of hydrogen and subsequent hydrogen storage with metal hydrides (MH). The current work presents a thermodynamic analysis and comparison between steady state ASPEN Plus

  11. Characterization of Hydrogen-Storage Properties and Physical Properties of Zinc Borohydride and Transition Metals-Added Magnesium Hydride

    Directory of Open Access Journals (Sweden)

    Young Jun KWAK

    2017-02-01

    Full Text Available In this work, 90 wt.% MgH2 + 5 wt.% Ni + 1.7 wt.% Zn(BH42 + 1.7 wt.% Ti + 1.7 wt.% Fe samples (named 90MgH2 + 5Ni + 1.7Zn(BH42 + 1.7Ti + 1.7Fe were prepared by milling in a planetary ball mill in a hydrogen atmosphere. The fraction of additives was small (10 wt.% in order to increase hydriding and dehydriding rates without decreasing the hydrogen storage capacity much. The hydrogen absorption and release properties of the prepared samples were investigated. 90MgH2 + 5Ni + 1.7Zn(BH42 + 1.7Ti + 1.7Fe had an effective hydrogen storage capacity of 5 wt.%. The activation of 90MgH2 + 5Ni + 1.7Zn(BH42 + 1.7Ti + 1.7Fe was completed after 2 hydriding-dehydriding cycles. At n = 3, the sample absorbed 4.14 wt.% H for 5 min and 5.00 wt.% H for 60 min at 593 K under 12 bar H2. The sample dehydrided at the 3rd hydriding-dehydriding cycle contained Mg and small amounts of β-MgH2, MgO, Mg2Ni, TiH1.924, and Fe. The BET specific surface areas of the sample after milling in a hydrogen atmosphere and after 3 hydriding-dehydriding cycles were 57.9 and 53.2 m2/g, respectively.DOI: http://dx.doi.org/10.5755/j01.ms.23.1.14878

  12. Characterization of Hydrogen-Storage Properties and Physical Properties of Zinc Borohydride and Transition Metals-Added Magnesium Hydride

    Directory of Open Access Journals (Sweden)

    Young Jun KWAK

    2017-02-01

    Full Text Available In this work, 90 wt.% MgH2 + 5 wt.% Ni + 1.7 wt.% Zn(BH42 + 1.7 wt.% Ti + 1.7 wt.% Fe samples (named 90MgH2 + 5Ni + 1.7Zn(BH42 + 1.7Ti + 1.7Fe were prepared by milling in a planetary ball mill in a hydrogen atmosphere. The fraction of additives was small (10 wt.% in order to increase hydriding and dehydriding rates without decreasing the hydrogen storage capacity much. The hydrogen absorption and release properties of the prepared samples were investigated. 90MgH2 + 5Ni + 1.7Zn(BH42 + 1.7Ti + 1.7Fe had an effective hydrogen storage capacity of 5 wt.%. The activation of 90MgH2 + 5Ni + 1.7Zn(BH42 + 1.7Ti + 1.7Fe was completed after 2 hydriding-dehydriding cycles. At n = 3, the sample absorbed 4.14 wt.% H for 5 min and 5.00 wt.% H for 60 min at 593 K under 12 bar H2. The sample dehydrided at the 3rd hydriding-dehydriding cycle contained Mg and small amounts of β-MgH2, MgO, Mg2Ni, TiH1.924, and Fe. The BET specific surface areas of the sample after milling in a hydrogen atmosphere and after 3 hydriding-dehydriding cycles were 57.9 and 53.2 m2/g, respectively.DOI: http://dx.doi.org/10.5755/j01.ms.23.1.14878

  13. Vodonik kao energetski vektor budućnosti - hidridi i baterije na vodonik / Hydrogen as an energy vector of the future: Hydrides and bacteria exploiting the hydrogen

    Directory of Open Access Journals (Sweden)

    Mitar Konjević

    2005-09-01

    Full Text Available Vodonik predstavlja ekološki čist i praktično neiscrpan energent, relativno lak za skladištenje, transport i korišćenje. Međutim, zbog visoke cene dobijanja još uvek ne konkuriše aktuelnim fosilnim gorivima. Ako se pretpostavlja da će vodonik predstavljati vrlo važan energetski vektor u budućnosti, interesantno je pokazati mogućnosti njegovog korišćenja u vidu hidrida i gorivnih ćelija. / Hydrogen represents the ecologically clean and practically inexhaustible energetic element, relatively easy for storage, transportation and exploitation. Nevertheless, due to high price of its production, hydrogen has not yet been a competition to actual fossil fuels. If we suppose that hydrogen will be pretty important vector in future, it is interesting to show the exploitation possibilities of hydrogen informs of hydrides and fuel cells.

  14. Ab initio study of magnesium and magnesium hydride nanoclusters and nanocrystals: examining optimal structures and compositions for efficient hydrogen storage.

    Science.gov (United States)

    Koukaras, Emmanuel N; Zdetsis, Aristides D; Sigalas, Michael M

    2012-09-26

    On the basis of the attractive possibility of efficient hydrogen storage in light metal hydrides, we have examined a large variety of Mg(n)H(m) nanoclusters and (MgH(2))(n) nanocrystals (n = 2-216, m = 2-436) using high level coupled cluster, CCSD(T), ab initio methods, and judicially chosen density functional calculations of comparable quality and (near chemical) accuracy. Our calculated desorption energies as a function of size and percentage of hydrogen have pinpointed optimal regions of sizes and concentrations of hydrogen which are in full agreement with recent experimental findings. Furthermore, our results reproduce the experimental desorption energy of 75.5 kJ/mol for the infinite system with remarkable accuracy (76.5 ± 1.5 kJ/mol).

  15. High-Pressure Raman and Calorimetry Studies of Vanadium(III) Alkyl Hydrides for Kubas-Type Hydrogen Storage.

    Science.gov (United States)

    Morris, Leah; Trudeau, Michel L; Reed, Daniel; Book, David; Antonelli, David M

    2016-03-16

    Reversible hydrogen storage under ambient conditions has been identified as a major bottleneck in enabling a future hydrogen economy. Herein, we report an amorphous vanadium(III) alkyl hydride gel that binds hydrogen through the Kubas interaction. The material possesses a gravimetric adsorption capacity of 5.42 wt % H2 at 120 bar and 298 K reversibly at saturation with no loss of capacity after ten cycles. This corresponds to a volumetric capacity of 75.4 kgH2  m(-3) . Raman experiments at 100 bar confirm that Kubas binding is involved in the adsorption mechanism. The material possesses an enthalpy of H2 adsorption of +0.52 kJ mol(-1) H2 , as measured directly by calorimetry, and this is practical for use in a vehicles without a complex heat management system.

  16. Research of new AB type hydrogen storage materials that can be used as a negative electrode in nickel -metal hydride battery; Recherche de nouveaux composes intermetalliques hydrurables de type AB utilisables comme electrode negative d`accumulateur nickel-hydrure

    Energy Technology Data Exchange (ETDEWEB)

    Jordy, Ch.

    1994-12-15

    The aim of this work is to determine new AB type hydrogen storage materials that can be used as a negative electrode in nickel-metal hydride battery. The main requested solid-gas hydrogenation properties are as follows : a reversible capacity higher than 400 mAh/g and a plateau pressure close to 0, 01 MPa at 25 deg C. Binary intermetallic compounds have been selected according to their high hydrogen capacity. The thermodynamic properties of the hydride have to be adjusted by partial substitution of the A and/or B elements. The selected binary intermetallic rate to the substitution was based on known thermodynamic models and on criteria on hydrogen atom occupation in interstitial sites. The only alloys, which could have interest, are the one which are homogeneous. Amongst them, the compounds Ti(Fe{sub 1-x}) where M=Ni,Co,Mn,Cr, showed a solid-gas capacity higher than 400 mAh/g and a plateau pressure close to 0,01 MPa at 25 deg C. Nevertheless, the electrochemical capacity is extremely low due to the iron corrosion in concentrated KOH. The electrochemical capacities of (Ti{sub 1-x-y} Zr{sub x}M{sub y})Ni compounds for M=V and Si are the most promising in the AB type since a 350 m Ah/g reversible capacity has been measured bY THE CONSTANT POTENTIAL METHOD. We also showed that the partial zirconium substitution made the martensitic transformation temperature higher. (author)

  17. The electrochemical Peltier heat of the standard hydrogen electrode reaction

    Energy Technology Data Exchange (ETDEWEB)

    Fang Zheng [Chemistry and Chemical Engineering College, Central South University, Changsha 410083 (China)], E-mail: zfang@csu.edu.cn; Wang Shaofen [School of Chemistry and Environmental Engineering, Changsha University of Science and Technology, Changsha 410077 (China); Zhang Zhenghua [Chemistry and Chemical Engineering College, Central South University, Changsha 410083 (China); Qiu Guanzhou [School of Minerals Processing and Bioengineering, Central South University, Changsha 410083 (China)

    2008-07-10

    A method for measuring the electrochemical Peltier heat (EPH) of a single electrode reaction has been developed and an absolute scale is suggested to obtain EPH of the standard hydrogen electrode. The scale is based on {phi}{sub 0}* = 0 and {delta}S{sub 0}* = 0 for any electrode reaction at zero Kelvin, in accord with the third law of thermodynamics. The relationships between entropy, enthalpy and free energy changes on this scale and on the conventional scale are derived. Calorimetric experiments were made on the Fe(CN){sub 6}{sup 3-}/Fe(CN){sub 6}{sup 4-} system at five different concentrations at 298.15 K, and EPH for the standard hydrogen electrode reaction is obtained. EPHs and the entropy change on the absolute scale for the studied redox are linearly related to concentration of electrolyte. The reversible electric work is almost concentration independent in the range of concentration studied.

  18. Thermochemical Energy Storage through De/Hydrogenation of Organic Liquids: Reactions of Organic Liquids on Metal Hydrides.

    Science.gov (United States)

    Ulmer, Ulrich; Cholewa, Martin; Diemant, Thomas; Bonatto Minella, Christian; Dittmeyer, Roland; Behm, R Jürgen; Fichtner, Maximilian

    2016-06-08

    A study of the reactions of liquid acetone and toluene on transition metal hydrides, which can be used in thermal energy or hydrogen storage applications, is presented. Hydrogen is confined in TiFe, Ti0.95Zr0.05Mn1.49V0.45Fe0.06 ("Hydralloy C5"), and V40Fe8Ti26Cr26 after contact with acetone. Toluene passivates V40Fe8Ti26Cr26 completely for hydrogen desorption while TiFe is only mildly deactivated and desorption is not blocked at all in the case of Hydralloy C5. LaNi5 is inert toward both organic liquids. Gas chromatography (GC) investigations reveal that CO, propane, and propene are formed during hydrogen desorption from V40Fe8Ti26Cr26 in liquid acetone, and methylcyclohexane is formed in the case of liquid toluene. These reactions do not occur if dehydrogenated samples are used, which indicates an enhanced surface reactivity during hydrogen desorption. Significant amounts of carbon-containing species are detected at the surface and subsurface of acetone- and toluene-treated V40Fe8Ti26Cr26 by X-ray photoelectron spectroscopy (XPS). The modification of the surface and subsurface chemistry and the resulting blocking of catalytic sites is believed to be responsible for the containment of hydrogen in the bulk. The surface passivation reactions occur only during hydrogen desorption of the samples.

  19. SSH2S: Hydrogen storage in complex hydrides for an auxiliary power unit based on high temperature proton exchange membrane fuel cells

    Science.gov (United States)

    Baricco, Marcello; Bang, Mads; Fichtner, Maximilian; Hauback, Bjorn; Linder, Marc; Luetto, Carlo; Moretto, Pietro; Sgroi, Mauro

    2017-02-01

    The main objective of the SSH2S (Fuel Cell Coupled Solid State Hydrogen Storage Tank) project was to develop a solid state hydrogen storage tank based on complex hydrides and to fully integrate it with a High Temperature Proton Exchange Membrane (HT-PEM) fuel cell stack. A mixed lithium amide/magnesium hydride system was used as the main storage material for the tank, due to its high gravimetric storage capacity and relatively low hydrogen desorption temperature. The mixed lithium amide/magnesium hydride system was coupled with a standard intermetallic compound to take advantage of its capability to release hydrogen at ambient temperature and to ensure a fast start-up of the system. The hydrogen storage tank was designed to feed a 1 kW HT-PEM stack for 2 h to be used for an Auxiliary Power Unit (APU). A full thermal integration was possible thanks to the high operation temperature of the fuel cell and to the relative low temperature (170 °C) for hydrogen release from the mixed lithium amide/magnesium hydride system.

  20. Surface analysis, hydrogen adsorption and electrochemical performance of alkali-reduce treated hydrogen storage alloy

    Institute of Scientific and Technical Information of China (English)

    陈卫祥; 徐铸德; 涂江平; 李海洋; 陈石; 袁俊; 鲍世宁

    2002-01-01

    The hydrogen storage alloy powders (MlNi4.0Co0.6Al0.4, Ml=rich-La mischmetal) were treated in a hot 6mol/L KOH+0.02mol/L KBH4 solution, the surface compositions and chemical states of the treated and untreated alloys were analyzed by XPS and EDX, the hydrogen adsorption on the surface of these alloys was evaluated by thermal desorption spectroscopy (TDS), the effects of the surface treatment on the electrochemical performances of the alloy electrodes were investigated. The results show that the hydrogen adsorption is greatly strengthened by the surface modification, and hence leads to marked improvement in the electrocatalytic activity, the treated alloy exhibits higher exchange current density and lower apparent activation energy for the hydrogen electrode reaction than the untreated alloy.

  1. An electrochemical hydrogen meter for measuring hydrogen in sodium using a ternary electrolyte mixture

    CERN Document Server

    Sridharan, R; Nagaraj, S; Gnanasekaran, T; Periaswami, G

    2003-01-01

    An electrochemical sensor for measuring hydrogen concentration in liquid sodium that is based on a ternary mixture of LiCl, CaCl sub 2 and CaHCl as the electrolyte has been developed. DSC experiments showed the eutectic temperature of this ternary system to be approx 725 K. Impedance spectroscopic analysis of the electrolyte indicated ionic conduction through a molten phase at approx 725 K. Two electrochemical hydrogen sensors were constructed using the ternary electrolyte of composition 70 mol% LiCl:16 mol% CaHCl:14 mol% CaCl sub 2 and tested at 723 K in a mini sodium loop and at hydrogen levels of 60-250 ppb in sodium. The sensors show linear response in this concentration range and are capable of detecting a change of 10 ppb hydrogen in sodium over a background level of 60 ppb. Identification of this electrolyte system and its use in a sensor for measuring hydrogen in sodium are described in this paper.

  2. Kinetic behaviour of low-Co AB{sub 5}-type metal hydride electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Tliha, M., E-mail: Mohamed.Tliha@esstt.rnu.tn [Laboratoire de Mecanique, Materiaux et Procedes, ESSTT, 5 Avenue Taha Hussein, 1008 Tunis (Tunisia); Boussami, S.; Mathlouthi, H.; Lamloumi, J. [Laboratoire de Mecanique, Materiaux et Procedes, ESSTT, 5 Avenue Taha Hussein, 1008 Tunis (Tunisia); Percheron-Guegan, A. [Laboratoire de Chimie Metallurgique des Terres Rares, GLVT, 2-8 Rue Henri Dunant 94320, Thiais Cedex (France)

    2010-11-15

    The kinetic behaviour of the LaNi{sub 3.55}Mn{sub 0.4}Al{sub 0.3}Co{sub 0.4}Fe{sub 0.35} metal hydride, used as a negative electrode in the nickel/metal hydride (Ni/MH) batteries, was investigated using electrochemical impedance spectroscopy (EIS) at different state of charge (SOC). Impedance measurements were performed in the frequency range from 50 kHz to 1 mHz. Electrochemical impedance spectrum of the metal hydride electrode was interpreted by an equivalent circuit including the different electrochemical processes taking place on the interface between the MH electrode and the electrolyte. Electrochemical kinetic parameters such as the charge-transfer resistance R{sub tc}, the exchange current density I{sub 0} and the hydrogen diffusion coefficient D{sub H} were determined at different state of charge. The results of EIS measurements indicate that the electrochemical reaction activity of the LaNi{sub 3.55}Mn{sub 0.4}Al{sub 0.3}Co{sub 0.4}Fe{sub 0.35} metal hydride electrode was markedly improved with increasing state of charge (SOC). The transformation {alpha}-{beta} is probably a limiting step in the mechanisms of hydrogenation of metal hydride electrode.

  3. Development of Hydrogen Storage Tank Systems Based on Complex Metal Hydrides

    Directory of Open Access Journals (Sweden)

    Morten B. Ley

    2015-09-01

    Full Text Available This review describes recent research in the development of tank systems based on complex metal hydrides for thermolysis and hydrolysis. Commercial applications using complex metal hydrides are limited, especially for thermolysis-based systems where so far only demonstration projects have been performed. Hydrolysis-based systems find their way in space, naval, military and defense applications due to their compatibility with proton exchange membrane (PEM fuel cells. Tank design, modeling, and development for thermolysis and hydrolysis systems as well as commercial applications of hydrolysis systems are described in more detail in this review. For thermolysis, mostly sodium aluminum hydride containing tanks were developed, and only a few examples with nitrides, ammonia borane and alane. For hydrolysis, sodium borohydride was the preferred material whereas ammonia borane found less popularity. Recycling of the sodium borohydride spent fuel remains an important part for their commercial viability.

  4. Development and Electrochemical Testing of Novel Bipolar Nickel Metal Hydride Batteries

    Institute of Scientific and Technical Information of China (English)

    DENG Chao; SHI Peng-fei

    2006-01-01

    Some aspects in the design and development of bipolar Ni/MH battery are presented. After optimizing sealing technique and modifying capacity ratio of two adjacent electrodes in one sub-cell, some bipolar Ni/MH stacks with 6 sub-cells have been assembled and investigated. Electrochemical testing results show the bipolar battery has excellent high rate discharge capability and fast recharge ability, and satisfactory charging efficiency in different states of charge. Moreover, the battery also displays good stability under pulse cycles in simulating hybrid vehicle working conditions.

  5. Hydrogen bonding and proton transfer to ruthenium hydride complex CpRuH(dppe): metal and hydride dichotomy.

    Science.gov (United States)

    Silantyev, Gleb A; Filippov, Oleg A; Tolstoy, Peter M; Belkova, Natalia V; Epstein, Lina M; Weisz, Klaus; Shubina, Elena S

    2013-02-18

    The combination of variable temperature (190-297 K) IR and NMR spectroscopy studies with quantum-chemical calculations at the DFT/B3PW91 and AIM level had the aim to determine the mechanism of proton transfer to CpRuH(dppe) (1, dppe = Ph(2)P(CH(2))(2)PPh(2)) and the structures of intermediates. Dihydrogen bond (DHB) formation was established in the case of interaction with weak proton donors like CF(3)CH(2)OH. Low-temperature protonation (at about 200 K) by stronger proton donors leads via DHB complex to the cationic nonclassical complex [CpRu(η(2)-H(2))(dppe)](+) (2). Thermodynamic parameters of DHB formation (for CF(3)CH(2)OH: ΔH°(HB) = -4.9 ± 0.2 kcal·mol(-1), ΔS°(HB) = -17.8 ± 0.7 cal·mol(-1)·K(-1)) and proton transfer (for (CF(3))(2)CHOH: ΔH°(PT) = -5.2 ± 0.3 kcal·mol(-1), ΔS°(PT) = -23 ± 1 cal·mol(-1)·K(-1)) were determined. Above 240 K 2 transforms into trans-[CpRu(H)(2)(dppe)](+) (3) yielding a mixture of 2 and 3 in 1:2 ratio. Kinetic analysis and activation parameters for the "[Ru(η(2)-H(2))](+) → trans-[Ru(H)(2)](+)" transformation indicate reversibility of this process in contrast to irreversible intramolecular isomerization of the Cp* analogue. Calculations show that the driving force of this process is greater stability (by 1.5 kcal·mol(-1) in ΔE scale) of the dihydride cation in comparison with the dihydrogen complex. The calculations of the potential energy profile indicate the low barrier for deprotonation of 2 suggesting that the formation of trans-[CpRu(H)(2)(dppe)](+) proceeds via deprotonation of [Ru(η(2)-H(2))](+) to DHB complex, formation of hydrogen bond with Ru atom and subsequent proton transfer to the metal site.

  6. Advanced Electrochemical Technologies for Hydrogen Production by Alternative Thermochemical Cycles

    Energy Technology Data Exchange (ETDEWEB)

    Lvov, Serguei; Chung, Mike; Fedkin, Mark; Lewis, Michele; Balashov, Victor; Chalkova, Elena; Akinfiev, Nikolay; Stork, Carol; Davis, Thomas; Gadala-Maria, Francis; Stanford, Thomas; Weidner, John; Law, Victor; Prindle, John

    2011-01-06

    Hydrogen fuel is a potentially major solution to the problem of climate change, as well as addressing urban air pollution issues. But a key future challenge for hydrogen as a clean energy carrier is a sustainable, low-cost method of producing it in large capacities. Most of the world's hydrogen is currently derived from fossil fuels through some type of reforming processes. Nuclear hydrogen production is an emerging and promising alternative to the reforming processes for carbon-free hydrogen production in the future. This report presents the main results of a research program carried out by a NERI Consortium, which consisted of Penn State University (PSU) (lead), University of South Carolina (USC), Tulane University (TU), and Argonne National Laboratory (ANL). Thermochemical water decomposition is an emerging technology for large-scale production of hydrogen. Typically using two or more intermediate compounds, a sequence of chemical and physical processes split water into hydrogen and oxygen, without releasing any pollutants externally to the atmosphere. These intermediate compounds are recycled internally within a closed loop. While previous studies have identified over 200 possible thermochemical cycles, only a few have progressed beyond theoretical calculations to working experimental demonstrations that establish scientific and practical feasibility of the thermochemical processes. The Cu-Cl cycle has a significant advantage over other cycles due to lower temperature requirements – around 530 °C and below. As a result, it can be eventually linked with the Generation IV thermal power stations. Advantages of the Cu-Cl cycle over others include lower operating temperatures, ability to utilize low-grade waste heat to improve energy efficiency, and potentially lower cost materials. Another significant advantage is a relatively low voltage required for the electrochemical step (thus low electricity input). Other advantages include common chemical agents and

  7. Electrochemical performance of nickel/metal hydride batteries under unconventional conditions and degradation analysis

    Institute of Scientific and Technical Information of China (English)

    李丽; 吴锋; 杨凯; 王敬; 陈实

    2004-01-01

    The charge-discharge performance and cycle stability of D size Ni/MH batteries at -20 ℃, 25 ℃ and 55℃ were examined. The results show that the decline rate of Ni/MH battery discharge capacity at -20 ℃ and 55 ℃ are 12.1% and 13.6% ,and the average discharge voltage decreases by a value of 0.13 V and 0.06 V respectively,cycling stability declines obviously at various temperatures. The capacity degradation of Ni/MH batteries under low temperature is reversible, belonging to transient degradation and that of high and normal temperatures are not reversible, belonging to permanent degradation. Electrochemical impedance spectroscopy, scanning electron microscope and energy dispersive X-ray analyzer were introduced to study the main causes of cycling deterioration of Ni/MH batteries.

  8. Filiform-mode hydride corrosion of uranium surfaces

    Science.gov (United States)

    Hill, M. A.; Schulze, R. K.; Bingert, J. F.; Field, R. D.; McCabe, R. J.; Papin, P. A.

    2013-11-01

    Hydride nucleation and growth has previously been studied in uranium with an air-formed oxide. Preferred directional growth of uranium hydride has not been observed, presumably due to the constraint of the oxide layer and/or the presence of a surface layer distorted by mechanical grinding and polishing. Instead, hydrides typically first form as subsurface blisters that do not exhibit preferred growth directionality. By eliminating the strained surface layer through electropolishing, removing the natural oxide through ion sputtering, avoiding exposure of the uranium to air, and then exposing uranium to high purity hydrogen in an environmental cell, hydride growth patterns emerge that correspond to defect structures within the microstructure. These hydride growth patterns are similar to filiform corrosion, a type of corrosion that frequently forms under thin protective films. This work describes the first reported observation of filiform-like corrosion in uranium. The uranium hydride initiates at defects, but grows into filaments up to 20 μm wide, and tends to form in straight lines, largely propagating along twin boundaries. Propagation is driven by hydrogen reaction at the filament head, promoted by more efficient delivery of reactant. However, this phenomenon does not involve an electrochemical process associated with conventional filiform corrosion and is therefore described as filiform-like. Hydride growth was observed using optical microscopy for a period of nearly three years. Sample characterization included automated electron backscatter diffraction (EBSD) measurements to determine growth directions. Observation of this anomalous hydride growth provides clues as to the mechanisms operating in uranium hydriding for more conventionally prepared sample surfaces.

  9. Enhanced hydrogen desorption properties of magnesium hydride by coupling non-metal doping and nano-confinement

    Science.gov (United States)

    He, Daliang; Wang, Yulong; Wu, Chengzhang; Li, Qian; Ding, Weizhong; Sun, Chenghua

    2015-12-01

    Magnesium hydride (MgH2) offers excellent capacity to store hydrogen, but it suffers from the high desorption temperature (>283 °C for starting release hydrogen). In this work, we calculated the hydrogen desorption energy of Mg76H152 clusters with/without non-metal dopants by density functional theory method. Phosphorus (P), as identified as the best dopant, can reduce the reaction energy for releasing one hydrogen molecule from 0.75 eV (bulk MgH2) to 0.20 eV. Inspired by the calculation, P-doped ordered mesoporous carbon (CMK-3) was synthesized by one-step method and employed as the scaffold for loading MgH2 nanoparticles, forming MgH2@P/CMK-3. Element analysis shows that phosphorus dopants have been incorporated into the CMK-3 scaffold and magnesium and phosphorus elements are well-distributed in carbon scaffold hosts. Tests of hydrogen desorption confirmed that P-doping can remarkably enhance the hydrogen release properties of nanoconfined MgH2 at low temperature, specifically ˜1.5 wt. % H2 released from MgH2@P/CMK-3 below 200 °C. This work, based on the combination of computational calculations and experimental studies, demonstrated that the combined approach of non-metal doping and nano-confinement is promising for enhancing the hydrogen desorption properties of MgH2, which provides a strategy to address the challenge of hydrogen desorption from MgH2 at mild operational conditions.

  10. Surface modification of a proton exchange membrane and hydrogen storage in a metal hydride for fuel cells

    Science.gov (United States)

    Andrews, Lisa

    promising option. Effective hydrogen storage methods must be used as sources of available hydrogen. One possibility is to use hydrogen stored in a solid chemical compound such as magnesium hydride. The kinetics of hydrogen release from the hydrolysis of magnesium hydride with 2 wt% acetic acid was examined. The hydrogen produced was supplied to a fuel cell and the amount of hydrogen consumed by the fuel cell was determined. Carbon nanotubes also can play a role in energy sources and as components in fuel cells. VUV photo-oxidized single walled carbon nanotubes (SWNT) paper was grafted with polyacrylic acid and analyzed using XPS.

  11. Reversible Li-insertion in nanoscaffolds: A promising strategy to alter the hydrogen sorption properties of Li-based complex hydrides

    NARCIS (Netherlands)

    Ngene, Peter; Verkuijlen, Margriet H. W.; Barre, Charlotte; Kentgens, Arno P. M.; de Jongh, Petra E.

    Intercalation and de-intercalation of lithium into graphene layers is a well-established phenomenon in Li-ion battery technology. Here we show how this phenomenon can be exploited to destabilize, and alter the hydrogen sorption behaviour of Li-based metal hydrides (LiBH4 and LiAlH4), thereby

  12. Reversible Li-insertion in nanoscaffolds: A promising strategy to alter the hydrogen sorption properties of Li-based complex hydrides

    NARCIS (Netherlands)

    Ngene, Peter; Verkuijlen, Margriet H. W.; Barre, Charlotte; Kentgens, Arno P. M.; de Jongh, Petra E.

    2016-01-01

    Intercalation and de-intercalation of lithium into graphene layers is a well-established phenomenon in Li-ion battery technology. Here we show how this phenomenon can be exploited to destabilize, and alter the hydrogen sorption behaviour of Li-based metal hydrides (LiBH4 and LiAlH4), thereby achievi

  13. Promising gaseous and electrochemical hydrogen storage properties of porous Mg-Pd films under mild conditions.

    Science.gov (United States)

    Xin, Gongbiao; Yuan, Huiping; Jiang, Lijun; Wang, Shumao; Liu, Xiaopeng; Li, Xingguo

    2015-05-28

    In this paper, the gaseous and electrochemical hydrogen storage properties of 200 nm Mg-Pd thin films with different morphologies have been investigated. The results show that Mg-Pd films become porous with the increase of substrate temperature. Porous Mg-Pd films exhibit superior gaseous and electrochemical hydrogen storage behaviors under mild conditions, including rapid hydrogen sorption kinetics, a large hydrogen storage amount, high electrochemical discharge capacity, and a fast hydrogen diffusion rate. The excellent behaviors of porous Mg-Pd films might be ascribed to the significantly shortened hydrogen diffusion paths and the large contact areas between the hydrogen gas and the solid Mg phases, which are elucidative for the development and applications of thick Mg-Pd films.

  14. A simulation study on the hydrogen storage properties of fullerene family molecules Cx(x = 56,60,70) and their hydrides

    Science.gov (United States)

    Dai, Wei; Xiao, Ming; Chen, Mu-Qing; Xu, Jia-Jing; Tang, Yong-Jian

    2016-08-01

    Hydrogen storage is a key factor for the application of hydrogen energy. From first principle calculation, we have acquired the energy barrier for hydrogen molecules to pass through the hexagonal rings and pentagonal rings of the fullerene. Then the absorption energy and energy barrier are used to analyze the hydrogen adsorption capacity of the fullerene family and their hydrides. We have also studied the hydrogen storage properties of the fullerene family and their hydrides by grand canonical Monte Carlo method. It is found that the weight density of hydrogen storage at ambient temperature and pressure can reach 7.71 wt.%. The results show that it is difficult for hydrogen to get into the carbon cage of the fullerene because of the high energy barrier, while it is beneficial to destroy the fullerene structure for the processes of absorption and desorption. Meanwhile, fullerene hydrogenation is an effective method to improve the hydrogen storage properties. Our study facilitates the design and synthesis of hydrogen storage materials, and provides theoretical support to improve the hydrogen storage capability for materials.

  15. Beyond Metal-Hydrides: Non-Transition-Metal and Metal-Free Ligand-Centered Electrocatalytic Hydrogen Evolution and Hydrogen Oxidation.

    Science.gov (United States)

    Haddad, Andrew Z; Garabato, Brady D; Kozlowski, Pawel M; Buchanan, Robert M; Grapperhaus, Craig A

    2016-06-29

    A new pathway for homogeneous electrocatalytic H2 evolution and H2 oxidation has been developed using a redox active thiosemicarbazone and its zinc complex as seminal metal-free and transition-metal-free examples. Diacetyl-bis(N-4-methyl-3-thiosemicarbazone) and zinc diacetyl-bis(N-4-methyl-3-thiosemicarbazide) display the highest reported TOFs of any homogeneous ligand-centered H2 evolution catalyst, 1320 and 1170 s(-1), respectively, while the zinc complex also displays one of the highest reported TOF values for H2 oxidation, 72 s(-1), of any homogeneous catalyst. Catalysis proceeds via ligand-centered proton-transfer and electron-transfer events while avoiding traditional metal-hydride intermediates. The unique mechanism is consistent with electrochemical results and is further supported by density functional theory. The results identify a new direction for the design of electrocatalysts for H2 evolution and H2 oxidation that are not reliant on metal-hydride intermediates.

  16. Electrochemical preparation of hematite nanostructured films for solar hydrogen production

    Directory of Open Access Journals (Sweden)

    Ebadzadeh T.

    2012-10-01

    Full Text Available Photoelectrochemical water splitting is a clean and promising technique for using a renewable source of energy, i.e., solar energy, to produce hydrogen. In this work electrochemical formation of iron oxyhydroxide and its conversion to hematite (α- Fe2O3 through thermal treatment have been studied. Oxyhydroxide iron compounds have been prepared onto SnO2/F covered glass substrate by potential cycling with two different potential sweep rate values; then calcined at 520 °C in air to obtain α-Fe2O3 nanostrutured films for their implementation as photoanode in a photoelectrochemical cell. X-ray diffraction analysis allowed finding that iron oxides films have nanocrystalline character. Scanning electron microscopy revealed that films have nanostructured morphology. The obtained results are discussed considering the influence of potential sweep rate employed during the preparation of iron oxyhydroxide film on optical, structural and morphological properties of hematite nanostructured films. Results show that films have acceptable characteristics as photoanode in a photoelectrochemical cell for hydrogen generation from water.

  17. Large-scale screening of metal hydrides for hydrogen storage from first-principles calculations based on equilibrium reaction thermodynamics.

    Science.gov (United States)

    Kim, Ki Chul; Kulkarni, Anant D; Johnson, J Karl; Sholl, David S

    2011-04-21

    Systematic thermodynamics calculations based on density functional theory-calculated energies for crystalline solids have been a useful complement to experimental studies of hydrogen storage in metal hydrides. We report the most comprehensive set of thermodynamics calculations for mixtures of light metal hydrides to date by performing grand canonical linear programming screening on a database of 359 compounds, including 147 compounds not previously examined by us. This database is used to categorize the reaction thermodynamics of all mixtures containing any four non-H elements among Al, B, C, Ca, K, Li, Mg, N, Na, Sc, Si, Ti, and V. Reactions are categorized according to the amount of H(2) that is released and the reaction's enthalpy. This approach identifies 74 distinct single step reactions having that a storage capacity >6 wt.% and zero temperature heats of reaction 15 ≤ΔU(0)≤ 75 kJ mol(-1) H(2). Many of these reactions, however, are likely to be problematic experimentally because of the role of refractory compounds, B(12)H(12)-containing compounds, or carbon. The single most promising reaction identified in this way involves LiNH(2)/LiH/KBH(4), storing 7.48 wt.% H(2) and having ΔU(0) = 43.6 kJ mol(-1) H(2). We also examined the complete range of reaction mixtures to identify multi-step reactions with useful properties; this yielded 23 multi-step reactions of potential interest.

  18. Catalytic Hydrogenation of Organic Compounds without H2 Supply: An Electrochemical System

    Science.gov (United States)

    Navarro, Daniela Maria do Amaral Ferraz; Navarro, Marcelo

    2004-01-01

    An experiment developed for an undergraduate organic chemistry laboratory course that can be used to introduce the catalytic hydrogenation reaction, catalysis electrochemical principles and gas chromatography is presented. The organic compounds hydrogenated by the electrocatalytic hydrogenation (ECH) process were styrene, benzaldehyde and…

  19. Hydrogen embrittlement, revisited by in situ electrochemical nanoindentation

    Energy Technology Data Exchange (ETDEWEB)

    Barnoush, Afrooz

    2007-07-01

    The fine scale mechanical probing capability of NI-AFM was used to examine hydrogen interaction with plasticity. To realize this, an electrochemical three electrode setup was incorporated into the NI-AFM. The developed ECNI-AFM is capable of performing nanoindentation as well as imaging surfaces inside electrolytes. The developed ECNI-AFM setup was used to examine the effect of cathodically charged hydrogen on dislocation nucleation in pure metals and alloys. It was shown that hydrogen reduces the pop-in load in all of the tested materials except Cu. The reduced pop-in load can be interpreted as the HELP mechanism. Classical dislocation theory was used to model the homogeneous dislocation nucleation and it was shown that H reduces the activation energy for dislocation nucleation in H sensitive metals which are not undergoing a phase transformation. The activation energy for dislocation nucleation is related to the material specific parameters; shear modulus {mu}, dislocation core radius {rho} and in the case of partial dislocation nucleation, stacking fault energy {gamma}. These material properties can be influenced by H resulting in a reduced activation energy for dislocation nucleation. The universality of cohesion in bulk metals relates the reduction of the shear modulus to the reduction of the cohesion, meaning HEDE mechanism. The increase in the core radius of a dislocation due to H is a direct evidence of decrease in dislocation line energy and H segregation on the dislocation line. In the case of partial dislocations, the H can segregate on to the stacking fault ribbon and decrease {gamma}. This inhibits the cross slip process and enhances the slip planarity. Thus, HELP and HEDE are the two sides of a coin resulting in H embrittlement. However depending on the experimental approach utilized to probe the H effect, either HELP or HEDE can be observed. In this study, however, by utilizing a proper experimental approach, it was possible to resolve the

  20. Hydrogen production for micro-fuel-cell from activated Al-Sn-Zn-X (X: hydride or halide) mixture in water

    Energy Technology Data Exchange (ETDEWEB)

    Fan, Mei Qiang [Materials and Thermochemistry Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023 (China); Department of Materials Science and Engineering, China Jiliang University, Hangzhou, 310018 (China); Sun, Li Xian [Materials and Thermochemistry Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023 (China); Xu, Fen [College of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029 (China)

    2011-02-15

    A systematic investigation of hydrogen production from milled Al-Sn-Zn-X (X: hydride or halide) mixtures in pure water was performed at room temperature. The hydrolysis mechanism of the mixtures was based on the work of micro-galvanic cell between aluminum and tin in water where aluminum reacted with water to generate AlOOH (Boehmite) and hydrogen. It was found that many effects such as milling time, temperature, additives and mass ratio had a significant role in the hydrogen production rate, especially that of the additives (hydride or halide) led to reduction of crystallite size and accumulation of uniform mixing. They also produced a lot of heat and the conductive ions which simulated the work of micro-galvanic cell. The milled Al-Sn-Zn-X (X: hydride or halide) mixtures had high reactivity and Al-Sn-Zn-MgH{sub 2} mixture produced 790 mL g{sup -1} hydrogen in 5 min of the hydrolysis reaction with the activation energy of 17.570 kJ mol{sup -1}, corresponding to 7.04 wt.% hydrogen excluding water mass. Therefore, a new method of CO{sub 2} free and safe hydrogen production for micro-fuel-cell was obtained from the activated aluminum alloys in water. (author)

  1. Electrochemical properties of hypo-stoichiometric Y-doped AB{sub 2} metal hydride alloys at ultra-low temperature

    Energy Technology Data Exchange (ETDEWEB)

    Young, K., E-mail: kwo.young@basf.com [BASF/Battery Materials-Ovonic, 2983 Waterview Drive, Rochester Hills, MI 48309 (United States); Department of Chemical Engineering, Wayne State University, Detroit, MI 48202 (United States); Wong, D.F. [BASF/Battery Materials-Ovonic, 2983 Waterview Drive, Rochester Hills, MI 48309 (United States); Department of Chemical Engineering, Wayne State University, Detroit, MI 48202 (United States); Nei, J.; Reichman, B. [BASF/Battery Materials-Ovonic, 2983 Waterview Drive, Rochester Hills, MI 48309 (United States)

    2015-09-15

    Highlights: • By altering the stoichiometry, the abundance of secondary phases can be engineered. • While TiNi is beneficial, YNi is detrimental to low temperature performance. • By increasing TiNi to YNi ratio, the −40 °C low temperature performance is improved. • Y element has a limited solubility in AB{sub 2} Laves phase. - Abstract: The structure, gaseous phase, and electrochemical hydrogen storage properties of two series of Y-doped AB{sub 2} metal hydride alloys were compared. While the stoichiometry (B/A ratio) of the average alloy composition of the first series is maintained at 1.99 (Ti{sub 12}Zr{sub 21.5}V{sub 10}Cr{sub 7.5}Mn{sub 8.1}Co{sub 8.0−x}Ni{sub 32.2}Y{sub x}Sn{sub 0.3}Al{sub 0.4}), those in the second series decrease from 1.99 to 1.83 ((TiZr)(VCrMnNiSnAl){sub 1.75}Co{sub 0.24−3x}Y{sub x}). Since the solubility of Y in the main phase (C14) is limited (0.1–0.2 at.%), the influences of Y are through the changes in the composition and abundance of the main and secondary phases. While TiNi phase is considered beneficial to activation, surface reaction area, and surface charge-transfer, YNi phase is on the contrary. By adjusting the stoichiometry, we were able to increase the TiNi-to-YNi ratio and lower the −40 °C charge-transfer resistance by increasing the surface reaction area while maintaining the same surface catalytic ability. The lowest −40 °C charge-transfer resistance was obtained through an AB{sub 2} alloy with 0.4 at.% Y and a B/A ratio of 1.93. Further improvement in the ultra-low temperature performance of the AB{sub 1.93} alloy is expected by combining the current result with other modifiers, such as Si, to improve the surface catalytic ability.

  2. Novel electrochemical reactions related to electrodeposition and electrochemical synthesis

    Directory of Open Access Journals (Sweden)

    Ito Y.

    2003-01-01

    Full Text Available Novel electrochemical reactions in molten salts related to electrodeposition and electrochemical synthesis are reviewed to show their usefulness and possibilities in producing functional materials. Surface nitriding of various metals and stainless steels is possible by the use of anodic reaction of nitride ion (N3- in LiCl-KCl-Li3N melts. Electrochemical hydrogen absorption/desorption reaction occurs in molten salts containing hydride ion (H-. Electrochemical implantation and displantation can be applied to form transition metal-rare earth metal alloys in LiCl-KCl melts containing rare earth chlorides. As non-conventional electrochemical reactions, direct electrochemical reduction of SiO2 to Si, discharge electrolysis to form metal oxide particles and electrochemical plantation of Zr on ceramics are described.

  3. Hydrogenation of AB{sub 5} and AB{sub 2} metal hydride alloys studied by in situ X-ray diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Wang, L. [Department of Chemical Engineering and Materials Science, Wayne State University, Detroit, MI 48202 (United States); BASF – Battery Materials Ovonic, 2983 Waterview Drive, Rochester Hills, MI 48309 (United States); Young, K., E-mail: kwo.young@basf.com [BASF – Battery Materials Ovonic, 2983 Waterview Drive, Rochester Hills, MI 48309 (United States); Nei, J.; Pawlik, D. [BASF – Battery Materials Ovonic, 2983 Waterview Drive, Rochester Hills, MI 48309 (United States); Ng, K.Y.S. [Department of Chemical Engineering and Materials Science, Wayne State University, Detroit, MI 48202 (United States)

    2014-12-15

    Highlights: • Hydrogenation process of an AB{sub 5} alloy and two AB{sub 2} alloys were studied by quasi in-situ XRD. • In both AB{sub 5} and AB{sub 2} metal alloy, hydrogen occupation sites on the half-plane were taken first. • In the C14/C15 mixed alloy, C14 phase is the main hydrogen storage phase with a lower equilibrium pressure. • In the C14/C15 mixed alloy, C15 phase is the catalyst hydrogen storage phase with a higher equilibrium pressure. • Small amount of C15 was hydrided first but not completed until C14 phase was fully hydrided. - Abstract: The evolution of lattice constants and abundances of metal (α) and metal hydride (β) phases during the hydrogenation process of an AB{sub 5} alloy with a CaCu{sub 5} crystal structure, an AB{sub 2} alloy with a predominating C14 structure, and a C14/C15-mixed AB{sub 2} alloy were reported. The preferred hydrogen insertion sites at different states of charge in both the α and β phases were studied based on the lattice parameter changes during hydrogenation. During the hydrogenation of the AB{sub 5} alloy, the ratio between lattice parameters a and c (a/c ratio) in the α phase decreases, stabilizes, and then decreases again while that in the β phase decreases and then stabilizes. The trends in unit cell volume changes are increasing, plateauing, and increasing again in the α phase and increasing followed by plateauing in the β phase as the hydrogenation level increases. In the C14-predominant AB{sub 2} alloy, the a/c ratio in the α phase increases at the beginning and then stabilizes while that in the β phase remains about the same and then increases during the addition of hydrogen. Moreover, the unit cell volume in the α phase increases slightly during hydrogenation, comparing to the increasing, decreasing, and then increasing trend in the β phase. In the C14/C15 mixed AB{sub 2} alloy, hydrogenation of the C15 phase starts at the beginning and promotes the hydrogenation of the C14 phase. The C14

  4. Coupling hydrogen separation with butanone hydrogenation in an electrochemical hydrogen pump with sulfonated poly (phthalazinone ether sulfone ketone) membrane

    Science.gov (United States)

    Huang, Shiqi; Wang, Tao; Wu, Xuemei; Xiao, Wu; Yu, Miao; Chen, Wei; Zhang, Fengxiang; He, Gaohong

    2016-09-01

    This work reports the novel work of coupling H2/CO2 separation with biomass-derived butanone hydrogenation in non-fluorinated sulfonated poly (phthalazinone ether sulfone ketone) (SPPESK) electrochemical hydrogen pump (EHP) reactor. Due to higher resistance to swelling, SPPESK-based EHP reactor exhibits more excellent reaction rate in elevated temperature (60 °C) and higher butanone concentration (2 M) as 270, 260 nmol cm-2 s-1, respectively, higher than 240, 200 nmol cm-2 s-1of Nafion-based EHP reactors. Also, the SPPESK-based EHP reactor remains 90% of initial hydrogenation rate after 4 batches, better than that of Nafion-based EHP reactors, which is only 62%. The energy efficiency of EHP separator reaches 40% under H2/CO2 mixture feed mode, and electricity of about 0.3 kWh is consumed per Nm3 H2 product, being superior to energy consumption compared with alternative processes like PSA and electrolysis of water. In addition, SPPESK-based EHP exhibits better hydrogenation stability due to lower CO2 permeation than Nafion. With increasing CO2 content in H2 feed, hydrogenation rate almost keeps constant at around 210 nmol cm-2 s-1 in SPPESK-based EHP reactor while decreases fast to 50 nmol cm-2 s-1 in Nafion/PTFE-based EHP reactor. These results show integration of gas separation with hydrogenation reactor is feasible in SPPESK-based EHP reactor.

  5. Enhanced Hydrogen Generation Properties of MgH2-Based Hydrides by Breaking the Magnesium Hydroxide Passivation Layer

    Directory of Open Access Journals (Sweden)

    Liuzhang Ouyang

    2015-05-01

    Full Text Available Due to its relatively low cost, high hydrogen yield, and environmentally friendly hydrolysis byproducts, magnesium hydride (MgH2 appears to be an attractive candidate for hydrogen generation. However, the hydrolysis reaction of MgH2 is rapidly inhibited by the formation of a magnesium hydroxide passivation layer. To improve the hydrolysis properties of MgH2-based hydrides we investigated three different approaches: ball milling, synthesis of MgH2-based composites, and tuning of the solution composition. We demonstrate that the formation of a composite system, such as the MgH2/LaH3 composite, through ball milling and in situ synthesis, can improve the hydrolysis properties of MgH2 in pure water. Furthermore, the addition of Ni to the MgH2/LaH3 composite resulted in the synthesis of LaH3/MgH2/Ni composites. The LaH3/MgH2/Ni composites exhibited a higher hydrolysis rate—120 mL/(g·min of H2 in the first 5 min—than the MgH2/LaH3 composite— 95 mL/(g·min—without the formation of the magnesium hydroxide passivation layer. Moreover, the yield rate was controlled by manipulation of the particle size via ball milling. The hydrolysis of MgH2 was also improved by optimizing the solution. The MgH2 produced 1711.2 mL/g of H2 in 10 min at 298 K in the 27.1% ammonium chloride solution, and the hydrolytic conversion rate reached the value of 99.5%.

  6. Actuation of Pneumatic Artificial Muscle via Hydrogen Absorption/Desorption of Metal Hydride-LaNi5

    Directory of Open Access Journals (Sweden)

    Thanana Nuchkrua

    2015-01-01

    Full Text Available This paper presents experimental studies on mechanical actuations of a pneumatic artificial muscle (PAM, which is driven by hydrogen gas based metal hydride (MH. The dynamic performances of hydrogen absorption/desorption, taking place within a MH reactor, are controlled via implementing cooling/heating effects of a thermoelectric module (TEM. Hydrogen pressure is applied as a driving force to commanding work outputs of the PAM as desired mechanical actuations. Due to strong inherent nonlinearity, a conventional proportional integral derivative (PID control law is not capable of regulating thermodynamic variables of the HM reaction according to desired performances of the PAM. In this study, the fuzzy adaptive PID control is proposed in manipulating the MH reaction via the TEM. This viability of the proposed methodology is confirmed by the fact that the gains of PID control law are adapted by fuzzy rule-based tuning scheme at various operating conditions of the MH reactor. The experimental results show that the proposed control technique is much more effective than a PID control in both transient and steady state performances of the MH reactor for servo mechanical actuation of the PAM.

  7. Mechanochemical activation and synthesis of nanomaterials for hydrogen storage and conversion in electrochemical power sources.

    Science.gov (United States)

    Wronski, Zbigniew S; Varin, Robert A; Czujko, Tom

    2009-07-01

    In this study we discuss a process of mechanical activation employed in place of chemical or thermal activation to improve the mobility and reactivity of hydrogen atoms and ions in nanomaterials for energy applications: rechargeable batteries and hydrogen storage for fuel cell systems. Two materials are discussed. Both are used or intended for use in power sources. One is nickel hydroxide, Ni(OH)2, which converts to oxyhydroxide in the positive Ni electrode of rechargeable metal hydride batteries. The other is a complex hydride, Mg(AIH4)2, intended for use in reversible, solid-state hydrogen storage for fuel cells. The feature shared by these unlikely materials (hydroxide and hydride) is a sheet-like hexagonal crystal structure. The mechanical activation was conducted in high-energy ball mills. We discuss and demonstrate that the mechanical excitation of atoms and ions imparted on these powders stems from the same class of phenomena. These are (i) proliferation of structural defects, in particular stacking faults in a sheet-like structure of hexagonal crystals, and (ii) possible fragmentation of a faulted structure into a mosaic of layered nanocrystals. The hydrogen atoms bonded in such nanocrystals may be inserted and abstracted more easily from OH- hydroxyl group in Ni(OH)2 and AlH4- hydride complex in Mg(AlH4)2 during hydrogen charge and discharge reactions. However, the effects of mechanical excitation imparted on these powders are different. While the Ni(OH)2 powder is greatly activated for cycling in batteries, the Mg(AlH4)2 complex hydride phase is greatly destabilized for use in reversible hydrogen storage. Such a "synchronic" view of the structure-property relationship in respect to materials involved in hydrogen energy storage and conversion is supported in experiments employing X-ray diffraction (XRD), differential scanning calorimetry (DSC) and direct imaging of the structure with a high-resolution transmission-electron microscope (HREM), as well as in

  8. Hydrogen bonding to carbonyl hydride complex Cp*Mo(PMe(3))(2)(CO)H and its role in proton transfer.

    Science.gov (United States)

    Dub, Pavel A; Filippov, Oleg A; Belkova, Natalia V; Daran, Jean-Claude; Epstein, Lina M; Poli, Rinaldo; Shubina, Elena S

    2010-02-28

    The interaction of the carbonyl hydride complex Cp*Mo(PMe(3))(2)(CO)H with Brønsted (fluorinated alcohols, (CF(3))(n)CH(3-n)OH (n = 1-3), and CF(3)COOH) and Lewis (Hg(C(6)F(5))(2), BF(3).OEt(2)) acids was studied by variable temperature IR and NMR ((1)H, (31)P, (13)C) spectroscopies in combination with DFT/B3LYP calculations. Among the two functionalities potentially capable of the interaction - carbonyl and hydride ligands - the first was found to be the preferential binding site for weak acids, yielding CO...HOR or CO...Hg complexes as well as CO...(HOR)(2) adducts. For stronger proton donors ((CF(3))(3)COH, CF(3)COOH) hydrogen-bonding to the hydride ligand can be revealed as an intermediate of the proton transfer reaction. Whereas proton transfer to the CO ligand is not feasible, protonation of the hydride ligand yields an (eta(2)-H(2)) complex. Above 230 K dihydrogen evolution is observed leading to decomposition. Among the decomposition products compound [Cp*Mo(PMe(3))(3)(CO)](+)[(CF(3))(3)CO.2HOC(CF(3))(3)](-) resulting from a phosphine transfer reaction was characterized by X-ray diffraction. Reaction with BF(3).OEt(2) was found to produce [Cp*Mo(PMe(3))(2)(CO)BF(4)] via initial attack of the hydride ligand.

  9. Hydriding and dehydriding rates and hydrogen-storage capacity of Mg–14Ni–3Fe2O3–3Ti prepared by reactive mechanical grinding

    Indian Academy of Sciences (India)

    Myoung Youp Song; Young Jun Kwak; Hye Ryoung Park; Byoung-Goan Kim

    2013-08-01

    The magnesium prepared by mechanical grinding under H2 (reactive mechanical grinding) with transition elements or oxides showed relatively high hydriding and dehydriding rates when the content of additives was about 20 wt%. Ni (expected to increase hydriding and dehydriding rates) was chosen as transition element to be added. Fe2O3 (expected to increase hydriding rate) was selected as an oxide to be added. Ti was also selected since, it was considered to increase the hydriding and dehydriding rates by forming Ti hydride. A sample, Mg–14Ni–3Fe2O3–3Ti, was prepared by reactive mechanical grinding and its hydrogen storage properties were investigated. This sample absorbed 4.02 wt% H for 5 min, 4.15 wt% H for 10 min and 4.42 wt% H for 60 min at = 2. It desorbed 2.46 wt% H for 10 min, 3.98 wt% H for 30 min and 4.20 wt% H for 60 min at = 2.

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

    Science.gov (United States)

    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.

  11. Experimental Hydrogen Plant with Metal Hydrides to Store and Generate Electrical Power

    Science.gov (United States)

    Gonzatti, Frank; Nizolli, Vinícius; Ferrigolo, Fredi Zancan; Farret, Felix Alberto; de Mello, Marcos Augusto Silva

    2016-02-01

    Generation of electrical energy with renewable sources is interruptible due to the primary energy characteristics (sun, wind, hydro, etc.). In these cases, it is necessary to use energy storage so increasing penetrability of these sources connected to the distribution system. This paper discusses in details some equipment and accessories of an integrated power plant using fuel cell stack, electrolyzer and metal hydrides. During the plant operation were collected the power consumption data and established the efficiency of each plant component. These data demonstrated an overall efficiency of about 11% due to the low efficiencies of the commercial electrolyzers and power inverters used in the experiments.

  12. A computational study on novel carbon-based lithium materials for hydrogen storage and the role of carbon in destabilizing complex metal hydrides

    Science.gov (United States)

    Ghouri, Mohammed Minhaj

    One of the major impediments in the way of the realization of hydrogen economy is the storage of hydrogen gas. This involves both the storage for stationary applications as well as that of storage onboard vehicles for transportation applications. For obvious reasons, the system targets for the automotive applications are more stringent. There are many approaches which are still being researched for the storage of hydrogen for vehicular applications. Among them are the high pressure storage of hydrogen gas and the storing of liquid hydrogen in super insulated cryogenic cylinders. While both of them have been demonstrated practically, the high stakes of their respective shortcomings is hindering the wide spread application of these methods. Thus different solid state storage materials are being looked upon as promising solutions. Metal hydrides are a class of solid state hydrogen storage materials which are formed by the reaction of metals or their alloys with hydrogen. These materials have very good gravimetric storage densities, but are very stable thermodynamically to desorp hydrogen at room temperatures. Research is going on to improve the thermodynamics and the reaction kinetics of different metal hydrides. This dissertation tries to address the problem of high thermodynamic stability of the existing metal hydrides in two ways. First, a novel carbon based lithium material is proposed as a viable storage option based on its promising thermodynamic heat of formation. Pure beryllium (Be) clusters and the carbon-beryllium (C-Be) clusters are studied in detail using the Density Functional Theory (DFT) computational methods. Their interactions with hydrogen molecule are further studied. The results of these calculations indicate that hydrogen is more strongly physisorbed to the beryllium atom in the C-Be cluster, rather than to a carbon atom. After these initial studies, we calculated the geometries and the energies of more than 100 different carbon based lithium

  13. Effect of Gaseous Impurities on Long-Term Thermal Cycling and Aging Properties of Complex Hydrides for Hydrogen Storage

    Energy Technology Data Exchange (ETDEWEB)

    Chandra, Dhanesh [Primary Contact; Lamb, Joshua; Chien, Wen-Ming; Talekar, Anjali; and Pal, Narendra

    2011-03-28

    This program was dedicated to understanding the effect of impurities on Long-Term Thermal Cycling and aging properties of Complex Hydrides for Hydrogen Storage. At the start of the program we found reversibility between Li2NH+LiH LiH+LiNH2 (yielding ~5.8 wt.%H capacity). Then we tested the effect of impurity in H2 gas by pressure cycling at 255°C; first with industrial gas containing ppm levels of O2 and H2O as major impurities. Both these impurities had a significant impact on the reversibility and decreased the capacity by 2.65 wt.%H. Further increase in number of cycles from 500 to 1100 showed only a 0.2 wt%H more weight loss, showing some capacity is still maintained after a significant number of cycles. The loss of capacity is attributed to the formation of ~55 wt% LiH and ~30% Li2O, as major contaminant phases, along with the hydride Li2NH phase; suggesting loss of nitrogen during cycling. The effect of 100 ppm H2O in H2 also showed a decrease of ~2.5 wt.%H (after 560 cycles), and 100ppm O2 in H2; a loss of ~4.1 wt.%. Methane impurity (100 ppm, 100cycles), showed a very small capacity loss of 0.9 wt.%H under similar conditions. However, when Li3N was pressure cycled with 100ppmN2-H2 there were beneficial effects were observed (255oC); the reversible capacity increased to 8.4wt.%H after 853 cycles. Furthermore, with 20 mol.%N2-H2 capacity increased to ~10 wt.%H after 516 cycles. We attribute this enhancement to the reaction of nitrogen with liquid lithium during cycling as the Gibbs free energy of formation of Li3N (Go = -98.7 kJ/mol) is more negative than that of LiH (Go = -50.3 kJ/mol). We propose that the mitigation of hydrogen capacity losses is due to the destabilization of the LiH phase that tends to accumulate during cycling. Also more Li2NH phase was found in the cycled product. Mixed Alanates (3LiNH2:Li3AlH6) showed that 7 wt% hydrogen desorbed under dynamic vacuum. Equilibrium experiments (maximum 12 bar H2) showed up to 4wt% hydrogen reversibly

  14. Electrochemical reduction of hydrogen peroxide on stainless steel

    Indian Academy of Sciences (India)

    S Patra; N Munichandraiah

    2009-09-01

    Electrochemical reduction of hydrogen peroxide is studied on a sand-blasted stainless steel (SSS) electrode in an aqueous solution of NaClO4. The cyclic voltammetric reduction of H2O2 at low concentrations is characterized by a cathodic peak at -0.40 V versus standard calomel electrode (SCE). Cyclic voltammetry is studied by varying the concentration of H2O2 in the range from 0.2 mM to 20 mM and the sweep rate in the range from 2 to 100 mV s-1. Voltammograms at concentrations of H2O2 higher than 2 mM or at high sweep rates consist of an additional current peak, which may be due to the reduction of adsorbed species formed during the reduction of H2O2. Amperometric determination of H2O2 at -0.50 V vs SCE provides the detection limit of 5 M H2O2. A plot of current density versus concentration has two segments suggesting a change in the mechanism of H2O2 reduction at concentrations of H2O2 ≥ 2 mM. From the rotating disc electrode study, diffusion co-efficient of H2O2 and rate constant for reduction of H2O2 are evaluated.

  15. Effect of design parameters on enhancement of hydrogen charging in metal hydride reactors

    Energy Technology Data Exchange (ETDEWEB)

    Kaplan, Y. [Mechanical Engineering Department, Nigde University, 51100 Nigde (Turkey)

    2009-03-15

    The effects of heat transfer mechanisms on the charging process in metal hydride reactors are studied under various charging pressures. Three different cylindrical reactors with the same base dimensions are designed and manufactured. The first one is a closed cylinder cooled with natural convection, the fins are manufactured around the second reactor and the third reactor is cooled with water circulating around the reactor. The temperatures of the reactor at several locations are measured during charging with a range of pressure of 1-10 bar. The third reactor shows the lowest temperature increase with the fastest charging time under all charging pressures investigated. The effective heat transfer coefficients of the reactors are also calculated according to the experimental results and they are found to be 5.5 {+-} 1 W m{sup -2} K{sup -1}, 35 {+-} 2 W m{sup -2} K{sup -1} and 113 {+-} 1 W m{sup -2} K{sup -1}, respectively. The experimental results showed that the charging of hydride reactors is mainly heat transfer dependent and the reactor with better cooling exhibits the fastest charging characteristics. (author)

  16. A composite of complex and chemical hydrides yields the first Al-based amidoborane with improved hydrogen storage properties.

    Science.gov (United States)

    Dovgaliuk, Iurii; Jepsen, Lars H; Safin, Damir A; Łodziana, Zbigniew; Dyadkin, Vadim; Jensen, Torben R; Devillers, Michel; Filinchuk, Yaroslav

    2015-10-05

    The first Al-based amidoborane Na[Al(NH2 BH3 )4 ] was obtained through a mechanochemical treatment of the NaAlH4 -4 AB (AB=NH3 BH3 ) composite releasing 4.5 wt % of pure hydrogen. The same amidoborane was also produced upon heating the composite at 70 °C. The crystal structure of Na[Al(NH2 BH3 )4 ], elucidated from synchrotron X-ray powder diffraction and confirmed by DFT calculations, contains the previously unknown tetrahedral ion [Al(NH2 BH3 )4 ](-) , with every NH2 BH3 (-) ligand coordinated to aluminum through nitrogen atoms. Combination of complex and chemical hydrides in the same compound was possible due to both the lower stability of the AlH bonds compared to the BH ones in borohydride, and due to the strong Lewis acidity of Al(3+) . According to the thermogravimetric analysis-differential scanning calorimetry-mass spectrometry (TGA-DSC-MS) studies, Na[Al(NH2 BH3 )4 ] releases in two steps 9 wt % of pure hydrogen. As a result of this decomposition, which was also supported by volumetric studies, the formation of NaBH4 and amorphous product(s) of the surmised composition AlN4 B3 H(0-3.6) were observed. Furthermore, volumetric experiments have also shown that the final residue can reversibly absorb about 27 % of the released hydrogen at 250 °C and p(H2 )=150 bar. Hydrogen re-absorption does not regenerate neither Na[Al(NH2 BH3 )4 ] nor starting materials, NaAlH4 and AB, but rather occurs within amorphous product(s). Detailed studies of the latter one(s) can open an avenue for a new family of reversible hydrogen storage materials. Finally, the NaAlH4 -4 AB composite might become a starting point towards a new series of aluminum-based tetraamidoboranes with improved hydrogen storage properties such as hydrogen storage density, hydrogen purity, and reversibility.

  17. Effect of Nb on Cracking and Hydrogen Content of Zirconium Hydride%铌对氢化锆裂纹行为和氢含量的影响

    Institute of Scientific and Technical Information of China (English)

    王建伟; 王力军; 陈伟东; 张建东

    2012-01-01

    Zirconium hydride was one of the most ideal moderators, especially for the space nuclear power system. But the high hydrogen level zirconium hydride was easy to crack during its preparation. Nb was the main adding element in the zirconium hydride moderator and affected the cracking behaviors and hydrogen content of the zirconium hydride, which was determined by the existing status of Nb in the zirconium hydride. The issues mentioned were investigated at present It indicated that the hydriding products of Zr-Nb alloys with different Nb content were all composed of mixed s phase zirconium hydrides of ZrH2, ZrH1.950 and ZrH1.801. Nb improved the structure and morphology of the zirconium hydride, decreased the defects and inhibited the cracking. In the case of high Nb level, the generated NbR, solid solution with low hydrogen content downgraded the whole hydrogen content of the alloy. The solubility of Nb in the zirconium hydride was low. For the zirconium hydride with low Nb content, majority of Nb was scattered on the surface of the zirconium hydride as small white grains of H-containing Zr-Nb solid solutioa.%氢化锫是一种理想的固体中子慢化材料,尤其适用于空间核电源的反应堆,但是高氢含量的氢化锫在制备过程中很容易形成裂纹.Nb是氢化锆中的主要添加元素,对氢化锆的裂纹形成和氢含量有一定影响,这是由Nb在氢化锆中的存在形式决定的,对此进行了研究.结果表明,在吸氢充分的情况下,不同Nb含量的Zr - Nb合金氢化后产物的主要组成都是ZrH2,ZrH1.950和ZrH1.801的ε相氢化锆混合物,Nb的添加对氢化锫的晶格常数和晶胞大小影响不大.Nb改善了氢化锫的多缺陷状态,减少了氢富集的位置,从而起到抑制裂纹产生的作用.常压下,Nb的添加会影响合金的最大吸氢量,尤其当Nb含量在10%以上时,会生成低氢含量的NbHx固溶体,影响锆合金的整体吸氢量.Nb在氢化锆中的固溶度较小,Nb含量较

  18. Hydrogen Storage and Release Properties of Transition Metal-Added Magnesium Hydride Alloy Fabricated by Grinding in a Hydrogen Atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, Sung Nam; Song, Myoung Youp [Chonbuk National University, Jeonju (Korea, Republic of); Park, Hye Ryoung [Chonnam National University, Gwangju (Korea, Republic of)

    2016-07-15

    90 wt% MgH{sub 2}+5 wt% Ni+2.5 wt% Fe+2.5 wt% Ti (called MgH{sub 2}+Ni+Fe+Ti), a hydrogen storage and release material, was fabricated by grinding in a hydrogen atmosphere, and then its quantities of stored and released hydrogen as a function of time were examined. A nanocrystalline MgH{sub 2}+Ni+Fe+Ti specimen was made by grinding in a hydrogen atmosphere and subsequent hydrogen storage-release cycling. The crystallite size of Mg and the strain of the Mg crystallite after ten hydrogen storage-release cycles, which were obtained using the Williamson-Hall method, were 38.6 (±1.4) nm and 0.025 (±0.0081) %, respectively. The MgH{sub 2}+Ni+Fe+Ti sample after the process of grinding in a hydrogen atmosphere was highly reactive with hydrogen. The sample exhibited an available storage capacity of hydrogen (the amount of hydrogen stored during 60 minutes) of about 5.7 wt%. At the first cycle, the MgH2+Ni+Fe+Ti sample stored hydrogen of 5.53 wt% in 5 minutes, 5.66 wt% in 10 minutes and 5.73 wt% in 60 minutes at 573 K and 12 bar of hydrogen. The MgH{sub 2}+Ni+Fe+Ti after activation released hydrogen of 0.56 wt% in 5 minutes, 1.26 wt% in 10 minutes, 2.64 wt% in 20 minutes, 3.82 wt% in 30 minutes, and 5.03 wt% in 60 minutes.

  19. Synergic catalytic effect of Ti hydride and Nb nanoparticles for improving hydrogenation and dehydrogenation kinetics of Mg-based nanocomposite

    Directory of Open Access Journals (Sweden)

    Xiujuan Ma

    2017-02-01

    Full Text Available The Mg-9.3 wt% (TiH1.971-TiH−0.7 wt% Nb nanocomposite has been synthesized by hydrogen plasma-metal reaction (HPMR approach to enhance the hydrogen sorption kinetics of Mg at moderate temperatures by providing nanosizing effect of increasing H “diffusion channels” and adding transition metallic catalysts. The Mg nanoparticles (NPs were in hexagonal shape range from 50 to 350 nm and the average size of the NPs was 177 nm. The small spherical TiH1.971, TiH and Nb NPs of about 25 nm uniformly decorated on the surface of the big Mg NPs. The Mg-TiH1.971-TiH-Nb nanocomposite could quickly absorb 5.6 wt% H2 within 5 min at 573 K and 4.5 wt% H2 within 5 min at 523 K, whereas the pure Mg prepared by HPMR could only absorb 4 and 1.5 wt% H2 at the same temperatures. TiH1.971, TiH and Nb NPs transformed into TiH2 and NbH during hydrogenation and recovered after dehydrogenation process. The apparent activation energies of the nanocomposite for hydrogenation and dehydrogenation were 45.0 and 50.7 kJ mol−1, which are much smaller than those of pure Mg NPs, 123.8 and 127.7 kJ mol−1. The improved sorption kinetics of the Mg-based nanocomposite at moderate temperatures and the small activation energy can be interpreted by the nanostructure of Mg and the synergic catalytic effects of Ti hydrides and Nb NPs.

  20. Sorption properties of nanocrystalline metal hydrides for the storage of hydrogen; Sorptionseigenschaften von nanokristallinen Metallhydriden fuer die Wasserstoffspeicherung

    Energy Technology Data Exchange (ETDEWEB)

    Oelerich, W.

    2000-07-01

    For the utilisation of hydrogen in emission-free automobiles new nanostructured Mg-based metal hydrides were developed. These materials show significantly faster absorption and desorption kinetics, which can be even further enhanced by additions of suitable catalysts. Contrary to conventional magnesium powder, hydrogenation at room temperature is demonstrated for the first time. During dehydrogenation at 250 C a desorption rate of 3 to 8 kW/kg with a capacity of 2.5 kWh/kg is achieved, that fulfills the technical requirements for automobile application. (orig.) [German] Im Hinblick auf den Einsatz von Wasserstoff in emissionsfreien Kraftfahrzeugen wurden neuartige nanostrukturierte Metallhydride auf Basis von Magnesium hergestellt. Diese Materialien zeigen eine deutlich schnellere Absorptions- und Desorptionskinetik, die sich durch den Zusatz von geeigneten Katalysatoren noch weiter steigern laesst. Im Gegensatz zu konventionellem Magnesiumpulver konnte erstmals eine Hydrierung bei Raumtemperatur demonstriert werden. Bei der Dehydrierung bei 250 C wird eine Desorptionsrate von 3 bis 8 kW/kg bei einer Kapazitaet von 2,5 kWh/kg erreicht, die die technischen Leistungsanforderungen von Kraftfahrzeugen erfuellt. (orig.)

  1. On-line electrochemically controlled in-tube solid phase microextraction of inorganic selenium followed by hydride generation atomic absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Asiabi, Hamid [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Yamini, Yadollah, E-mail: yyamini@modares.ac.ir [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Seidi, Shahram [Department of Analytical Chemistry, Faculty of Chemistry, K.N. Toosi University of Technology, Tehran (Iran, Islamic Republic of); Shamsayei, Maryam; Safari, Meysam; Rezaei, Fatemeh [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of)

    2016-05-30

    In this work, for the first time, a rapid, simple and sensitive microextraction procedure is demonstrated for the matrix separation, preconcentration and determination of inorganic selenium species in water samples using an electrochemically controlled in-tube solid phase microextraction (EC-in-tube SPME) followed by hydride generation atomic absorption spectrometry (HG-AAS). In this approach, in which EC-in-tube SPME and HG-AAS system were combined, the total analysis time, was decreased and the accuracy, repeatability and sensitivity were increased. In addition, to increases extraction efficiency, a novel nanostructured composite coating consisting of polypyrrole (PPy) doped with ethyleneglycol dimethacrylate (EGDMA) was prepared on the inner surface of a stainless-steel tube by a facile electrodeposition method. To evaluate the offered setup and the new PPy-EGDMA coating, it was used to extract inorganic selenium species in water samples. Extraction of inorganic selenium species was carried out by applying a positive potential through the inner surface of coated in-tube under flow conditions. Under the optimized conditions, selenium was detected in amounts as small as 4.0 parts per trillion. The method showed good linearity in the range of 0.012–200 ng mL{sup −1}, with coefficients of determination better than 0.9996. The intra- and inter-assay precisions (RSD%, n = 5) were in the range of 2.0–2.5% and 2.7–3.2%, respectively. The validated method was successfully applied for the analysis of inorganic selenium species in some water samples and satisfactory results were obtained. - Graphical abstract: An electrochemically controlled in-tube solid phase microextraction followed by hydride generation atomic absorption spectrometry was developed for extraction and determination ultra-trace amounts of Se in aqueous solutions. - Highlights: • A nanostructured composite coating consisting of PPy doped with EGDMA was prepared. • The coating was

  2. 6 CFM Electrochemical Hydrogen Pump and Compressor Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Hydrogen is an essential resource for space missions. NASA has a need for equipment to generate, handle and store hydrogen. In terms of handling hydrogen,...

  3. 6 CFM Electrochemical Hydrogen Pump and Compressor Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Hydrogen is an essential resource for space missions. NASA has a need for equipment to generate, handle and store hydrogen. In terms of handling hydrogen,...

  4. Eye readable metal hydride based hydrogen tape sensor for health applications

    NARCIS (Netherlands)

    Ngene, P.; Radeva, T.; Westerwaal, R.; Schreuders, H.; Dam, B.

    Using the change in the intrinsic optical properties of YMg-based thin films upon exposure to hydrogen, we observe the presence of hydrogen at concentrations as low as 20 ppm just by a change in color. The eye-visible color change circumvents the use of any electronics in this device, thereby making

  5. Eye readable metal hydride based hydrogen tape sensor for health applications

    NARCIS (Netherlands)

    Ngene, P.; Radeva, T.; Westerwaal, R.; Schreuders, H.; Dam, B.

    Using the change in the intrinsic optical properties of YMg-based thin films upon exposure to hydrogen, we observe the presence of hydrogen at concentrations as low as 20 ppm just by a change in color. The eye-visible color change circumvents the use of any electronics in this device, thereby making

  6. Adsorption of molecular hydrogen on an ultrathin layer of Ni(111) hydride

    NARCIS (Netherlands)

    Shan, J. J.; Kleyn, A. W.; Juurlink, L. B. F.

    2009-01-01

    We have used high resolution electron energy loss spectroscopy and temperature-programmed desorption to study the interaction of atomic hydrogen with Ni(1 1 1). Our results agree mostly with previous reports. We find that exposing Ni(1 1 1) to atomic hydrogen below 90 K leads to a 125 K TPD feature

  7. Simultaneous dehydrogenation of organic compounds and hydrogen removal by hydride forming alloys

    NARCIS (Netherlands)

    Appelman, W.J.T.M.; Kuczynski, M.; Versteeg, G.F.

    1992-01-01

    The applicability of hydrogen-absorbing metals in dehydrogenation reactions was investigated. Based on thermodynamic considerations, operating ranges were defined within which an increase of the reactant conversion can he achieved owing to an in situ hydrogen removal by the alloy. Low plateau pressu

  8. In-situ Hydrogen Sorption 2D-ACAR Facility for the Study of Metal Hydrides for Hydrogen Storage

    NARCIS (Netherlands)

    Legerstee, W.J.; De Roode, J.; Anastasopol, A.; Falub, C.V.; Eijt, S.W.H.

    2012-01-01

    We developed a dedicated hydrogen sorption setup coupled to a positron 2D-ACAR (two-dimensional Angular Correlation of Annihilation Radiation) setup employing a 22Na-source, which will enable to collect 2D-ACAR momentum distributions in-situ as a function of temperature, hydrogen pressure and

  9. Study on Kinetics of Hydrogen Absorption by Metal Hydride Slurries Ⅱ. Hydrogenation of Benzene Catalyzed by MlNi5

    Institute of Scientific and Technical Information of China (English)

    安越; 陈长聘; 徐国华; 蔡官明; 王启东

    2002-01-01

    The feasibility of the hydrogenation of benzene into cyclohexane over the hydrogen storage alloy MlNi5 catalyst was studied in the temperature range of 402~463 K. The results show that the reaction order is zero and the energy of activation is 28.9 kJmol-1.

  10. In-situ Hydrogen Sorption 2D-ACAR Facility for the Study of Metal Hydrides for Hydrogen Storage

    NARCIS (Netherlands)

    Legerstee, W.J.; De Roode, J.; Anastasopol, A.; Falub, C.V.; Eijt, S.W.H.

    2012-01-01

    We developed a dedicated hydrogen sorption setup coupled to a positron 2D-ACAR (two-dimensional Angular Correlation of Annihilation Radiation) setup employing a 22Na-source, which will enable to collect 2D-ACAR momentum distributions in-situ as a function of temperature, hydrogen pressure and hydrog

  11. Characterization of ceramic materials for electrochemical hydrogen sensors

    Energy Technology Data Exchange (ETDEWEB)

    Serret, P.; Colominas, S. [Electrochemical Methods Laboratory - Analytical Chemistry Department ETS Institut Quimic de Sarria, Universitat Ramon Llull, Via Augusta, 390, 08017 Barcelona (Spain); Reyes, G. [Industrial Engineering Department ETS Institut Quimic de Sarria, Universitat Ramon Llull, Via Augusta, 390, 08017 Barcelona (Spain); Abella, J., E-mail: jordi.abella@iqs.es [Electrochemical Methods Laboratory - Analytical Chemistry Department ETS Institut Quimic de Sarria, Universitat Ramon Llull, Via Augusta, 390, 08017 Barcelona (Spain)

    2011-10-15

    Accurate and reliable tritium management is of basic importance for the correct operation conditions of the blanket tritium cycle. The Electrochemical Methods Lab at Institut Quimic de Sarria (IQS) is working in the design and development of tritium sensors, based on proton solid state electrolytes to be used in molten lithium-lead eutectic. Different solid electrolyte proton conductors have been synthesized (Sr{sub 3}CaZr{sub 0.9}Ta{sub 1.1}O{sub 8.55}, SrCe{sub 0.95}Yb{sub 0.05}O{sub 3-{alpha}}, CaZr{sub 0.9}In{sub 0.1}O{sub 3-{alpha}}, Ba{sub 3}(Ca{sub 1.18}Nb{sub 1.82})O{sub 9-{alpha}}) in order to be evaluated in a testing apparatus for hydrogen gas. Potentiometric measurements of the synthesized ceramic elements have been performed. In all experiments the working temperature was 500 {sup o}C. The sensors constructed using the proton conductor element Sr{sub 3}CaZr{sub 0.9}Ta{sub 1.1}O{sub 8.55} exhibited stable output potential and its value was close to the theoretical value calculated with the Nernst equation. When the proton conductor elements SrCe{sub 0.95}Yb{sub 0.05}O{sub 3-{alpha}} and CaZr{sub 0.9}In{sub 0.1}O{sub 3-{alpha}} and Ba{sub 3}(Ca{sub 1.18}Nb{sub 1.82})O{sub 9-{alpha}} were used a deviation higher than 100 mV between theoretical and experimental data was obtained.

  12. Effect of the Cerium Oxide (CeO2) on the Structural and Electrochemical Properties of the LaNi5Ce Metal Hydride Anode

    Science.gov (United States)

    Utami Hapsari, Ade; Zulfia, Anne; Raharjo, Jarot; Agustanhakri

    2017-07-01

    One of negative electrode, AB5-type alloy electrodes, have been extensively studied and applied in rechargeable Ni-MH batteries due to their excellent electrochemical characteristics. Some researchers have found that addition of rare earth oxides (La, Ce, Pr, Er, Tm, Yb) to AB5-type alloy (MH) electrode improves battery performance significantly. Cerium Oxide (CeO2) is a light rare earth oxide is widely obtained from the processing of tailings in mining activities. During this time, there is still little data for research applications of cerium oxide for electrode materials. In this paper, the effects of adding CeO2 on the performance metal hydride electrode were investigated. In order to study the effects of CeO2 on the performance of anode material, 1%, 2%, and 3% of weight ratio CeO2 was mixed to LaNi5 as an negative electrode. The powder mixtures were mechanically milled at a speed of rpm 240 for 2 hours using ball mill. The powder mixtures were characterized by X-Ray Diffraction (XRD) and Scanning Electron Microscope (SEM). Electrochemical characteristics were measured using electrochemical impedance spectroscopy (EIS). The powder mixing showed the presence of Ce atom substitution into LaNi5 structures that affect the electrochemical properties of the material. The addition of cerium oxide at LaNi5 increase of the value of impedance. However, the addition of the value of impedance at 1% CeO2 is not significant when compared with the addition of 2% and 3% CeO2 that actually make the electrochemical properties of LaNi5 worst. Although the addition of 1% CeO2 also slightly increases the impedance value of LaNi5, but the addition of 1% CeO2 showed increase the corrosion resistance than without the addition of CeO2 and the addition of 2% and 3% CeO2.

  13. Fabrication of Nickel Nanotube Using Anodic Oxidation and Electrochemical Deposition Technologies and Its Hydrogen Storage Property

    Directory of Open Access Journals (Sweden)

    Yan Lv

    2016-01-01

    Full Text Available Electrochemical deposition technique was utilized to fabricate nickel nanotubes with the assistance of AAO templates. The topography and element component of the nickel nanotubes were characterized by TEM and EDS. Furthermore, the nickel nanotube was made into microelectrode and its electrochemical hydrogen storage property was studied using cyclic voltammetry. The results showed that the diameter of nickel nanotubes fabricated was around 20–100 mm, and the length of the nanotube could reach micron grade. The nickel nanotubes had hydrogen storage property, and the hydrogen storage performance was higher than that of nickel powder.

  14. Non-oxidative coupling reaction of methane to ethane and hydrogen catalyzed by the silica-supported tantalum hydride: ([triple bond]SiO)2Ta-H.

    Science.gov (United States)

    Soulivong, Daravong; Norsic, Sébastien; Taoufik, Mostafa; Copéret, Christophe; Thivolle-Cazat, Jean; Chakka, Sudhakar; Basset, Jean-Marie

    2008-04-16

    Silica-supported tantalum hydride, (SiO)2Ta-H (1), proves to be the first single-site catalyst for the direct non-oxidative coupling transformation of methane into ethane and hydrogen at moderate temperatures, with a high selectivity (>98%). The reaction likely involves the tantalum-methyl-methylidene species as a key intermediate, where the methyl ligand can migrate onto the tantalum-methylidene affording the tantalum-ethyl.

  15. Complex and liquid hydrides for energy storage

    Energy Technology Data Exchange (ETDEWEB)

    Callini, Elsa; Atakli, Zuleyha Özlem Kocabas; Hauback, Bjørn C.; Orimo, Shin-ichi; Jensen, Craig; Dornheim, Martin; Grant, David; Cho, Young Whan; Chen, Ping; Hjörvarsson, Bjørgvin; de Jongh, Petra; Weidenthaler, Claudia; Baricco, Marcello; Paskevicius, Mark; Jensen, Torben R.; Bowden, Mark E.; Autrey, Thomas S.; Züttel, Andreas

    2016-03-10

    The research on complex hydrides for hydrogen storage was imitated by the discovery of Ti as a hydrogen sorption catalyst in NaAlH4 by Boris Bogdanovic in 1996. A large number of new complex hydride materials in various forms and combinations have been synthesized and characterized and the knowledge on the properties of complex hydrides and the synthesis methods has grown enormously since then. A significant part of the research groups active in the field of complex hydrides are collaborators in the IEA task 32. This paper reports about the important issues in the field of the complex hydride research, i.e. the synthesis of borohydrides, the thermodynamics of complex hydrides and their thermodynamic properties, the effects of size and confinement, the hydrogen sorption mechanism and the complex hydride composites as well as the properties of liquid complex hydrides. This paper is the result of the collaboration of several groups and excellent summary of the recent achievements.

  16. Synthesis and characterization of light-metal-based hydrides for hydrogen storage materials

    Science.gov (United States)

    Choi, Young Joon

    In the past few years, research and development on the use of hydrogen as a fuel for various applications have gathered momentum in response to the demand for cleaner fuels and substitutes to fossil fuels. The use of hydrogen for automobiles, one of the most important applications of hydrogen fuel, requires an on-board hydrogen storage system that can be regenerated on-board or off-board. However, one of the key obstacles to this application is that current available storage technologies do not meet the capacity and efficiency requirements for achieving the commercial viability. In this study, two solid-state hydrogen storage systems, i.e. Mg-Ti-H and Li-Al-B-H, are investigated. Among a variety of MgH2/TiH2 ratios and milling conditions, the 10MgH2/TiH2 sample milled in a dual-planetary high-energy mill for 4 hours under 15 MPa hydrogen pressure were found to be the optimal materials, displaying a substantially reduced activation energy and enthalpy change for MgH2 dehydrogenation. PCT analysis demonstrated that the system showed excellent cycle stability attributed to the inhibition of coarsening by TiH2. Lithium borohydride (LiBH4) is one of the promising candidates as a superior hydrogen storage because of its high theoretical storage capacity (18.5 wt.%). In this work, the promising hydrogen storage properties of combined systems of Li3AlH6/LiBH4 and Al/LiBH 4, exhibiting the favorable formation of AlB2 during dehydrogenation, were presented based on TGA and XRD analyses. Additionally, the characterization of the intermediate and final products of the dehydrogenation and rehydrogenation of the above systems by solid-state NMR analyses were presented. This has verified and further clarified the paths and intermediate products of the reversible hydrogen release and uptake by the mixtures.

  17. Effect of hydrogen and hydrides on the viscoplastic behaviour of the recrystallized zircaloy-4; Effet de l'hydrogene et des hydrures sur le comportement viscoplastique du zircaloy-4 recristallise

    Energy Technology Data Exchange (ETDEWEB)

    Rupa, N

    2000-04-15

    Zircaloy-4 is the main material of PWR fuel assemblies. In service as during the storage, the integrity of these compounds has to be guaranteed in spite of the presence of hydrogen (in solution in the zirconium matrix) and of hydrides (which precipitate when the amount of hydrogen is higher than the solubility limit). The aim of this work is to characterize the hydrogen and hydrides effect on the viscoplastic behaviour of the non irradiated recrystallized zircaloy-4. The presence of hydrogen in solid solution induces a decrease of the mechanical properties: the creep kinetics are then increased and the tensile stresses decreased. This decrease is particularly visible in conditions of oxygen/dislocations dynamic interactions (revealed on the material without hydrogen). The advanced hypothesis, strengthened by the atomic simulation results, is that the hydrogen facilitates the dislocations movement, in diminishing the effects of anchoring by the interstitials, and/or in increasing the intrinsic mobility of dislocations. The hydrides effect induces a hardening of the material (decrease of the creep kinetics, increase of the tensile stresses and of the relaxed stresses) compensating the decrease by hydrogen. The hardening mechanism is due to an increase of the internal constraints, determined by load-unload tests. For the very weak plastic deformations, the hydrides are an obstacle to the dislocations gliding. They are then passed (that corresponds to a saturation of the internal constraint). The TEM observations as well as the results obtained on the titanium indicate that the precipitates are then submitted to a deformation mechanism. (O.M.)

  18. Electrochemical Detection of Transient Cobalt Hydride Intermediates of Electrocatalytic Hydrogen Production

    Energy Technology Data Exchange (ETDEWEB)

    Wiedner, Eric S.; Bullock, R. Morris

    2016-07-06

    We report the use of variable scan rate cyclic voltammetry to detect transient CoIIIH and CoIIH intermediates of electrocatalytic H2 production by CoII(dmgBF2)2(CH3CN)2 and [CoII(PtBu2NPh2)(CH3CN)3]2+. In both cases, reduction of the CoIIIH intermediate was observed to coincide with the CoII/I couple, and the resulting CoIIH intermediate is protonated by acid to afford H2. Our studies indicate that in electrocatalytic H2 production, protonation of CoIIH is rate-limiting for CoII(dmgBF2)2(CH3CN)2, and protonation of CoI is rate-limiting for [CoII(PtBu2NPh2)(CH3CN)3]2+. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  19. Destabilisation of magnesium hydride by germanium as a new potential multicomponent hydrogen storage system.

    Science.gov (United States)

    Walker, Gavin S; Abbas, Marwa; Grant, David M; Udeh, Chima

    2011-07-28

    MgH(2) has too high an operating temperature for many hydrogen storage applications. However, MgH(2) ball-milled with Ge leads to a thermodynamic destabilisation of >50 kJ mol(-1)(H(2)). This has dramatically reduced the temperature of dehydrogenation to 130 °C, opening up the potential for Mg-based multicomponent systems as hydrogen stores for a range of applications.

  20. New nanomaterials for hydrogen storage. A new class of aluminum hydrides; Neue Nanomaterialien zur Wasserstoffspeicherung. Eine neue Klasse von Aluminiumhydriden

    Energy Technology Data Exchange (ETDEWEB)

    Cordes, Joern

    2009-02-13

    In this work, Aluminum was vaporized in a PACIS cluster source, while molecular Hydrogen was also provided, thus producing Aluminum hydride clusters. These clusters were mass selected and investigated via Photoelectron Spectroscopy with anions in order to determine their electronic structure. In a cooperation with Puru Jena et al. at the Virginia Commonwealth University, electronic and geometric structures of the clusters were also calculated using Density Functional Theory. A group of clusters, specifically Al{sub 4}H{sub 4}, Al{sub 4}H{sub 6} and a series of clusters Al{sub n}H{sub n+2} (5 {<=} n {<=} 8) showed large HOMO-LUMO-Gaps and relatively small adiabatic electron affinities, hinting towards an increased stability of these clusters. The resemblance of the structures of already known and stable Boranes (BnHm) led to investigations whether ''Wade's Rules'' could also be applied to the new Alanes Al{sub n}H{sub m}. Comparison of the experimentally found values for the HOMO-LUMO-Gap, Adiabatic electron Affinity and Vertical Detachment Energy with the calculated values led to geometric structures of the ground states that, in case of the clusters Al{sub n}H{sub n+2} (5 {<=} n {<=} 8) follow Wade's (n+1) rule: They adopt hollow, cage-like closo-structures with one terminal Hydrogen atom per Aluminum atom and two additional Hydrogen atoms on bridge-sites. The clusters Al{sub 4}H{sub 4} and Al{sub 4}H{sub 6} have tetrahedron-shaped structures. While Al{sub 4}H{sub 4} is a perfect tetrahedron, Al{sub 4}H{sub 6} adopts a slightly distorted tetrahedral geometry with D{sub 2d} symmetry and two Hydrogen atoms on bridge sites. Furthermore, Al{sub 4}H{sub 6} showed the biggest HOMO-LUMO-Gap of all investigated clusters with a value of 1.9 {+-} 0.1 eV. These findings seem to contradict Wade's (n+1) rule, but can be understood in terms of the Polyhedral Skeletal Electron Pair Theory (PSEPT). The molecular orbitals predicted by the PSEPT

  1. Excellent catalytic effects of highly crumpled graphene nanosheets on hydrogenation/dehydrogenation of magnesium hydride

    Science.gov (United States)

    Liu, Guang; Wang, Yijing; Xu, Changchang; Qiu, Fangyuan; An, Cuihua; Li, Li; Jiao, Lifang; Yuan, Huatang

    2013-01-01

    Highly crumpled graphene nanosheets (GNS) with a BET surface area as high as 1159 m2 g-1 was fabricated by a thermal exfoliation method. A systematic investigation was performed on the hydrogen sorption properties of MgH2-5 wt% GNS nanocomposites acquired by ball-milling. It was found that the as-synthesized GNS exhibited a superior catalytic effect on hydrogenation/dehydrogenation of MgH2. Differential Scanning Calorimetry (DSC) and isothermal hydrogenation/dehydrogenation measurements indicated that both hydrogen sorption capacity and dehydrogenation/hydrogenation kinetics of the composites improved with increasing milling time. The composites MgH2-GNS milled for 20 h can absorb 6.6 wt% H2 within 1 min at 300 °C and 6.3 wt% within 40 min at 200 °C, even at 150 °C, it can also absorb 6.0 wt% H2 within 180 min. It was also demonstrated that MgH2-GNS-20 h could release 6.1 wt% H2 at 300 °C within 40 min. In addition, microstructure measurements based on XRD, SEM, TEM as well as Raman spectra revealed that the grain size of thus-prepared MgH2-GNS nanocomposites decreased with increasing milling time, moreover, the graphene layers were broken into smaller graphene nanosheets in a disordered and irregular manner during milling. It was confirmed that these smaller graphene nanosheets on the composite surface, providing more edge sites and hydrogen diffusion channels, prevented the nanograins from sintering and agglomerating, thus, leading to promotion of the hydrogenation/dehydrogenation kinetics of MgH2.Highly crumpled graphene nanosheets (GNS) with a BET surface area as high as 1159 m2 g-1 was fabricated by a thermal exfoliation method. A systematic investigation was performed on the hydrogen sorption properties of MgH2-5 wt% GNS nanocomposites acquired by ball-milling. It was found that the as-synthesized GNS exhibited a superior catalytic effect on hydrogenation/dehydrogenation of MgH2. Differential Scanning Calorimetry (DSC) and isothermal hydrogenation

  2. Catalytic effect of chlorides compounds on hydrogen sorption properties of magnesium hydride

    Energy Technology Data Exchange (ETDEWEB)

    Conceição, M.O.T. da; Santos, D.S. dos, E-mail: dilson@metalmat.ufrj.br

    2014-12-05

    Highlights: • The NbCl{sub 5} and ZrCl{sub 4} showed to be promising catalysts. • The MgH{sub 2} + 5 wt.% NbCl{sub 5} composite reached the hydrogen capacity of 6.0 wt.% in 6 min. • The MgH{sub 2} + 5 wt.% ZrCl{sub 4} desorbed 6.2 wt.% of H{sub 2} in 4 min. - Abstract: The hydrogen sorption kinetics properties of MgH{sub 2} based composites obtained by mechanical milling were investigated. The composites analyzed in this paper were MgH{sub 2} ball milled with 5 wt.% of NbCl{sub 3}, NbCl{sub 5} and ZrCl{sub 4} chlorides. The samples were investigated using X-ray diffraction, XRD, differential scanning calorimetry, DSC and hydrogen absorption and desorption kinetics tests at 300 and 350 °C. DSC curves showed that the hydrogen desorption peak temperature of all samples milled with catalyst was lower when compared to MgH{sub 2} milled without catalyst. The NbCl{sub 5} catalyzed MgH{sub 2} showed the faster absorption kinetics attaining a total hydrogen capacity of 6 wt.% in 6 min at 300 °C and the sample containing NbCl{sub 3} showed the faster desorption kinetics, desorbing 5.5 wt.% of H{sub 2} in 10 min at 300 °C.

  3. Hydrogenation, structure and magnetic properties of La(Fe0.91Si0.09)13 hydrides and deuterides

    Institute of Scientific and Technical Information of China (English)

    Wang Zhi-Cui; He Lun-Hua; F.Cuevas; M.Latroche; Shen Jun; Wang Fang-Wei

    2011-01-01

    Hydrogenation, crystal structure and magnetic properties of La(Fe0.91Si0.09)13H(D)y have been studied by pressure-composition isotherms (PCI), X-ray diffraction (XRD), differential scanning calorimetry (DSC) and magnetization measurements. The maximum absorption capacity is found to be 1.9 H(D) atoms per formula unit as a solid solution. All hydrides and deuterides crystallize in the NaZn13-type cubic structure with the lattice parameter increasing linearly with H(D) concentration. The H(D) absorption enhances the Curie temperature significantly. The magnetic entropy change of the highly H-absorbed compound La(Fe0.g1Si0.09)13H1.81 reaches ~26 J/kg.K under a magnetic field change of 5 T near the Curie temperature TC = 350 K. No observable isotope effect seems to imply that only the magnetovolume effect is responsible for the strong interplay between magnetism and lattice.

  4. The effect of metal oxide additives on the hydrogen sorption behaviour of magnesium hydride

    OpenAIRE

    2007-01-01

    MgH2 is considered to be one of the most promising options for a solid state hydrogen storage material. For practical use it is still imperative to find a convenient means of overcoming its slow kinetics and high stability. In this investigation, a range of binary and ternary metal oxides of aluminium, silicon, titanium, and zirconium, as well as Pd-modified Ti02 samples, were prepared and characterised. The prepared oxides were ball milled with MgH2, and the hydrogen sorption behaviour of th...

  5. Effect of multi-wall carbon nanotubes supported nano-nickel and TiF{sub 3} addition on hydrogen storage properties of magnesium hydride

    Energy Technology Data Exchange (ETDEWEB)

    Su, Wei; Zhu, Yunfeng, E-mail: yfzhu@njtech.edu.cn; Zhang, Jiguang; Liu, Yana; Yang, Yang; Mao, Qifeng; Li, Liquan

    2016-06-05

    Multi-wall carbon nanotubes supported nano-nickel (Ni/MWCNTs) with superior catalytic effects was introduced to magnesium hydride by the process of hydriding combustion synthesis (HCS) and mechanical milling (MM). The effect of different Ni/MWCNTs contents (5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%) on the hydrogenation and dehydrogenation properties of the composite was investigated systematically. It is revealed that Mg{sub 85}-(Ni/MWCNTs){sub 15} composite shows the best comprehensive hydrogen storage properties, which absorbs 5.68 wt.% hydrogen within 100 s at 373 K and releases 4.31 wt.% hydrogen within 1800 s at 523 K under initial hydrogen pressures of 3.0 and 0.005 MPa, respectively. The in situ formed nano-Mg{sub 2}Ni and MWCNTs have excellent catalytic effect on the hydrogenation and dehydrogenation performances of MgH{sub 2}. To further improve the hydrogen absorption/desorption properties, TiF{sub 3} was added to the Mg–Ni/MWCNTs system. The result shows that TiF{sub 3} addition has little influence on the thermodynamic performance, but affects greatly the kinetic properties. The Mg{sub 85}-(Ni/MWCNTs){sub 15}-TiF{sub 3} composite exhibits an appreciably enhanced hydrogen desorption performance at low temperature, and the hydrogen desorption capacity within 1800 s at 473 K for the TiF{sub 3}-added composite is approximately four times the capacity of Mg{sub 85}-(Ni/MWCNTs){sub 15} under the same condition. The catalytic effects during hydrogenation and dehydrogenation have been discussed in the study. - Highlights: • The nanosized Ni/MWCNTs catalyst was successfully prepared. • Ni/MWCNTs shows superior catalytic effect on H absorption/desorption of Mg. • Mg{sub 85}-(Ni/MWCNTs){sub 15} composite shows the best hydrogen storage properties. • Ni/MWCNTs coupling with TiF{sub 3} improves the hydriding/dehydriding properties largely.

  6. Solid State NMR Characterization of Complex Metal Hydrides systems for Hydrogen Storage Applications

    Directory of Open Access Journals (Sweden)

    Son-Jong Hwang

    2011-12-01

    Full Text Available Solid state NMR is widely applied in studies of solid state chemistries for hydrogen storage reactions. Use of 11B MAS NMR in studies of metal borohydrides (BH4 is mainly focused, revisiting the issue of dodecaborane formation and observation of 11B{1H} Nuclear Overhauser Effect.

  7. Hydrogen storage and low-temperature electrochemical performances of A2B7 type La-Mg-Ni-Co-Al-Mo alloys

    Directory of Open Access Journals (Sweden)

    Jianguang Yuan

    2017-04-01

    Full Text Available The effect of Mo-addition on hydrogen storage and low-temperature electrochemical performances of La-Mg-Ni-Co-Al alloys is investigated. The alloys were synthetized via vacuum induction melting followed by annealing treatment at 1123 K for 8 h. The major phases in the annealed alloys are consisted of (La, Mg2Ni7, (La, Mg5Ni19 and LaNi5 phases. Mo-addition facilitates phase transformation of LaNi5 into (La, Mg2Ni7 and (La, Mg5Ni19 phases. Hydrogen absorption/desorption PCI curves indicates that the hydrogen storage capacity of the alloy increases remarkably with the addition of Mo. Furthermore, the La0.75Mg0.25Ni3.05Co0.2Al0.05Mo0.2 alloy shows excellent hydriding/dehydriding kinetics with a higher capacity, requiring only 100 s to reach its saturated hydrogen capacity of 1.58 wt% at low temperature of 303 K, and releasing 1.57 wt% hydrogen within 400 s at 338 K. Electrochemical experiments manifest that the Mo-added alloy electrode has perfect activation properties and the maximum discharge capacity. The low-temperature dischargeability shows that the La0.75Mg0.25Ni3.05Co0.2Al0.05Mo0.2 alloy exhibits the excellent low-temperature discharge performance, and the maximum discharge capacity is improved from 231.0 to 334.6 mAh/g at 253 K. The HRD property of the alloy electrode is enhanced, suggesting that Mo enhances the kinetic ability at low-temperature.

  8. Bioinspired Tungsten Dithiolene Catalysts for Hydrogen Evolution: A Combined Electrochemical, Photochemical, and Computational Study.

    Science.gov (United States)

    Gomez-Mingot, Maria; Porcher, Jean-Philippe; Todorova, Tanya K; Fogeron, Thibault; Mellot-Draznieks, Caroline; Li, Yun; Fontecave, Marc

    2015-10-29

    Bis(dithiolene)tungsten complexes, W(VI)O2 (L = dithiolene)2 and W(IV)O (L = dithiolene)2, which mimic the active site of formate dehydrogenases, have been characterized by cyclic voltammetry and controlled potential electrolysis in acetonitrile. They are shown to be able to catalyze the electroreduction of protons into hydrogen in acidic organic media, with good Faradaic yields (75-95%) and good activity (rate constants of 100 s(-1)), with relatively high overpotentials (700 mV). They also catalyze proton reduction into hydrogen upon visible light irradiation, in combination with [Ru(bipyridine)3](2+) as a photosensitizer and ascorbic acid as a sacrificial electron donor. On the basis of detailed DFT calculations, a reaction mechanism is proposed in which the starting W(VI)O2 (L = dithiolene)2 complex acts as a precatalyst and hydrogen is further formed from a key reduced W-hydroxo-hydride intermediate.

  9. Predicting formation enthalpies of metal hydrides

    DEFF Research Database (Denmark)

    Andreasen, A.

    2004-01-01

    In order for the hydrogen based society viz. a society in which hydrogen is the primary energy carrier to become realizable an efficient way of storing hydrogen is required. For this purpose metal hydrides are serious candidates. Metal hydrides are formedby chemical reaction between hydrogen...... and metal and for the stable hydrides this is associated with release of heat (#DELTA#H_f ). The more thermodynamically stable the hydride, the larger DHf, and the higher temperature is needed in order to desorphydrogen (reverse reaction) and vice versa. For practical application the temperature needed...

  10. Metal hydrides for lithium-ion batteries.

    Science.gov (United States)

    Oumellal, Y; Rougier, A; Nazri, G A; Tarascon, J-M; Aymard, L

    2008-11-01

    Classical electrodes for Li-ion technology operate via an insertion/de-insertion process. Recently, conversion electrodes have shown the capability of greater capacity, but have so far suffered from a marked hysteresis in voltage between charge and discharge, leading to poor energy efficiency and voltages. Here, we present the electrochemical reactivity of MgH(2) with Li that constitutes the first use of a metal-hydride electrode for Li-ion batteries. The MgH(2) electrode shows a large, reversible capacity of 1,480 mAh g(-1) at an average voltage of 0.5 V versus Li(+)/Li(o) which is suitable for the negative electrode. In addition, it shows the lowest polarization for conversion electrodes. The electrochemical reaction results in formation of a composite containing Mg embedded in a LiH matrix, which on charging converts back to MgH(2). Furthermore, the reaction is not specific to MgH(2), as other metal or intermetallic hydrides show similar reactivity towards Li. Equally promising, the reaction produces nanosized Mg and MgH(2), which show enhanced hydrogen sorption/desorption kinetics. We hope that such findings can pave the way for designing nanoscale active metal elements with applications in hydrogen storage and lithium-ion batteries.

  11. Atomistic understanding of hydrogen loading phenomenon into palladium cathode: A simple nanocluster approach and electrochemical evidence

    Indian Academy of Sciences (India)

    Mohsen Lashgari; Davood Matloubi

    2015-03-01

    The inherent potency of palladium to sorb hydrogen atoms was examined empirically and theoretically through various electrochemical methods and high-level quantum chemical calculations (HSE06) based on cluster model (CM) and density functional theory (DFT). The CM-DFT approach using QZVP/cc-PV6Z basis sets revealed a strong attraction between Pd nanoclusters and H atoms that generates some charged entities. This atomistically justifies why the electrochemical impedance of the system becomes less by the loading phenomenon. It is concluded that hydrogen atoms enter the palladium subsurface through hollow and bridge sites by diffusing as proton-like species and get loaded predominantly in the octahedral voids.

  12. A high-porosity carbon molybdenum sulphide composite with enhanced electrochemical hydrogen evolution and stability

    DEFF Research Database (Denmark)

    Laursen, Anders B.; Vesborg, Peter C. K.; Chorkendorff, Ib

    2013-01-01

    This work describes a highly active and stable acid activated carbon fibre and amorphous MoSx composite hydrogen evolution catalyst. The increased electrochemical-surface area is demonstrated to cause increased catalyst electrodeposition and activity. These composite electrodes also show an impro......This work describes a highly active and stable acid activated carbon fibre and amorphous MoSx composite hydrogen evolution catalyst. The increased electrochemical-surface area is demonstrated to cause increased catalyst electrodeposition and activity. These composite electrodes also show...

  13. Nucleation and growth mechanisms of nano magnesium hydride from the hydrogen sorption kinetics.

    Science.gov (United States)

    Mooij, Lennard; Dam, Bernard

    2013-07-21

    We use a combination of hydrogenography and Johnson-Mehl-Avrami-Kolmogorov (JMAK) analyses to identify (1) the driving force dependence of the nucleation and growth mechanism of MgH2 in thin film multilayers of Mg (10 nm) and (2) the nucleation and growth mechanism of Mg in the earlier formed MgH2, i.e. the hydrogen desorption process. We conclude that JMAK may be successfully applied to obtain the nucleation and growth mechanism of hydrogen absorption. The desorption mechanism, however, is not simply the reverse of the absorption mechanism. We find evidence that the barrier for nucleation of Mg is small. The dehydrogenation probably involves the formation of voids, which is energetically more favorable than elastic and plastic deformation of the multilayer.

  14. Maximising biohydrogen yields via continuous electrochemical hydrogen removal and carbon dioxide scrubbing.

    Science.gov (United States)

    Massanet-Nicolau, Jaime; Jones, Rhys Jon; Guwy, Alan; Dinsdale, Richard; Premier, Giuliano; Mulder, Martijn J J

    2016-10-01

    The use of electrochemical hydrogen removal (EHR) together with carbon dioxide removal (CDR) was demonstrated for the first time using a continuous hydrogen producing fermenter. CDR alone was found to increase hydrogen yields from 0.07molH2molhexose to 0.72molH2molhexose. When CDR was combined with EHR, hydrogen yields increased further to 1.79molH2molhexose. The pattern of carbohydrate utilisation and volatile fatty acid (VFA) production are consistent with the hypothesis that increased yields are the result of relieving end product inhibition and inhibition of microbial hydrogen consumption. In situ removal of hydrogen and carbon dioxide as demonstrated here not only increase hydrogen yield but also produces a relatively pure product gas and unlike other approaches can be used to enhance conventional, mesophilic, CSTR type fermentation of low grade/high solids biomass.

  15. Rechargeable metal hydrides for spacecraft application

    Science.gov (United States)

    Perry, J. L.

    1988-01-01

    Storing hydrogen on board the Space Station presents both safety and logistics problems. Conventional storage using pressurized bottles requires large masses, pressures, and volumes to handle the hydrogen to be used in experiments in the U.S. Laboratory Module and residual hydrogen generated by the ECLSS. Rechargeable metal hydrides may be competitive with conventional storage techniques. The basic theory of hydride behavior is presented and the engineering properties of LaNi5 are discussed to gain a clear understanding of the potential of metal hydrides for handling spacecraft hydrogen resources. Applications to Space Station and the safety of metal hydrides are presented and compared to conventional hydride storage. This comparison indicates that metal hydrides may be safer and require lower pressures, less volume, and less mass to store an equivalent mass of hydrogen.

  16. Cyclic hydrogenation stability of γ-hydrides for Ti{sub 25}V{sub 35}Cr{sub 40} alloys doped with carbon

    Energy Technology Data Exchange (ETDEWEB)

    Shen, Chia-Chieh, E-mail: ccshen@saturn.yzu.edu.tw [Department of Mechanical Engineering, Yuan Ze University, Chungli 32003, Taiwan (China); Graduate School of Renewable Energy and Engineering, Yuan Ze University, Chungli 32003, Taiwan (China); Fuel Cell Center, Yuan Ze University, Chungli 32003, Taiwan (China); Li, Hsueh-Chih [Graduate School of Renewable Energy and Engineering, Yuan Ze University, Chungli 32003, Taiwan (China)

    2015-11-05

    An automatic Sievert's apparatus equipped with a temperature-programmed desorption spectrometer was constructed to study the stability of annealed Ti{sub 25}V{sub 35}Cr{sub 40}C{sub x} (x = 0 and 0.1) alloy under cyclic hydrogenation at 6 N H{sub 2}. The specimens were tested at 30 °C with a hydrogen loading of around 1.00 H/M, which enabled the phase transformation from β-to γ-hydrides. After 500 cycles, 83% and 90% of the initial hydrogen capacities were preserved for Ti{sub 25}V{sub 35}Cr{sub 40} and Ti{sub 25}V{sub 35}Cr{sub 40}C{sub 0.1}, respectively. Therefore, a small amount of C doping was effective in reducing the hydrogenation degradation of Ti{sub 25}V{sub 35}Cr{sub 40}. The hydrogenation degradation of Ti{sub 25}V{sub 35}Cr{sub 40} was examined by measuring the P–C isotherms, temperature-programmed desorption spectra, and X-ray diffraction patterns. The degradation was ascribed to intrinsic disproportionation, i.e., Ti{sub 0.25}V{sub 0.35}Cr{sub 0.40} + 0.88H{sub 2} → yTiH{sub 2} + Ti{sub 0.25−y}V{sub 0.35}Cr{sub 0.40}H{sub 1.76–2y}, where the coefficient y indicates the amount of Ti-rich precipitate. The better cyclic hydrogenation stability of Ti{sub 25}V{sub 35}Cr{sub 40}C{sub 0.1} was related to the suppression of intrinsic disproportionation by the presence of carbon atoms in the body-centered-cubic lattice. - Highlights: • The stability of γ-hydride for Ti{sub 25}V{sub 35}Cr{sub 40} alloys was examined for 500 cycles. • The γ-hydride of Ti{sub 25}V{sub 35}Cr{sub 40} alloy degraded by intrinsic disproportionation. • The disproportionation of γ-hydride can be suppressed through carbon inclusion.

  17. Ternary LiBH4-MgH2-NaAlH4 hydride confined into nanoporous carbon host for reversible hydrogen storage

    Science.gov (United States)

    Plerdsranoy, Praphatsorn; Utke, Rapee

    2016-03-01

    Ternary hydride of LiBH4-MgH2-NaAlH4 confined into carbo n aerogel scaffold (CAS) via melt infiltration for reversible hydrogen storage is proposed. Nanoconfinement of hydrides into CAS is obtained together with surface occupation of some phases, such as Al and/or LiH. Regarding nanoconfinement, not only multiple-step decomposition of LiBH4-MgH2-NaAlH4 hydride reduces to about single step, but also reduction of dehydrogenation temperature is significantly observed, for example, ∆T up to 70 °C regarding last dehydrogenation step. Moreover, decomposition of NaBH4 in nanoconfined sample can be done at 360 °C (dehydrogenation temperature in this study), which is 115 and 180 °C lower than that of NaBH4 in milled LiBH4-MgH2-NaAlH4 and bulk NaBH4, respectively. The reaction of LiBH4+NaAlH4→LiAlH4+NaBH4 takes place during nanoconfinement and the decomposition of LiAlH4 is observed, resulting deficient hydrogen content liberated. However, hydrogen content released (1st cycle) and reproduced (2nd-4th cycles) from this ternary hydride enhances up to 11% and 22% of full hydrogen storage capacity due to nanoconfinement. After rehydrogenation (T=360 °C and P(H2)=50 bar H2 for 12 h), NaBH4, MgH2, and Li3AlH6 are reversible, whereas Li3AlH6 and NaBH4 in milled sample cannot be recovered due to deficient hydrogen pressure (T=360 °C and P(H2)=80 bar) and probably evaporation of molten sodium during dehydrogenation, respectively. The latter results in inferior hydrogen content reproduced from milled sample to nanoconfined sample.

  18. Steric Effect for Proton, Hydrogen-Atom, andHydride Transfer Reactions with Geometric Isomers of NADH-Model Ruthenium Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Fujita E.; Cohen, B.W.; Polyansky, D.E.; Achord, P.; Cabelli, D.; Muckerman, J.T.; Tanaka, K.; Thummel, R.P.; Zong, R.

    2012-01-01

    Two isomers, [Ru(1)]{sup 2+} (Ru = Ru(bpy){sub 2}, bpy = 2,2{prime}-bipyridine, 1 = 2-(pyrid-2{prime}-yl)-1-azaacridine) and [Ru(2)]{sup 2+} (2 = 3-(pyrid-2{prime}-yl)-4-azaacridine), are bio-inspired model compounds containing the nicotinamide functionality and can serve as precursors for the photogeneration of C-H hydrides for studying reactions pertinent to the photochemical reduction of metal-C{sub 1} complexes and/or carbon dioxide. While it has been shown that the structural differences between the azaacridine ligands of [Ru(1)]{sup 2+} and [Ru(2)]{sup 2+} have a significant effect on the mechanism of formation of the hydride donors, [Ru(1HH)]{sup 2+} and [Ru(2HH)]{sup 2+}, in aqueous solution, we describe the steric implications for proton, net-hydrogen-atom and net-hydride transfer reactions in this work. Protonation of [Ru(2{sup {sm_bullet}-})]{sup +} in aprotic and even protic media is slow compared to that of [Ru(1{sup {sm_bullet}-})]{sup +}. The net hydrogen-atom transfer between *[Ru(1)]{sup 2+} and hydroquinone (H{sub 2}Q) proceeds by one-step EPT, rather than stepwise electron-proton transfer. Such a reaction was not observed for *[Ru(2)]{sup 2+} because the non-coordinated N atom is not easily available for an interaction with H{sub 2}Q. Finally, the rate of the net hydride ion transfer from [Ru(1HH)]{sup 2+} to [Ph{sub 3}C]{sup +} is significantly slower than that of [Ru(2HH)]{sup 2+} owing to steric congestion at the donor site.

  19. Predicting impurity gases and phases during hydrogen evolution from complex metal hydrides using free energy minimization enabled by first-principles calculations.

    Science.gov (United States)

    Kim, Ki Chul; Allendorf, Mark D; Stavila, Vitalie; Sholl, David S

    2010-09-07

    First-principles calculations represent a potent tool for screening metal hydride mixtures that can reversibly store hydrogen. A number of promising new hydride systems with high hydrogen capacity and favorable thermodynamics have been predicted this way. An important limitation of these studies, however, is the assumption that H(2) is the only gas-phase product of the reaction, which is not always the case. This paper summarizes new theoretical and numerical approaches that can be used to predict thermodynamic equilibria in complex metal hydride systems with competing reaction pathways. We report thermochemical equilibrium calculations using data obtained from density functional theory (DFT) computations to describe the possible occurrence of gas-phase products other than H(2) in three complex hydrides, LiNH(2), LiBH(4), and Mg(BH(4))(2), and mixtures of these with the destabilizing compounds LiH, MgH(2), and C. The systems under investigation contain N, C, and/or B and thus have the potential to evolve N(2), NH(3), hydrocarbons, and/or boranes as well as H(2). Equilibria as a function of both temperature and total pressure are predicted. The results indicate that significant amounts of these species can form under some conditions. In particular, the thermodynamic model predicts formation of N(2) and NH(3) as products of LiNH(2) decomposition. Comparison with published experimental data indicates that N(2) formation must be kinetically limited. Our examination of C-containing systems indicates that methane is the stable gas-phase species at low temperatures, not H(2). On the other hand, very low amounts of boranes (primarily BH(3)) are predicted to form in B-containing systems.

  20. Lightweight hydride storage materials

    Energy Technology Data Exchange (ETDEWEB)

    Thomas, G.J.; Guthrie, S.E.; Bauer, W. [Sandia National Labs., Livermore, CA (United States)

    1995-09-01

    The need for lightweight hydrides in vehicular applications has prompted considerable research into the use of magnesium and its alloys. Although this earlier work has provided some improved performance in operating temperature and pressure, substantial improvements are needed before these materials will significantly enhance the performance of an engineered system on a vehicle. We are extending the work of previous investigators on Mg alloys to reduce the operating temperature and hydride heat of formation in light weight materials. Two important results will be discussed in this paper: (1) a promising new alloy hydride was found which has better pressure-temperature characteristics than any previous Mg alloy and, (2) a new fabrication process for existing Mg alloys was developed and demonstrated. The new alloy hydride is composed of magnesium, aluminum and nickel. It has an equilibrium hydrogen overpressure of 1.3 atm. at 200{degrees}C and a storage capacity between 3 and 4 wt.% hydrogen. A hydrogen release rate of approximately 5 x 10{sup -4} moles-H{sub 2}/gm-min was measured at 200{degrees}C. The hydride heat of formation was found to be 13.5 - 14 kcal/mole-H{sub 2}, somewhat lower than Mg{sub 2}Ni. The new fabrication method takes advantage of the high vapor transport of magnesium. It was found that Mg{sub 2}Ni produced by our low temperature process was better than conventional materials because it was single phase (no Mg phase) and could be fabricated with very small particle sizes. Hydride measurements on this material showed faster kinetic response than conventional material. The technique could potentially be applied to in-situ hydride bed fabrication with improved packing density, release kinetics, thermal properties and mechanical stability.

  1. Metal-free electrocatalytic hydrogen oxidation using frustrated Lewis pairs and carbon-based Lewis acids.

    Science.gov (United States)

    Lawrence, Elliot J; Clark, Ewan R; Curless, Liam D; Courtney, James M; Blagg, Robin J; Ingleson, Michael J; Wildgoose, Gregory G

    2016-04-21

    Whilst hydrogen is a potentially clean fuel for energy storage and utilisation technologies, its conversion to electricity comes at a high energetic cost. This demands the use of rare and expensive precious metal electrocatalysts. Electrochemical-frustrated Lewis pairs offer a metal-free, CO tolerant pathway to the electrocatalysis of hydrogen oxidation. They function by combining the hydrogen-activating ability of frustrated Lewis pairs (FLPs) with electrochemical oxidation of the resultant hydride. Here we present an electrochemical-FLP approach that utilises two different Lewis acids - a carbon-based N-methylacridinium cation that possesses excellent electrochemical attributes, and a borane that exhibits fast hydrogen cleavage kinetics and functions as a "hydride shuttle". This synergistic interaction provides a system that is electrocatalytic with respect to the carbon-based Lewis acid, decreases the required potential for hydrogen oxidation by 1 V, and can be recycled multiple times.

  2. Microstructure-Property Correlation in Magnesium-based Hydrogen Storage Systems: The Case for Ball-milled Magnesium Hydride Powder and Magnesium-based Multilayered Composites

    Science.gov (United States)

    Danaie, Mohsen

    The main focus of this thesis is the characterization of defects and microstructure in high-energy ball milled magnesium hydride powder and magnesium-based multilayered composites. Enhancement in kinetics of hydrogen cycling in magnesium can be achieved by applying severe plastic deformation. A literature survey reveals that, due to extreme instability of alpha-MgH 2 in transmission electron microscope (TEM), the physical parameters that researchers have studied are limited to particle size and grain size. By utilizing a cryogenic TEM sample holder, we extended the stability time of the hydride phase during TEM characterization. Milling for only 30 minutes resulted in a significant enhancement in desorption kinetics. A subsequent annealing cycle under pressurized hydrogen reverted the kinetics to its initial sluggish state. Cryo-TEM analysis of the milled hydride revealed that mechanical milling induces deformation twinning in the hydride microstructure. Milling did not alter the thermodynamics of desorption. Twins can enhance the kinetics by acting as preferential locations for the heterogeneous nucleation of metallic magnesium. We also looked at the phase transformation characteristics of desorption in MgH2. By using energy-filtered TEM, we investigated the morphology of the phases in a partially desorbed state. Our observations prove that desorption phase transformation in MgH2 is of "nucleation and growth" type, with a substantial energy barrier for nucleation. This is contrary to the generally assumed "core-shell" structure in most of the simulation models for this system. We also tested the hydrogen storage cycling behavior of bulk centimeter-scale Mg-Ti and Mg-SS multilayer composites synthesized by accumulative roll-bonding. Addition of either phase (Ti or SS) allows the reversible hydrogen sorption at 350°C, whereas identically roll-bonded pure magnesium cannot be absorbed. In the composites the first cycle of absorption (also called "activation

  3. Effect of TiO2 nanoparticles on the hydrogen sorption characteristics of magnesium hydride.

    Science.gov (United States)

    Pandey, Sunita K; Bhatnagar, Ashish; Shahi, Rohit R; Hudson, M Sterlin Leo; Singh, Milind K; Srivastava, O N

    2013-08-01

    The present paper explores the enhancement in hydrogen sorption behavior of MgH2 with TiO2 nanoparticles. The catalytic effect of TiO2 nanoparticles with different sizes (7, 25, 50, 100 and 250 nm) were used for improving the sorption characteristics of MgH2. The MgH2 catalyzed with 50 nm of TiO2 exhibited the optimum catalytic effect for hydrogen sorption behavior. The desorption temperature of MgH2 catalyzed through 50 nm TiO2 was found to be 310 degrees C. This is 80 degrees C lower as compared to MgH2 having a desorption temperature of 390 degrees C. It was noticed that the dehydrogenated MgH2 catalyzed with 50 nm TiO2 reabsorbed 5.1 wt% of H2 within 6 minutes at temperature and pressure of 250 degrees C and 50 atm, respectively. The 50 nm TiO2 catalyst lowered the absorption activation energy of MgH2 from - 92 to - 52.7 kJ mol(-1).

  4. Standard practice for evaluation of hydrogen uptake, permeation, and transport in metals by an electrochemical technique

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    1997-01-01

    1.1 This practice gives a procedure for the evaluation of hydrogen uptake, permeation, and transport in metals using an electrochemical technique which was developed by Devanathan and Stachurski. While this practice is primarily intended for laboratory use, such measurements have been conducted in field or plant applications. Therefore, with proper adaptations, this practice can also be applied to such situations. 1.2 This practice describes calculation of an effective diffusivity of hydrogen atoms in a metal and for distinguishing reversible and irreversible trapping. 1.3 This practice specifies the method for evaluating hydrogen uptake in metals based on the steady-state hydrogen flux. 1.4 This practice gives guidance on preparation of specimens, control and monitoring of the environmental variables, test procedures, and possible analyses of results. 1.5 This practice can be applied in principle to all metals and alloys which have a high solubility for hydrogen, and for which the hydrogen permeation is ...

  5. The effect of hydrogen on the morphology of n-type silicon electrodes under electrochemical conditions

    DEFF Research Database (Denmark)

    Goldar, A.; Roser, S.J.; Caruana, D.

    2001-01-01

    We study the electrochemical roughening of a silicon electrode surface during the hydrogen evolution reaction in a fluoride electrolyte using neutron reflection. We demonstrate that as the roughening process modifies the morphology of the silicon surface we can follow the changes by observing...

  6. Destabilization of magnesium hydride through interface engineering

    OpenAIRE

    Mooij, L.P.A.

    2013-01-01

    The aim of this thesis is to study the thermodynamics of hydrogenation of nanoconfined magnesium within a thin film multilayer model system. Magnesium hydride is a potential material for hydrogen storage, which is a key component in a renewable energy system based on hydrogen. In bulk form, magnesium hydride is very stable, which means that hydrogen is released only at elevated temperature. Furthermore, the kinetics of hydrogen sorption is slow, which further hampers the practical use of this...

  7. Reversible hydrogen storage property and structural analysis for face-centered cubic hydride Mg0.82Zr0.18H2 prepared by gigapascal hydrogen pressure method.

    Science.gov (United States)

    Takasaki, Tomoaki; Kyoi, Daisuke; Kitamura, Naoyuki; Tanase, Shigeo; Sakai, Tetsuo

    2007-12-27

    The face-centered cubic (fcc) type magnesium-zirconium hydride (Mg0.82Zr0.18Hx) was synthesized by means of the ultrahigh pressure (UHP) technique, which could generate 8 GPa of hydrogen pressure. The differential scanning calorimeter (DSC) measurements indicated that the fcc phase exhibited reversible hydrogen releasing and restoring properties under 0.5 MPa of hydrogen pressure. On the pressure-composition isotherms, the released and restored hydrogen capacities were estimated to be 3 approximately 3.5 wt %. The Rietveld analysis for synchrotron X-ray diffraction (XRD) data showed that the fcc phase had around 70 wt % mass fraction and was preserved without decomposition during hydrogen releasing and restoring cycles.

  8. Formation and characterisation of the silver hydride nanocluster cation [Ag3H2((Ph2 P)2CH2)](+) and its release of hydrogen.

    Science.gov (United States)

    Girod, Marion; Krstić, Marjan; Antoine, Rodolphe; MacAleese, Luke; Lemoine, Jérome; Zavras, Athanasios; Khairallah, George N; Bonačić-Koutecký, Vlasta; Dugourd, Philippe; O'Hair, Richard A J

    2014-12-08

    Multistage mass spectrometry and density functional theory (DFT) were used to characterise the small silver hydride nanocluster, [Ag3 H2 L](+) (where L=(Ph2 P)2 CH2 ) and its gas-phase unimolecular chemistry. Collision-induced dissociation (CID) yields [Ag2 HL](+) as the major product while laser-induced dissociation (LID) proceeds via H2 formation and subsequent release from [Ag3 H2 L](+) , giving rise to [Ag3 L](+) as the major product. Deuterium labelling studies on [Ag3 D2 L](+) prove that the source of H2 is from the hydrides and not from the ligand. Comparison of TD-DFT absorption patterns obtained for the optimised structures with action spectroscopy results, allows assignment of the measured features to structures of precursors and products. Molecular dynamics "on the fly" reveal that AgH loss is favoured in the ground state, but H2 formation and loss is preferred in the first excited state S1 , in agreement with CID and LID experimental findings. This indicates favourable photo-induced formation of H2 and subsequent release from [Ag3 H2 L](+) , an important finding in context of metal hydrides as a hydrogen storage medium, which can subsequently be released by heating or irradiation with light. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. From permanent magnets to rechargeable hydride electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Willems, J.J.G.; Buschow, K.H.J.

    1987-02-15

    A brief historical survey is given of how the study of coercitivity mechanisms in SmCo/sub 5/ permanent-magnet materials eventually led to the discovery of the favourable hydrogen sorption properties of the compound LaNi/sub 5/. It is shown how continued research by many investigators dealing with a variety of different physical and chemical properties has resulted in an advanced understanding of some of the principles that govern hydrogen absorption and which are responsible for the changes in physical properties that accompany it. The problems associated with various applications of LaNi/sub 5/-based hydrogen-storage materials are also briefly discussed. A large part of this paper is devoted to the applicability of LaNi/sub 5/-type materials in batteries. Research in this area has resulted in the development of a new type of rechargeable battery: the nickel-hydride cell. This battery can be charged and discharged at high rates and is relatively insensitive to overcharging and overdischarging. Special attention is given to the nature of the electrode degradation process and the effect of composition variations in LaNi/sub 5/-related materials on the lifetime of the corresponding hydride electrodes when subjected to severe electrochemical charge-discharge cycles.

  10. Computational Design, Theoretical and Experimental Investigation of Carbon Nanotube (CNT) - Metal Oxide/Metal Hydride Composite - A Practicable Hydrogen Storage Medium for Fuel Cell - 3

    Science.gov (United States)

    2012-08-29

    18 2 Theoretical Investigation First Principles Study of Hydrogen Storage in SWCNT Functionalized with metal complexes ( MgH2 , TiO2 & SnO2...10,10) armchair single walled carbon nanotube (SWCNT) functionalized with some metal complexes (Magnesium hydride ( MgH2 ), Titanium dioxide (TiO2...points scheme. As a beginning, single molecule of MgH2 (TiO2, SnO2) is attached to the CNT. The molecules are attached at a large distance in the outer

  11. Selective electrochemical generation of hydrogen peroxide from water oxidation

    CERN Document Server

    Viswanathan, Venkatasubramanian; Nørskov, Jens K

    2015-01-01

    Water is a life-giving source, fundamental to human existence, yet, over a billion people lack access to clean drinking water. Present techniques for water treatment such as piped, treated water rely on time and resource intensive centralized solutions. In this work, we propose a decentralized device concept that can utilize sunlight to split water into hydrogen and hydrogen peroxide. The hydrogen peroxide can oxidize organics while the hydrogen bubbles out. In enabling this device, we require an electrocatalyst that can oxidize water while suppressing the thermodynamically favored oxygen evolution and form hydrogen peroxide. Using density functional theory calculations, we show that the free energy of adsorbed OH$^*$ can be used as a descriptor to screen for selectivity trends between the 2e$^-$ water oxidation to H$_2$O$_2$ and the 4e$^-$ oxidation to O$_2$. We show that materials that bind oxygen intermediates sufficiently weakly, such as SnO$_2$, can activate hydrogen peroxide evolution. We present a rati...

  12. Research on Metal Hydride Compressor System

    Institute of Scientific and Technical Information of China (English)

    1999-01-01

    Ti-Zr series Laves phase hydrogen storage alloys with good hydrogen storage properties, such as large hydrogen capacity, rapid hydriding and dehydriding rate, high compression ratio, gentle plateau, small hysteresis, easily being activated and long cyclic stability etc. for metal hydride compressor have been investigated. In addition, a hydride compressor with special characteristics, namely, advanced filling method, good heat transfer effect and reasonable structural design etc. has also been constructed. A hydride compressor cryogenic system has been assembled coupling the compressor with a J-T micro-throttling refrigeration device and its cooling capacity can reach 0.4 W at 25 K.

  13. Research Surveys of Electrochemical Sensors for in-situ Determining Hydrogen in Steels

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The principle, construction and application of two types of electrochemical sensors-amperometric and potentiometric are surveyed. Both types of sensors are very sensitive to changes in temperature. The accuracy of hydrogen measurement depends on both the precision of sensors developed and the reliable technique of installation and security of sensors. The two types of sensors have been used for in-situ determining hydrogen permeated in steels owing to a corrosive reaction,a hydrogen gas circumstance at elevated temperatures and high pressure or also a pretreatment process such as pickling and plating process, etc.

  14. In situ μ+SR measurements on the hydrogen desorption reaction of magnesium hydride

    Science.gov (United States)

    Umegaki, I.; Nozaki, H.; Harada, M.; Higuchi, Y.; Noritake, T.; Matsumoto, M.; Towata, S.-i.; Ansaldo, E. J.; Brewer, J. H.; Koda, A.; Miyake, Y.; Sugiyama, J.

    2014-12-01

    In order to clarify the reason why the hydrogen desorption temperature (Td) of MgH2 is lowered by milling, we have studied the change in a local nuclear magnetic field with temperature by means of μ+SR. We have found a very clear oscillation in the ZF-spectrum at 2 K for the "milled" and "milled with Nb2O5" samples, while such oscillation is weaker for the "as prepared" MgH2. It was also found that the oscillation signal is stable up to 250 K and is assigned mainly due to the formation of a H-μ-H system. At temperatures above ambient T, we also found that the ZF-μ+SR spectrum exhibits a static Kubo-Toyabe behavior due to the nuclear magnetic field of 1H. Furthermore, it was clarified that rapid H diffusion starts well below Td only in the milled samples, leading to the conclusion that the consequent enhanced diffusion rate in MgH2 is essential to accelerate the desorption reaction and to decrease Td.

  15. Spectroelectrochemical analysis of the mechanism of (photo)electrochemical hydrogen evolution at a catalytic interface

    Science.gov (United States)

    Pastor, Ernest; Le Formal, Florian; Mayer, Matthew T.; Tilley, S. David; Francàs, Laia; Mesa, Camilo A.; Grätzel, Michael; Durrant, James R.

    2017-01-01

    Multi-electron heterogeneous catalysis is a pivotal element in the (photo)electrochemical generation of solar fuels. However, mechanistic studies of these systems are difficult to elucidate by means of electrochemical methods alone. Here we report a spectroelectrochemical analysis of hydrogen evolution on ruthenium oxide employed as an electrocatalyst and as part of a cuprous oxide-based photocathode. We use optical absorbance spectroscopy to quantify the densities of reduced ruthenium oxide species, and correlate these with current densities resulting from proton reduction. This enables us to compare directly the catalytic function of dark and light electrodes. We find that hydrogen evolution is second order in the density of active, doubly reduced species independent of whether these are generated by applied potential or light irradiation. Our observation of a second order rate law allows us to distinguish between the most common reaction paths and propose a mechanism involving the homolytic reductive elimination of hydrogen. PMID:28233785

  16. Influence of Temperature on Electrochemical Performances of Rare Earth Based Hydrogen Storage Material

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    In view of the higher temperature of large- size Ni/ MH battery in electric vehicle, the effect oftemperature on electrochemical performances of hydrogen storage alloy Ml ( NiCoMnTi )5 was investigated systematically.The results show that the electrochemical performances of alloy vary drastically with temperature changing.As temperature rises, the hydrogen equilibrium pressure increases, the width of hydrogen desorption plateau decreases and the gradient increases, leading to a decline of capacity.When temperature rises from 20 ℃ to 80 ℃, dischargeability is improved markedly.Higher temperatures also bring about a significant decrease in the cycling stability and self- discharge property.X-ray diffraction analysis indicates that the alloy has a single phase withCaCu5-type LaNi5 structure.

  17. Spectroelectrochemical analysis of the mechanism of (photo)electrochemical hydrogen evolution at a catalytic interface

    Science.gov (United States)

    Pastor, Ernest; Le Formal, Florian; Mayer, Matthew T.; Tilley, S. David; Francàs, Laia; Mesa, Camilo A.; Grätzel, Michael; Durrant, James R.

    2017-02-01

    Multi-electron heterogeneous catalysis is a pivotal element in the (photo)electrochemical generation of solar fuels. However, mechanistic studies of these systems are difficult to elucidate by means of electrochemical methods alone. Here we report a spectroelectrochemical analysis of hydrogen evolution on ruthenium oxide employed as an electrocatalyst and as part of a cuprous oxide-based photocathode. We use optical absorbance spectroscopy to quantify the densities of reduced ruthenium oxide species, and correlate these with current densities resulting from proton reduction. This enables us to compare directly the catalytic function of dark and light electrodes. We find that hydrogen evolution is second order in the density of active, doubly reduced species independent of whether these are generated by applied potential or light irradiation. Our observation of a second order rate law allows us to distinguish between the most common reaction paths and propose a mechanism involving the homolytic reductive elimination of hydrogen.

  18. [Electrochemically active microorganisms and electrolytically assisted fermentative hydrogen production--a review].

    Science.gov (United States)

    Li, Jianchang; Zhang, Wudi; Yin, Fang; Xu, Rui; Chen, Yubao

    2009-06-01

    Fermentative hydrogen production can be improved by electrolysis and electrochemically active microorganisms which are capable of using an electrode as an electron acceptor for the oxidation of organic matter, in particular, volatile acids produced after fermentation. Firstly volatile acids can be completely converted into CO2, electrons and protons on the surface of anode. Then the electrons flow to cathode through anode and wires, and at the same time the protons move to cathode through cation membrane between anode chamber and cathode chamber. Finally the electrons and the protons combine into hydrogen when they meet at the surface of cathode. In such a process, the fermentation barrier and the product inhibition can be avoided to improve the conversion of hydrogen. 8-9 mol H2/mol glucose of hydrogen potential can be obtained when glucose is used as substrate. This technology is very likely to be applied to produce hydrogen high efficiently from any energy crops, organic waste and wastewater.

  19. Influence of microstructure and mechanical stress on behavior of hydrogen in 500 nm Pd films

    Energy Technology Data Exchange (ETDEWEB)

    Vlček, Marián, E-mail: Marian.Vlcek@gmail.com [Faculty of Mathematics and Physics, Charles University in Prague, V Holešovičkách 2, CZ-18000 Praha 8 (Czech Republic); Lukáč, František; Vlach, Martin [Faculty of Mathematics and Physics, Charles University in Prague, V Holešovičkách 2, CZ-18000 Praha 8 (Czech Republic); Wagner, Stefan; Uchida, Helmut [Institute of Materials Physics, University of Göttingen, Friedrich-Hund-Platz 1, D-37077 Göttingen (Germany); Baehtz, Carsten; Shalimov, Artem [Institute of Ion Beam Physics and Materials Research, Helmholtz-Zentrum Dresden-Rossendorf, D-01314 Dresden (Germany); Pundt, Astrid [Institute of Materials Physics, University of Göttingen, Friedrich-Hund-Platz 1, D-37077 Göttingen (Germany); Čížek, Jakub [Faculty of Mathematics and Physics, Charles University in Prague, V Holešovičkách 2, CZ-18000 Praha 8 (Czech Republic)

    2015-10-05

    Highlights: • Influence of nano-structure and stresses on hydrogenation of Pd films was studied. • Nanocrystalline Pd films deposited on hard and soft substrates were compared. • It was found that nanocrystalline structure leads to narrowing of the miscibility gap. • Compressive in-plane stress suppresses the hydride formation. • The lattice constants for α-phase and the hydride phase are closer than in bulk Pd. - Abstract: Pd films can be used as a model system to examine the influence of microstructure and stress on the hydrogen absorption. In this work we study 500 nm Pd films deposited on different substrates with different binding strengths. The films were electrochemically loaded with hydrogen up to hydride concentration. Development of lattice constant during hydrogen loading of Pd films was investigated by in situ X-ray diffraction using synchrotron radiation. The influence of microstructure and mechanical stress in the films on the phase transition from Pd to Pd hydride was examined.

  20. Characteristics and Applications of Metal Hydrides

    Science.gov (United States)

    Egan, G. J.; Lynch, F. E.

    1987-01-01

    Report discusses engineering principles of uses of metal hydrides in spacecraft. Metal hydrides absorb, store, pump, compress, and expand hydrogen gas. Additionally, they release or absorb sizeable amounts of heat as they form and decompose - property adapted for thermal-energy management or for propulsion. Describes efforts to: Identify heat sources and sinks suitable for driving metal hydride thermal cycles in spacecraft; develop concepts for hydride subsystems employing available heating and cooling methods; and produce data base on estimated sizes, masses, and performances of hydride devices for spacecraft.

  1. Hydrogen Extraction Characteristics of Electrochemical Hydrogen Pump Using Proton-conducting Ceramics CaZr0.9In0.1O3-α

    Institute of Scientific and Technical Information of China (English)

    XIA; Ti-rui; YANG; Hong-guang; HE; Chang-shui; YANG; Li-ling; ZHAO; Wei-wei; LIU; Zhen-xing

    2013-01-01

    To develop high-efficiency and economical hydrogen isotope purification and recovery processes for a tritium extraction system in a fusion reactor,hydrogen extraction characteristics of an electrochemical hydrogen pump using a one-end closed tube made of proton-conducting ceramic CaZr0.9In0.1O3-α(effective electrode area was 160 cm2)were studied.The hydrogen pumping characteristics were evaluated over the

  2. Hydrogen Storage Properties of New Hydrogen-Rich BH3NH3-Metal Hydride (TiH2, ZrH2, MgH2, and/or CaH2) Composite Systems

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Young Joon; Xu, Yimin; Shaw, Wendy J.; Ronnebro, Ewa

    2012-04-19

    Ammonia borane (AB = NH3BH3) is one of the most attractive materials for chemical hydrogen storage due to its high hydrogen contents of 19.6 wt.%, however, impurity levels of borazine, ammonia and diborane in conjunction with foaming and exothermic hydrogen release calls for finding ways to mitigate the decomposition reactions. In this paper we present a solution by mixing AB with metal hydrides (TiH2, ZrH2, MgH2 and CaH2) which have endothermic hydrogen release in order to control the heat release and impurity levels from AB upon decomposition. The composite materials were prepared by mechanical ball milling, and their H2 release properties were characterized by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The formation of volatile products from decomposition side reactions, such as borazine (N3B3H6) was determined by mass spectrometry (MS). Sieverts type pressure-composition-temperature (PCT) gas-solid reaction instrument was adopted to observe the kinetics of the H2 release reactions of the combined systems and neat AB. In situ 11B MAS-NMR revealed a destabilized decomposition pathway. We found that by adding specific metal hydrides to AB we can eliminate the impurities and mitigate the heat release.

  3. Tin Oxide Nanorod Array-Based Electrochemical Hydrogen Peroxide Biosensor

    Directory of Open Access Journals (Sweden)

    Liu Jinping

    2010-01-01

    Full Text Available Abstract SnO2 nanorod array grown directly on alloy substrate has been employed as the working electrode of H2O2 biosensor. Single-crystalline SnO2 nanorods provide not only low isoelectric point and enough void spaces for facile horseradish peroxidase (HRP immobilization but also numerous conductive channels for electron transport to and from current collector; thus, leading to direct electrochemistry of HRP. The nanorod array-based biosensor demonstrates high H2O2 sensing performance in terms of excellent sensitivity (379 μA mM−1 cm−2, low detection limit (0.2 μM and high selectivity with the apparent Michaelis–Menten constant estimated to be as small as 33.9 μM. Our work further demonstrates the advantages of ordered array architecture in electrochemical device application and sheds light on the construction of other high-performance enzymatic biosensors.

  4. Electrochemical promotion of NO reduction by hydrogen on a platinum/polybenzimidazole catalyst

    DEFF Research Database (Denmark)

    Petrushina, Irina; Bandur, Viktor; Cappeln, Frederik Vilhelm;

    2003-01-01

    The electrochemical promotion of catalytic NO reduction by hydrogen was studied using a (NO, H-2, Ar), Pt polybenzimidazole (PBI)-H3PO4\\Pt, (H-2, Ar) fuel cell at 135degreesC. A mixture of NO/H-2/Ar was used as the working mixture at one electrode and a mixture of H-2/Ar was used as reference...... and 140 mL/min, respectively), NO reduction increased 20 times even without polarization compared to the high gas flow rate. The electrochemical promotion effect occurs at positive polarization with a maximum increase at approximately 0.08 V and with 1.5 times the zero polarization value. The promotion...... at the negative polarization can be attributed to the electrochemical production of the promoters. At low gas flow rates, a charge-induced change of the strength of chemisorptive bonds can take place....

  5. Effects of chemical coating with Ni on electrochemical properties of Mg2Ni hydrogen storage alloys

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The effects of nickel coating on the electrochemical properties of Mg2Ni hydrogen storage alloys are presented in this paper. X-ray diffraction (XRD) and scanning electron microscope (SEM) techniques were employed to examine the crystal structure and surface morphologies of the bare and Ni-coated Mg2Ni alloys. The electrochemical properties of alloys were characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results showed that Ni coating not only decreased the charge transfer resistance, but also decreased the H atom diflusion resistance for Mg2Ni alloys. It was also found that Ni coating effectively improved the discharge capacity, but decreased the cycling performance of the as-synthesized Ni-coated Mg2Ni alloys. The discharge current has a great impact on the cycling performance of the as-synthesized Ni-coated Mg2Ni alloys.

  6. Catalytic effect of nanoparticle 3d-transition metals on hydrogen storage properties in magnesium hydride MgH2 prepared by mechanical milling.

    Science.gov (United States)

    Hanada, Nobuko; Ichikawa, Takayuki; Fujii, Hironobu

    2005-04-21

    We examined the catalytic effect of nanoparticle 3d-transition metals on hydrogen desorption (HD) properties of MgH(2) prepared by mechanical ball milling method. All the MgH(2) composites prepared by adding a small amount of nanoparticle Fe(nano), Co(nano), Ni(nano), and Cu(nano) metals and by ball milling for 2 h showed much better HD properties than the pure ball-milled MgH(2) itself. In particular, the 2 mol % Ni(nano)-doped MgH(2) composite prepared by soft milling for a short milling time of 15 min under a slow milling revolution speed of 200 rpm shows the most superior hydrogen storage properties: A large amount of hydrogen ( approximately 6.5 wt %) is desorbed in the temperature range from 150 to 250 degrees C at a heating rate of 5 degrees C/min under He gas flow with no partial pressure of hydrogen. The EDX micrographs corresponding to Mg and Ni elemental profiles indicated that nanoparticle Ni metals as catalyst homogeneously dispersed on the surface of MgH(2). In addition, it was confirmed that the product revealed good reversible hydriding/dehydriding cycles even at 150 degrees C. The hydrogen desorption kinetics of catalyzed and noncatalyzed MgH(2) could be understood by a modified first-order reaction model, in which the surface condition was taken into account.

  7. Electrochemical synthesis of macroporous zinc oxide layers by employing hydrogen peroxide as oxygen precursor

    Energy Technology Data Exchange (ETDEWEB)

    Ramirez, Daniel [Laboratoire d' Electrochimie et Chimie Analytique (UMR CNRS 7575), Ecole Nationale Superieure de Chimie de Paris (ENSCP) (France); Instituto de Quimica, Pontificia Universidad Catolica de Valparaiso, Valparaiso (Chile); Bartlett, Philip; Abdelsalam, Mamdouh [School of Chemistry, University of Southampton (United Kingdom); Gomez, Humberto [Instituto de Quimica, Pontificia Universidad Catolica de Valparaiso, Valparaiso (Chile); Lincot, Daniel [Laboratoire d' Electrochimie et Chimie Analytique (UMR CNRS 7575), Ecole Nationale Superieure de Chimie de Paris (ENSCP) (France)

    2008-10-15

    Two- and three-dimensional ordered porous zinc oxide (ZnO) films were prepared by electrodeposition on Indium Tin Oxide coated glass, using two- and three-dimensional poly(styrene) opal templates. The oxide was formed by electrochemical reduction of hydrogen peroxide in aqueous zinc perchlorate solution. Scanning electron microscopy measurements showed well ordered inverse opal structures for macroporous ZnO. At high hydrogen peroxide concentration, dense inner conformal filling was achieved for 2D and 3D structures. The formation of nanocrystalline ZnO was checked by X-ray diffraction. (copyright 2008 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  8. Electrochemical separation of hydrogen from reformate using PEM fuel cell technology

    Energy Technology Data Exchange (ETDEWEB)

    Gardner, C.L. [Department of Chemical Engineering and Centre for Catalysis Research and Innovation, University of Ottawa, Ottawa, Ontario K1N 6N5 (Canada); Ternan, M. [EnPross Inc., 147 Banning Road, Ottawa, Ontario K2L 1C5 (Canada)

    2007-09-27

    This article is an examination of the feasibility of electrochemically separating hydrogen obtained by steam reforming a hydrocarbon or alcohol source. A potential advantage of this process is that the carbon dioxide rich exhaust stream should be able to be captured and stored thereby reducing greenhouse gas emissions. Results are presented for the performance of the anode of proton exchange membrane (PEM) electrochemical cell for the separation of hydrogen from a H{sub 2}-CO{sub 2} gas mixture and from a H{sub 2}-CO{sub 2}-CO gas mixture. Experiments were carried out using a single cell state-of-the-art PEM fuel cell. The anode was fed with either a H{sub 2}-CO{sub 2} gas mixture or a H{sub 2}-CO{sub 2}-CO gas mixture and hydrogen was evolved at the cathode. All experiments were performed at room temperature and atmospheric pressure. With the H{sub 2}-CO{sub 2} gas mixture the hydrogen extraction efficiency is quite high. When the gas mixture included CO, however, the hydrogen extraction efficiency is relatively poor. To improve the efficiency for the separation of the gas mixture containing CO, the effect of periodic pulsing on the anode potential was examined. Results show that pulsing can substantially reduce the anode potential thereby improving the overall efficiency of the separation process although the anode potential of the CO poisoned and pulsed cell still lies above that of an unpoisoned cell. (author)

  9. Electrochemical separation of hydrogen from reformate using PEM fuel cell technology

    Science.gov (United States)

    Gardner, C. L.; Ternan, M.

    This article is an examination of the feasibility of electrochemically separating hydrogen obtained by steam reforming a hydrocarbon or alcohol source. A potential advantage of this process is that the carbon dioxide rich exhaust stream should be able to be captured and stored thereby reducing greenhouse gas emissions. Results are presented for the performance of the anode of proton exchange membrane (PEM) electrochemical cell for the separation of hydrogen from a H 2-CO 2 gas mixture and from a H 2-CO 2-CO gas mixture. Experiments were carried out using a single cell state-of-the-art PEM fuel cell. The anode was fed with either a H 2-CO 2 gas mixture or a H 2-CO 2-CO gas mixture and hydrogen was evolved at the cathode. All experiments were performed at room temperature and atmospheric pressure. With the H 2-CO 2 gas mixture the hydrogen extraction efficiency is quite high. When the gas mixture included CO, however, the hydrogen extraction efficiency is relatively poor. To improve the efficiency for the separation of the gas mixture containing CO, the effect of periodic pulsing on the anode potential was examined. Results show that pulsing can substantially reduce the anode potential thereby improving the overall efficiency of the separation process although the anode potential of the CO poisoned and pulsed cell still lies above that of an unpoisoned cell.

  10. Hydrogen evolution activity and electrochemical stability of selected transition metal carbides in concentrated phosphoric acid

    DEFF Research Database (Denmark)

    Tomás García, Antonio Luis; Jensen, Jens Oluf; Bjerrum, Niels J.

    2014-01-01

    Alternative catalysts based on carbides of Group 5 (niobium and tantalum) and 6 (chromium, molybdenum and tungsten) metals were prepared as films on the metallic substrates. The electrochemical activities of these carbide electrodes towards the hydrogen evolution reaction (HER) in concentrated......, attributable to the different electronic structures. Tungsten carbide among the studied electrode samples exhibited the highest HER activity. Upon anodic potential scans in the presence of oxygen, chromium, tantalum and tungsten carbides displayed passivation due to the formation of stable surface layers...

  11. Electrochemical impedance studies of AB{sub 5}-type hydrogen storage alloy

    Energy Technology Data Exchange (ETDEWEB)

    Slepski, Pawel; Darowicki, Kazimierz; Andrearczyk, Karolina [Department of Electrochemistry Corrosion and Materials Engineering, Gdansk University of Technology, 11/12 Narutowicza Street, 80-233 Gdansk (Poland); Kopczyk, Maciej; Sierczynska, Agnieszka [Institute of Non-ferrous Metals, Department in Poznan, Central Laboratory of Batteries and Cells, 12 Forteczna Street, 61-362 Poznan (Poland)

    2010-05-01

    Electrochemical impedance spectroscopy technique was used to describe behavior of AB{sub 5}-type hydrogen storage alloy. Impedance investigations were performed during cyclic voltammetry measurement and charge/discharge cycles. The comprehensive interpretation of instantaneous impedance spectra obtained in potentiostatic mode allowed further to interpret impedance results in galvanostatic mode. Proposed methodology enabled to trace electrical parameters as a function of state of charge (SOC) and depth of discharge (DOD). (author)

  12. Reversible electrochemical storage of hydrogen in Ti{sub 51-x}Zr{sub x}Ni{sub 49} (0 {<=} x {<=} 24) alloys; Stockage electrochimique reversible de l'hydrogene dans les alliages Ti{sub 51-x}Zr{sub x}Ni{sub 49} (0 {<=} x {<=} 24)

    Energy Technology Data Exchange (ETDEWEB)

    Guiose, B.; Cuevas, F.; Decamps, B.; Percheron-Guegan, A. [Centre National de la Recherche Scientifique (CNRS), Lab. de Chimie Metallurgique des Terres Rares, 94 - Thiais (France)

    2007-07-01

    The substitution of Ti by Zr in the TiNi compound allows to obtain, by solid-gas reaction, hydrides of martensitic phase. These hydrides, of strong hydrogen storage capacity, have a thermodynamic stability which increases with the Zr amount. Moreover, they can absorb until 2.5 hydrogen atoms by AB formula (H/AB; A: Ti, Zr; B: Ni) for only 1.5 H/AB for the hydride of austenitic phase. The electrochemical properties of the alloys of composition Ti{sub 51-x}Zr{sub x}Ni{sub 49} (0 {<=} x {<=} 24) have been studied: discharge capacity, equilibrium potential and cycling resistance. The results show that the capacity discharged by the substituted alloys are more important (370 mAh/g for x=6 by instance) than those of the binary alloy Ti{sub 51}Ni{sub 49} (150 mAh/g). These values correspond to the hydrogen quantity which participates in a reversible way to the hydrogenation/dehydrogenation processes. Nevertheless, the activation period increases with the Zr amount. Moreover, the cycling lifetime of these electrodes is short (decrease of 90% in some twenty cycles for x=6, 12 and 18 and in 37 cycles for x=24) compared to those of the binary alloy (decrease of 40% in some hundred cycles). This short lifetime is explained by the formation of passivation layers due to the use of potash as electrolyte. Scanning and transmission electron microscopies are used for characterizing the nature of these layers in order to understand their formation mechanism and to avoid them. (O.M.)

  13. Complex transition metal hydrides incorporating ionic hydrogen: Synthesis and characterization of Na{sub 2}Mg{sub 2}FeH{sub 8} and Na{sub 2}Mg{sub 2}RuH{sub 8}

    Energy Technology Data Exchange (ETDEWEB)

    Humphries, Terry D., E-mail: terry_humphries81@hotmail.com [WPI-Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan); Takagi, Shigeyuki; Li, Guanqiao; Matsuo, Motoaki; Sato, Toyoto [Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan); Sørby, Magnus H.; Deledda, Stefano; Hauback, Bjørn C. [Physics Department, Institute for Energy Technology, Kjeller NO-2027 (Norway); Orimo, Shin-ichi [WPI-Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan); Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan)

    2015-10-05

    Highlights: • Structures of Na{sub 2}Mg{sub 2}FeH{sub 8} and Na{sub 2}Mg{sub 2}RuH{sub 8} have been determined by XRD and PND. • Compounds incorporate independently coordinated ionic and covalent hydrogen. • [TH{sub 6}]{sup 4−} anion is surrounded by a cubic array of four Mg{sup 2+} and four Na{sup +} cations. • H{sup −} anions are octahedrally coordinated by four Na{sup +} and two Mg{sup 2+} cations. • Vibrational modes of the H{sup −} anions and complex hydride anion are observed. - Abstract: A new class of quaternary complex transition metal hydrides (Na{sub 2}Mg{sub 2}TH{sub 8} (T = Fe, Ru)) have been synthesized and their structures determined by combined synchrotron radiation X-ray and powder neutron diffraction. The compounds can be considered as a link between ionic and complex hydrides in terms of incorporating independently coordinated ionic and covalent hydrogen. These novel isostructural complex transition metal hydrides crystallize in the orthorhombic space group Pbam, where the octahedral complex hydride anion is surrounded by a cubic array of four Mg{sup 2+} and four Na{sup +} cations, forming distinct two-dimensional layers. An intriguing feature of these materials is the distorted octahedral coordination of the isolated H{sup −} anions by four Na{sup +} and two Mg{sup 2+} cations, which form layers between the transition metal containing layers. The vibrational modes of the H{sup −} anions and complex hydride anion are independently observed for the first time in a quaternary complex transition metal hydride system by Raman and IR spectroscopy.

  14. Luminescent properties of aluminum hydride

    Energy Technology Data Exchange (ETDEWEB)

    Baraban, A.P.; Gabis, I.E.; Dmitriev, V.A. [Saint-Petersburg State University, Department of Physics, Saint-Petersburg 198504 (Russian Federation); Dobrotvorskii, M.A., E-mail: mstislavd@gmail.com [Saint-Petersburg State University, Department of Physics, Saint-Petersburg 198504 (Russian Federation); Kuznetsov, V.G. [Saint-Petersburg State University, Department of Physics, Saint-Petersburg 198504 (Russian Federation); Matveeva, O.P. [National Mineral Resources University, Saint Petersburg 199106 (Russian Federation); Titov, S.A. [Petersburg State University of Railway Transport, Saint-Petersburg 190031 (Russian Federation); Voyt, A.P.; Elets, D.I. [Saint-Petersburg State University, Department of Physics, Saint-Petersburg 198504 (Russian Federation)

    2015-10-15

    We studied cathodoluminescence and photoluminescence of α-AlH{sub 3}– a likely candidate for use as possible hydrogen carrier in hydrogen-fueled vehicles. Luminescence properties of original α-AlH{sub 3} and α-AlH{sub 3} irradiated with ultraviolet were compared. The latter procedure leads to activation of thermal decomposition of α-AlH{sub 3} and thus has a practical implementation. We showed that the original and UV-modified aluminum hydride contain luminescence centers ‐ structural defects of the same type, presumably hydrogen vacancies, characterized by a single set of characteristic bands of radiation. The observed luminescence is the result of radiative intracenter relaxation of the luminescence center (hydrogen vacancy) excited by electrons or photons, and its intensity is defined by the concentration of vacancies, and the area of their possible excitation. UV-activation of the dehydrogenation process of aluminum hydride leads to changes in the spatial distribution of the luminescence centers. For short times of exposure their concentration increases mainly in the surface regions of the crystals. At high exposures, this process extends to the bulk of the aluminum hydride and ends with a decrease in concentration of luminescence centers in the surface region. - Highlights: • Aluminum hydride contains hydrogen vacancies which serve as luminescence centers. • The luminescence is the result of radiative relaxation of excited centers. • Hydride UV-irradiation alters distribution and concentration of luminescence centers.

  15. New synthesis route for ternary transition metal amides as well as ultrafast amide-hydride hydrogen storage materials.

    Science.gov (United States)

    Cao, Hujun; Santoru, Antonio; Pistidda, Claudio; Richter, Theresia M M; Chaudhary, Anna-Lisa; Gizer, Gökhan; Niewa, Rainer; Chen, Ping; Klassen, Thomas; Dornheim, Martin

    2016-04-14

    K2[Mn(NH2)4] and K2[Zn(NH2)4] were successfully synthesized via a mechanochemical method. The mixture of K2[Mn(NH2)4] and LiH showed excellent rehydrogenation properties. In fact, after dehydrogenation K2[Mn(NH2)4]-8LiH fully rehydrogenates within 60 seconds at ca. 230 °C and 5 MPa of H2. This is one of the fastest rehydrogenation rates in amide-hydride systems known to date. This work also shows a strategy for the synthesis of transition metal nitrides by decomposition of the mixtures of M[M'(NH2)n] (where M is an alkali or alkaline earth metal and M' is a transition metal) and metal hydrides.

  16. Non-dispersive atomic-fluorescence spectrometry of trace amounts of bismuth by introduction of its gaseous hydride into a premixed argon (entrained air)-hydrogen flame.

    Science.gov (United States)

    Kobayashi, S; Nakahara, T; Musha, S

    1979-10-01

    A method has been developed for the determination of bismuth by generation of its gaseous hydride and introduction of the hydride into a premixed argon (entrained air)-hydrogen flame, the atomic-fluorescence lines from which are all detected by use of a non-dispersive system. The detection limit is 5 pg/ml, or 0.1 ng of bismuth, but the reagent blank found in a 20-ml sample volume was approximately 2 ng of bismuth. Analytical working curves obtained by measuring peak-heights and integrated peak-areas of the signals are linear over a range of about four orders of magnitude from the detection limit. Perchloric, phosphoric and sulphuric acids up to 2.0M concentration give no interference, but nitric acid gives slight depression of the signal. The presence of silver, gold, nickel, palladium, platinum, selenium and tellurium in 1000-fold ratio to bismuth causes pronounced depression of the signal, whereas mercury and tin slightly enhance the atomic-fluorescence signal. The method has been applied to the determination of bismuth in aluminium-base alloys and sulphide ores with use of the standard additions method. The results are in good agreement with those obtained by flame atomic-absorption spectrometry and optical emission spectrometry with an inductively coupled plasma.

  17. O2 insertion into group 9 metal-hydride bonds: evidence for oxygen activation through the hydrogen-atom-abstraction mechanism.

    Science.gov (United States)

    Keith, Jason M; Teets, Thomas S; Nocera, Daniel G

    2012-09-03

    A detailed density functional study was performed to examine the reaction of mixed-valence dirhodium and diiridium species [M(2)(0,II)(tfepma)(2)(CN(t)Bu)(2)(Cl)(2) (1, tfepma = MeN[P(OCH(2)CF(3))(2)](2), CN(t)Bu = tert-butyl isocyaninde)] with HCl and oxygen with an interest in examining the pathways for oxygen insertion into the intermediate metal hydride to form hydroperoxo species. The O(2) hydrogen atom abstraction mechanism for both the Rh and Ir was found to be feasible. This is the first time this mechanism has been applied to a Rh system and only the second time it has been examined for a system other than Pd. The competing trans HCl reductive elimination pathway was also examined and found to be greatly dependent on the stereochemistry of the starting hydride primarily due to the intermediate formed upon the loss of Cl(-). As a result, the reductive elimination pathway was more favorable by 11.5 kcal/mol for the experimentally observed Ir stereoisomer, while the two pathways were isoenergetic for the other stereoisomer of the Rh complex. All findings are consistent with the kinetics study previously performed.

  18. Best mix of primary energy resources by renewable energy and fossil fuel with CCS in view of security,stability and sustainability——A vision on hydrogen supply chain by organic chemical hydride method

    Institute of Scientific and Technical Information of China (English)

    Junichi; SAKAGUCHI

    2010-01-01

    The best mix scenario by renewable energy and fossil fuel with or without CCS(Carbon Dioxide Capture and Storage) would be a solution to compromise Greenhouse Gases emission issue caused by carbon dioxide(CO2),and depletion of crude oil and natural gas reserves.As fossil fuel with pre-combustion CCS means hydrogen manufacturing and also hydrogen can be produced via electrolysis with renewable energy,it is desirable to establish transportation and storage systems of hydrogen as a clean energy.In this paper a vision on Hydrogen Supply Chain by Organic Chemical Hydride(OCH) Method as well as comparison of CCS configuration are discussed.

  19. Thermodynamic diagnosis of the properties and mechanism of dihydropyridine-type compounds as hydride source in acetonitrile with "Molecule ID Card".

    Science.gov (United States)

    Zhu, Xiao-Qing; Tan, Yue; Cao, Chao-Tun

    2010-02-11

    A series of 45 dihydropyridine-type organic compounds as hydride source were designed and synthesized. The thermodynamic driving forces (defined as enthalpy changes or redox potentials in this work) of the dihydropyridines to release hydride anions, hydrogen atoms (hydrogen for short), and electrons in acetonitrile, the thermodynamic driving forces of the radical cations of the dihydropyridines to release protons and hydrogens in acetonitrile, and the thermodynamic driving forces of the neutral pyridine-type radicals of the dihydropyridines to release electron in acetonitrile were determined by using titration calorimetry and electrochemical methods. The rates and activation parameters of hydride transfer from the dihydropyridines to acridinium perclorate, a well-known hydride acceptor, were determined by using UV-vis absorption spectroscopy technique. The relationship between the thermodynamic driving forces and kinetic rate of the hydride transfer was examined. Thermodynamic characteristic graph (TCG) of the dihydropyridines as an efficient "Molecule ID Card" was introduced. The TCG can be used to quantitatively diagnose or predict the characteristic chemical properties of the dihydropyridines and their various reaction intermediates. The mechanism of hydride transfer from the dihydropyridines to acridinium perclorate was diagnosed and elucidated by using the determined thermodynamic parameters and the activation parameters.

  20. Mechanism of electrochemical reduction of hydrogen peroxide on copper in acidic sulfate solutions.

    Science.gov (United States)

    Stewart, Karen L; Gewirth, Andrew A

    2007-09-11

    Hydrogen peroxide is a commonly used oxidizer component in chemical mechanical planarization slurries, used in the processing of Cu metallization in microelectronics applications. We studied the electrochemical reduction of hydrogen peroxide on Cu in 0.1 M H2SO4 solutions using methods including cyclic voltammetry, rotating disk electrode experiments, surface-enhanced Raman spectroscopy, and density functional theory (DFT) calculations. The spectroscopy reveals that the hydrogen peroxide molecule is reduced at negative potentials to form a Cu-OH surface species in acidic solutions, a result consistent with the insight from Tafel slope measurements. DFT calculations support the instability of peroxide relative to the surface-coordinated hydroxide on both Cu(111) and Cu(100) surfaces.

  1. ON-SITE APPLICABILITY OF HYDROGEN PEROXIDE PRODUCING MICROBIAL ELECTROCHEMICAL CELLS COUPLED WITH UV IN WASTEWATER DISINFECTION STUDY

    Science.gov (United States)

    There is an increased interest in the application of microbial electrochemical cell (MEC) for the recovery of value-added products such as hydrogen gas and hydrogen peroxide (H2O2) from wastewater. H2O2 has strong oxidation capability and produces hydroxyl radicals when coupled w...

  2. On-site applicability of hydrogen peroxide producing microbial electrochemical cells (MECs) coupled with UV in wastewater disinfection study

    Science.gov (United States)

    Background: There is an increased interest in the application of microbial electrochemical cell (MEC) for the recovery of value-added products such as hydrogen gas and hydrogen peroxide (H2O2) from wastewater. H2O2 has strong oxidation capability and produces hydroxyl radicals wh...

  3. Electrochemical removal of hydrogen atoms in Mg-doped GaN epitaxial layers

    Energy Technology Data Exchange (ETDEWEB)

    Lee, June Key, E-mail: junekey@jnu.ac.kr, E-mail: hskim7@jbnu.ac.kr; Hyeon, Gil Yong; Tawfik, Wael Z.; Choi, Hee Seok [Department of Materials Science and Engineering, and Optoelectronics Convergence Research Center, Chonnam National University, Gwangju 500-757 (Korea, Republic of); Ryu, Sang-Wan [Department of Physics and Optoelectronics Convergence Research Center, Chonnam National University, Gwangju 500-757 (Korea, Republic of); Jeong, Tak [Korea Photonics Technology Institute, Gwangju 500-460 (Korea, Republic of); Jung, Eunjin; Kim, Hyunsoo, E-mail: junekey@jnu.ac.kr, E-mail: hskim7@jbnu.ac.kr [School of Semiconductor and Chemical Engineering, Semiconductor Physics Research Center, Chonbuk National University, Jeonju 561-756 (Korea, Republic of)

    2015-05-14

    Hydrogen atoms inside of an Mg-doped GaN epitaxial layer were effectively removed by the electrochemical potentiostatic activation (EPA) method. The role of hydrogen was investigated in terms of the device performance of light-emitting diodes (LEDs). The effect of the main process parameters for EPA such as solution type, voltage, and time was studied and optimized for application to LED fabrication. In optimized conditions, the light output of 385-nm LEDs was improved by about 26% at 30 mA, which was caused by the reduction of the hydrogen concentration by ∼35%. Further removal of hydrogen seems to be involved in the breaking of Ga-H bonds that passivate the nitrogen vacancies. An EPA process with high voltage breaks not only Mg-H bonds that generate hole carriers but also Ga-H bonds that generate electron carriers, thus causing compensation that impedes the practical increase of hole concentration, regardless of the drastic removal of hydrogen atoms. A decrease in hydrogen concentration affects the current-voltage characteristics, reducing the reverse current by about one order and altering the forward current behavior in the low voltage region.

  4. A nanostructured Ni/graphene hybrid for enhanced electrochemical hydrogen storage

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Moon-Hyung; Min, Young-Je [Department of Chemistry and Green-Nano Materials Research Center, Kyungpook National University, Taegu 702-701 (Korea, Republic of); Gwak, Gyeong-Hyeon [Department of Chemistry and Medical Chemistry, College of Science and Technology, Yonsei University, Wonju, Gangwondo 220-710 (Korea, Republic of); Paek, Seung-Min, E-mail: smpaek@knu.ac.kr [Department of Chemistry and Green-Nano Materials Research Center, Kyungpook National University, Taegu 702-701 (Korea, Republic of); Oh, Jae-Min, E-mail: jaemin.oh@yonsei.ac.kr [Department of Chemistry and Medical Chemistry, College of Science and Technology, Yonsei University, Wonju, Gangwondo 220-710 (Korea, Republic of)

    2014-10-15

    Highlights: • Graphene oxide(GO) was hybridized with the Ni(OH){sub 2}. • The Ni(OH){sub 2}/GO was reduced to Ni/graphene. • XRD, TEM, and X-ray absorption spectroscopy were examined. • The hydrogen storage property of Ni/graphene was significantly enhanced. - Abstract: To fabricate electrochemical hydrogen storage materials with delaminated structure, the graphene oxide (GO) in the ethylene glycol solution was reassembled in the presence of the precursor of Ni nanoparticles, and then, the reassembled hybrid was reduced under hydrogen atmosphere to obtain Ni/graphene hybrid. X-ray diffraction patterns and X-ray absorption spectscopic (XAS) analysis clearly show that Ni nanoparticles in Ni/graphene hybrid maintain its nanosized nature even after hybridization with graphene nanosheet (GNS). According to the TEM analysis, the Ni nanoparticles with an average size of 5.2 nm are homogeneously distributed onto the GNS in such a way that the nanoporous structure with much amount of void spaces could be fabricated. The obtained Ni/GNS exhibits a hydrogen storage capacity of 160 mA h/g, while the specific capacity of the graphene nanosheet was only 21 mA h/g. A flexible delaminated structure of Ni/GNS nanocomposite could provide additional intercalation sites for accommodation of hydrogen, leading to the enhancement of hydrogen storage capacity.

  5. In operando neutron diffraction study of LaNdMgNi9H13 as a metal hydride battery anode

    Science.gov (United States)

    Nazer, N. S.; Denys, R. V.; Yartys, V. A.; Hu, Wei-Kang; Latroche, M.; Cuevas, F.; Hauback, B. C.; Henry, P. F.; Arnberg, L.

    2017-03-01

    La2MgNi9-related alloys are superior metal hydride battery anodes as compared to the commercial AB5 alloys. Nd-substituted La2-yNdyMgNi9 intermetallics are of particular interest because of increased diffusion rate of hydrogen and thus improved performance at high discharge currents. The present work presents in operando characterization of the LaNdMgNi9 intermetallic as anode for the nickel metal hydride (Ni-MH) battery. We have studied the structural evolution of LaNdMgNi9 during its charge and discharge using in situ neutron powder diffraction. The work included experiments using deuterium gas and electrochemical charge-discharge measurements. The alloy exhibited a high electrochemical discharge capacity (373 mAh/g) which is 20% higher than the AB5 type alloys. A saturated β-deuteride synthesized by solid-gas reaction at PD2 = 1.6 MPa contained 12.9 deuterium atoms per formula unit (D/f.u.) which resulted in a volume expansion of 26.1%. During the electrochemical charging, the volume expansion (23.4%) and D-contents were found to be slightly reduced. The reversible electrochemical cycling is performed through the formation of a two-phase mixture of the α-solid solution and β-hydride phases. Nd substitution contributes to the high-rate dischargeability, while maintaining a good cyclic stability. Electrochemical Impedance Spectroscopy (EIS) was used to characterize the anode electrode on cycling. A mathematical model for the impedance response of a porous electrode was utilized. The EIS showed a decreased hydrogen transport rate during the long-term cycling, which indicated a corresponding slowing down of the electrochemical processes at the surface of the metal hydride anode.

  6. Electrochemical interfacial influences on deoxygenation and hydrogenation reactions in CO reduction on a Cu(100) surface.

    Science.gov (United States)

    Sheng, Tian; Lin, Wen-Feng; Sun, Shi-Gang

    2016-06-01

    Electroreduction of CO2 to hydrocarbons on a copper surface has attracted much attention in the last few decades for providing a sustainable way for energy storage. During the CO2 and further CO electroreduction processes, deoxygenation that is C-O bond dissociation, and hydrogenation that is C-H bond formation, are two main types of surface reactions catalyzed by the copper electrode. In this work, by performing the state-of-the-art constrained ab initio molecular dynamics simulations, we have systematically investigated deoxygenation and hydrogenation reactions involving two important intermediates, COHads and CHOads, under various conditions of (i) on a Cu(100) surface without water molecules, (ii) at the water/Cu(100) interface and (iii) at the charged water/Cu(100) interface, in order to elucidate the electrochemical interfacial influences. It has been found that the electrochemical interface can facilitate considerably the C-O bond dissociation via changing the reaction mechanisms. However, C-H bond formation has not been affected by the presence of water or electrical charge. Furthermore, the promotional roles of an aqueous environment and negative electrode potential in deoxygenation have been clarified, respectively. This fundamental study provides an atomic level insight into the significance of the electrochemical interface towards electrocatalysis, which is of general importance for understanding electrochemistry.

  7. Highly regioselective hydride transfer, oxidative dehydrogenation, and hydrogen-atom abstraction in the thermal gas-phase chemistry of [Zn(OH)](+)/C3H8.

    Science.gov (United States)

    Wu, Xiao-Nan; Zhao, Hai-Tao; Li, Jilai; Schlangen, Maria; Schwarz, Helmut

    2014-12-28

    The thermal reactions of [Zn(OH)](+) with C3H8 have been studied by means of gas-phase experiments and computational investigation. Two types of C-H bond activation are observed in the experiment, and pertinent mechanistic features include inter alia: (i) the metal center of [Zn(OH)](+) serves as active site in the hydride transfer to generate [i-C3H7](+) as major product, (ii) generally, a high regioselectivity is accompanied by remarkable chemoselectivity: for example, the activation of a methyl C-H bond results mainly in the formation of water and [Zn(C3,H7)](+). According to computational work, this ionic product corresponds to [HZn(CH3CH=CH2)](+). Attack of the zinc center at a secondary C-H bond leads preferentially to hydride transfer, thus giving rise to the generation of [i-C3H7](+); (iii) upon oxidative dehydrogenation (ODH), liberation of CH3CH2=CH2 occurs to produce [HZn(H2O)](+). Both, ODH as well as H2O loss proceed through the same intermediate which is characterized by the fact that a methylene hydrogen atom from the substrate is transferred to the zinc and one hydrogen atom from the methyl group to the OH group of [Zn(OH)](+). The combined experimental/computational gas-phase study of C-H bond activation by zinc hydroxide provides mechanistic insight into related zinc-catalyzed large-scale processes and identifies the crucial role that the Lewis-acid character of zinc plays.

  8. Hydride mobility in trinuclear sulfido clusters with the core [Rh3(μ-H)(μ3-S)2]: molecular models for hydrogen migration on metal sulfide hydrotreating catalysts.

    Science.gov (United States)

    Jiménez, M Victoria; Lahoz, Fernando J; Lukešová, Lenka; Miranda, José R; Modrego, Francisco J; Nguyen, Duc H; Oro, Luis A; Pérez-Torrente, Jesús J

    2011-07-11

    The treatment of [{Rh(μ-SH){P(OPh)(3)}(2)}(2)] with [{M(μ-Cl)(diolef)}(2)] (diolef=diolefin) in the presence of NEt(3) affords the hydrido-sulfido clusters [Rh(3)(μ-H)(μ(3)-S)(2)(diolef){P(OPh)(3)}(4)] (diolef=1,5-cyclooctadiene (cod) for 1, 2,5-norbornadiene (nbd) for 2, and tetrafluorobenzo[5,6]bicyclo[2.2.2]octa-2,5,7-triene (tfb) for 3) and [Rh(2)Ir(μ-H)(μ(3)-S)(2)(cod){P(OPh)(3)}(4)] (4). Cluster 1 can be also obtained by treating [{Rh(μ-SH){P(OPh)(3)}(2)}(2)] with [{Rh(μ-OMe)(cod)}(2)], although the main product of the reaction with [{Ir(μ-OMe)(cod)}(2)] was [RhIr(2)(μ-H)(μ(3)-S)(2)(cod)(2){P(OPh)(3)}(2)] (5). The molecular structures of clusters 1 and 4 have been determined by X-ray diffraction methods. The deprotonation of a hydrosulfido ligand in [{Rh(μ-SH)(CO)(PPh(3))}(2)] by [M(acac)(diolef)] (acac=acetylacetonate) results in the formation of hydrido-sulfido clusters [Rh(3)(μ-H)(μ(3)-S)(2)(CO)(2) (diolef)(PPh(3))(2)] (diolef=cod for 6, nbd for 7) and [Rh(2)Ir(μ-H)(μ(3)-S)(2)(CO)(2)(cod)(PPh(3))(2)] (8). Clusters 1-3 and 5 exist in solution as two interconverting isomers with the bridging hydride ligand at different edges. Cluster 8 exists as three isomers that arise from the disposition of the PPh(3) ligands in the cluster (cis and trans) and the location of the hydride ligand. The dynamic behaviour of clusters with bulky triphenylphosphite ligands, which involves hydrogen migration from rhodium to sulfur with a switch from hydride to proton character, is significant to understand hydrogen diffusion on the surface of metal sulfide hydrotreating catalysts.

  9. Electrolytic hydriding of LaFe{sub 13-x}Si{sub x} alloys for energy efficient magnetic cooling

    Energy Technology Data Exchange (ETDEWEB)

    Lyubina, Julia; Hannemann, Ullrich; Ryan, Mary P. [Department of Materials, Imperial College London (United Kingdom); Cohen, Lesley F. [Department of Physics, Imperial College London (United Kingdom)

    2012-04-17

    An effective, low-temperature and readily available electrochemical method for tuning the operation temperature of LaFe{sub 13-x}Si{sub x}-type alloys is demonstrated. Electrolytically hydrided materials have the same high level magnetic properties as in high temperature gas-phase processed materials and offer an advantage of higher hydrogen absorption rate in the ferromagnetic state. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  10. Improvement of the efficiency of a space oxygen-hydrogen electrochemical generator

    Science.gov (United States)

    Glukhikh, I. N.; Shcherbakov, A. N.; Chelyaev, V. F.

    2014-12-01

    This paper describes the method used for cooling of an on-board oxygen-hydrogen electrochemical generator (ECG). Apart from electric power, such a unit produces water of reaction and heat; the latter is an additional load on the thermal control system of a space vehicle. This load is undesirable in long-duration space flights, when specific energy characteristics of on-board systems are the determining factors. It is suggested to partially compensate the energy consumption by the thermal control system of a space vehicle required for cooling of the electrochemical generator through evaporation of water of reaction from the generator into a vacuum (or through ice sublimation if the pressure in the ambient space is lower than that in the triple point of water.) Such method of cooling of an electrochemical generator improves specific energy parameters of an on-board electric power supply system, and, due to the presence of the negative feedback, it makes the operation of this system more stable. Estimates suggest that it is possible to compensate approximately one half of heat released from the generator through evaporation of its water of reaction at the electrical efficiency of the electrochemical generator equal to 60%. In this case, even minor increase in the efficiency of the generator would result in a considerable increase in the efficiency of the evaporative system intended for its cooling.

  11. Review of magnesium hydride-based materials: development and optimisation

    NARCIS (Netherlands)

    Crivello, J. -C.; Dam, B.; Denys, R. V.; Dornheim, M.; Grant, D. M.; Huot, J.; Jensen, T. R.; de Jongh, P.|info:eu-repo/dai/nl/186125372; Latroche, M.; Milanese, C.; Milcius, D.; Walker, G. S.; Webb, C. J.; Zlotea, C.; Yartys, V. A.

    Magnesium hydride has been studied extensively for applications as a hydrogen storage material owing to the favourable cost and high gravimetric and volumetric hydrogen densities. However, its high enthalpy of decomposition necessitates high working temperatures for hydrogen desorption while the

  12. A hydrogen peroxide electrochemical sensor based on silver nanoparticles decorated three-dimensional graphene

    Energy Technology Data Exchange (ETDEWEB)

    Zhan, Beibei; Liu, Changbing; Shi, Huaxia; Li, Chen; Wang, Lianhui [Key Laboratory for Organic Electronics and Information Displays (KLOEID), Nanjing University of Posts and Telecommunications, Nanjing 210023 (China); Huang, Wei, E-mail: iamxcdong@njtech.edu.cn, E-mail: iamwhuang@njtech.edu.cn; Dong, Xiaochen, E-mail: iamxcdong@njtech.edu.cn, E-mail: iamwhuang@njtech.edu.cn [Key Laboratory for Organic Electronics and Information Displays (KLOEID), Nanjing University of Posts and Telecommunications, Nanjing 210023 (China); Jiangsu-Singapore Joint Research Center for Organic/Bio-Electronics and Information Displays and Institute of Advanced Materials (IAM), Nanjing Tech University, 30 South Puzhu Road, Nanjing 211816 (China)

    2014-06-16

    A facile strategy has been developed to synthesize sliver nanoparticles (Ag NPs) decorated three-dimensional graphene (3DG) through hydrothermal process. The AgNPs-3DG composites are directly fabricated into a free standing sensing electrode for electrochemical detection of hydrogen peroxide (H{sub 2}O{sub 2}) in phosphate buffered solutions. Various techniques equipments including scanning electron microscopy, X-ray diffraction, and Raman spectroscopy are used to characterize the morphology and structure of the as-prepared composite. The electrochemical experiments reveal the AgNPs-3DG based biosensor exhibits fast amperometric sensing, low detection limitation, wide linear responding range, and perfect selectivity for non-enzyme H{sub 2}O{sub 2} detection, indicating the well synergistic effect of Ag NPs high electrocatalytic activity and 3DG high conductivity and large surface area.

  13. Electrochemical hydrogen production from thermochemical cycles using a proton exchange membrane electrolyzer

    Energy Technology Data Exchange (ETDEWEB)

    Sivasubramanian, PremKumar; Ramasamy, Ramaraja P.; Holland, Charles E.; Weidner, John W. [Center for Electrochemical Engineering, Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208 (United States); Freire, Francisco J. [Chlorine Recycle Consultants, Miami Beach, FL 33140 (United States)

    2007-03-15

    The electrochemical step in two thermochemical cycles for hydrogen production is reported. One cycle involves the electrochemical oxidation of sulfur dioxide to sulfuric acid (both water and SO{sub 2} are reactants). The other cycle involves the oxidation of anhydrous hydrogen bromide to bromine (anhydrous HBr is the only reactant). In both cycles, protons are reduced at the cathode to produce hydrogen. The novelty of this work is that both anode reactions are carried out in the gas phase of a proton exchange membrane (PEM) electrolyzer, which enhances the transport rate of reactants to the electrode surface. The HBr process achieved 2.0A/cm{sup 2} at 1.91 V. The SO{sub 2} process reached 0.4A/cm{sup 2}, but behind this current density the cell experienced mass transfer limitations of water across the membrane. However, the voltage required to achieve 0.4A/cm{sup 2} was 0.835 V, compared to 1.025 V for the HBr process at this current density. (author)

  14. Effect of hydrogen uptake on the electrochemical corrosion of N18 zircaloy under gamma irradiation

    Science.gov (United States)

    Xin, Z. Y.; Ling, Y. H.; Bai, Y. K.; Zeng, C.; Wang, S.; Clara, J. C.

    2016-12-01

    It has been well recognized that dramatic hydrogen uptake occurred in zircaloy after kinetic transition and porous structure was observed subsequently due to phase transformation of tetragonal to monoclinic zirconia. Therefore, how hydrogen solute and gamma-induced capillary-embedded hydrolysis influence the corrosion of zircaloy is an intriguing issue. In this work, the effect of hydrogen uptake and gamma irradiation on corrosion of N18 zircaloy was studied. Raman spectra and atomic force microscopy (AFM) were employed to analyse phase structure and surface morphology. Potentiodynamic polarization and electrochemical impedance spectroscopy were utilized to qualitatively evaluate the electron transfer properties of the oxide film formed on the zircaloy surface after corrosion. The depth profile and surface chemical states of involving elements were analysed by auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS), respectively. It was found that hydrogen permeation can decline the integrity and impedance semicircle of the oxide films, the more the hydrogen uptake is; the smaller magnitude of impedance will be. In view of the gamma irradiation, it is demonstrated that it promotes the corrosion rate slightly. Based on the irradiation theory and existing phenomena, the underlying mechanism is proposed.

  15. Solar-powered electrochemical oxidation of organic compounds coupled with the cathodic production of molecular hydrogen.

    Science.gov (United States)

    Park, Hyunwoong; Vecitis, Chad D; Hoffmann, Michael R

    2008-08-21

    A Bi-doped TiO2 anode, which is prepared from a mixed metal oxide coating deposited on Ti metal, is shown to be efficient for conventional water splitting. In this hybrid photovoltaic-electrochemical system, a photovoltaic (PV) cell is used to convert solar light to electricity, which is then used to oxidize a series of phenolic compounds at the semiconductor anode to carbon dioxide with the simultaneous production of molecular hydrogen from water/proton reduction at the stainless steel cathode. Degradation of phenol in the presence of a background NaCl electrolyte produces chlorinated phenols as reaction intermediates, which are subsequently oxidized completely to carbon dioxide and low-molecular weight carboxylic acids. The anodic current efficiency for the complete oxidation of phenolic compounds ranges from 3% to 17%, while the cathodic current efficiency and the energy efficiency for hydrogen gas generation range from 68% to 95% and 30% to 70%, respectively.

  16. Hydrogen Production From Crude Bio-oil and Biomass Char by Electrochemical Catalytic Reforming

    Institute of Scientific and Technical Information of China (English)

    Xing-long Li; Shen Ning; Li-xia Yuan; Quan-xin Li

    2011-01-01

    We reports an efficient approach for production of hydrogen from crude bio-oil and biomass char in the dual fixed-bed system by using the electrochemical catalytic reforming method.The maximal absolute hydrogen yield reached 110.9 g H2/kg dry biomass.The product gas was a mixed gas containing 72%H2,26%CO2,1.9%CO,and a trace amount of CH4.It was observed that adding biomass char (a by-product of pyrolysis of biomass) could remarkably increase the absolute H2 yield (about 20%-50%).The higher reforming temperature could enhance the steam reforming reaction of organic compounds in crude bio-oil and the reaction of CO and H2O.In addition,the CuZn-Al2O3 catalyst in the water-gas shift bed could also increase the absolute H2 yield via shifting CO to CO2.

  17. Hydrogen Production From Crude Bio-oil and Biomass Char by Electrochemical Catalytic Reforming

    Science.gov (United States)

    Li, Xing-long; Ning, Shen; Yuan, Li-xia; Li, Quan-xin

    2011-08-01

    We reports an efficient approach for production of hydrogen from crude bio-oil and biomass char in the dual fixed-bed system by using the electrochemical catalytic reforming method. The maximal absolute hydrogen yield reached 110.9 g H2/kg dry biomass. The product gas was a mixed gas containing 72%H2, 26%CO2, 1.9%CO, and a trace amount of CH4. It was observed that adding biomass char (a by-product of pyrolysis of biomass) could remarkably increase the absolute H2 yield (about 20%-50%). The higher reforming temperature could enhance the steam reforming reaction of organic compounds in crude bio-oil and the reaction of CO and H2O. In addition, the CuZn-Al2O3 catalyst in the water-gas shift bed could also increase the absolute H2 yield via shifting CO to CO2.

  18. Electrochemical behavior of hydrogen peroxide sensor based on new methylene blue as mediator

    Institute of Scientific and Technical Information of China (English)

    MA Jie; WU Hai; ZHU Yaqi

    2007-01-01

    A novel amperometric hydrogen peroxide sensor was proposed by co-immobilizing new methylene blue (NMB) and Horseradish peroxidase (HRP) on glassy carbon electrode through covalent binding.The electrochemical behavior of the sensor was studied extensively in 0.1 mol/L phosphate buffering solution (pH = 7.0).The experiments showed NMB could effectively transfer electrons between hydrogen peroxide and glassy carbon electrode.The electron transfer coefficient and apparent reaction rate constant were determined to be 0.861 and 1.27 s-1.The kinetic characteristics and responses of sensor on HzO2 were investigated.The Michaelis constant is 8.27 mol/L and the linear dependence of current on H2O2 is in the range of 2.5-100 μmol/L.At the same time,the effects of solution pH,buffer capacity,and temperature on the sensor were examined.

  19. Ca7Ge-type hydride Mg6VNaxHy (0 ≤ x ≤ 1): High pressure synthesis, synchrotron X-ray analysis and hydrogen storage properties

    Science.gov (United States)

    Takeichi, N.; Yan, J.; Yang, X.; Shida, K.; Tanaka, H.; Kiyobayashi, T.; Kuriyama, N.; Sakai, T.

    2012-07-01

    A powder mixture of MgH2:VH2:NaH = 6:1:n is treated under 8 GPa at 873 K using an eight-anvil apparatus in order to investigate the influence of NaH addition to Mg6VHy, a Ca7Ge-type FCC hydride. Synchrotron radiation X-ray diffraction (SR-XRD) of the obtained sample reveals that Na occupies the vacant 4b site in Mg6VHy to form Mg6VNaxHy (0 ≤ x ≤ 1) as the main product while retaining its Ca7Ge-type structure. The Rietveld analysis of the SR-XRD data suggests that the bond lengths between hydrogen and magnesium remain constant through the Na addition. All the samples reversibly desorb and absorb hydrogen at 620-630 and 590-600 K, respectively, under 0.5 MPa (H2). These temperatures are, respectively, about 70 and 120 K lower than those of MgH2. The hydrogen capacity of the main product phase, Mg6VNaxHy, is estimated to be 5-6 mass% from the pressure-composition isotherms (PCIs) by taking its content rate in the specimen into account. The reaction enthalpies calculated from the van't Hoff relation of the PCIs do not significantly differ from that of MgH2. The bond lengths and energies between hydrogen and magnesium are not affected by the perturbation by the NaH addition in the lattice in Mg6VNaxHy.

  20. Transition metal (Co, Ni) nanoparticles wrapped with carbon and their superior catalytic activities for the reversible hydrogen storage of magnesium hydride.

    Science.gov (United States)

    Huang, Xu; Xiao, Xuezhang; Zhang, Wei; Fan, Xiulin; Zhang, Liuting; Cheng, Changjun; Li, Shouquan; Ge, Hongwei; Wang, Qidong; Chen, Lixin

    2017-02-01

    Magnesium hydride (MgH2) exhibits long-term stability and has recently been developed as a safe alternative to store hydrogen in the solid state, due to its high capacity of 7.6 wt% H2 and low cost compared to other metal hydrides. However, the high activation energy and poor kinetics of MgH2 lead to inadequate hydrogen storage properties, resulting in low energy efficiency. Nano-catalysis is deemed to be the most effective strategy in improving the kinetics performance of hydrogen storage materials. In this work, robust and efficient architectures of carbon-wrapped transition metal (Co/C, Ni/C) nanoparticles (8-16 nm) were prepared and used as catalysts in the MgH2 system via ball milling to improve its de/rehydrogenation kinetics. Between the two kinds of nano-catalysts, the Ni/C nanoparticles exhibit a better catalytic efficiency. MgH2 doped with 6% Ni/C (MgH2-6%Ni/C) exhibits a peak dehydrogenation temperature of 275.7 °C, which is 142.7, 54.2 and 32.5 °C lower than that of commercial MgH2, milled MgH2 and MgH2 doped with 6% Co/C (MgH2-6%Co/C), respectively. MgH2 doped with 6% Ni/C can release about 6.1 wt% H2 at 250 °C. More importantly, the dehydrogenated MgH2-6%Ni/C is even able to uptake 5.0 wt% H2 at 100 °C within 20 s. Moreover, a cycling test of MgH2 doped with 8% Ni/C demonstrates its excellent hydrogen absorption/desorption stability with respect to both capacity (up to 6.5 wt%) and kinetics (within 8 min at 275 °C for dehydrogenation and within 10 s at 200 °C for rehydrogenation). Mechanistic research reveals that the in situ formed Mg2Ni and Mg2NiH4 nanoparticles can be regarded as advanced catalytically active species in the MgH2-Ni/C system. Meanwhile, the carbon attached around the surface of transition metal nanoparticles can successfully inhibit the aggregation of the catalysts and achieve the steadily, prompting de/rehydrogenation during the subsequent cycling process. The intrinsic catalytic effects and the uniform distributions of Mg2Ni

  1. Nuclear magnetic resonance studies of hydrogen motion in nanostructured Laves-phase hydrides ZrCr(2)H(x) and TaV(2)H(x).

    Science.gov (United States)

    Soloninin, A V; Buzlukov, A L; Skripov, A V; Aleksashin, B A; Tankeyev, A P; Yermakov, A Ye; Mushnikov, N V; Uimin, M A; Gaviko, V S

    2008-07-09

    In order to study the mobility of hydrogen in nanostructured Laves-phase hydrides, we have measured the proton nuclear magnetic resonance (NMR) spectra and the proton spin-lattice and spin-spin relaxation rates in two nanostructured systems prepared by ball milling: ZrCr(2)H(3) and TaV(2)H(1+δ). The proton NMR measurements have been performed at the resonance frequencies of 14, 23.8 and 90 MHz over the temperature ranges 11-424 K (for coarse-grained samples) and 11-384 K (for nanostructured samples). Hydrogen mobility in the ball-milled ZrCr(2)H(3) is found to decrease strongly with increasing milling time. The experimental data suggest that this effect is related to the growth of the fraction of highly distorted intergrain regions where H mobility is much lower than in the crystalline grains. For the nanostructured TaV(2)H(1+δ) system, the ball milling is found to lead to a slight decrease in the long-range H mobility and to a suppression of the fast localized H motion in the crystalline grains.

  2. Complex transition metal hydrides incorporating ionic hydrogen: thermal decomposition pathway of Na2Mg2FeH8 and Na2Mg2RuH8.

    Science.gov (United States)

    Humphries, Terry D; Matsuo, Motoaki; Li, Guanqiao; Orimo, Shin-Ichi

    2015-03-28

    Complex transition metal hydrides have potential technological application as hydrogen storage materials, smart windows and sensors. Recent exploration of these materials has revealed that the incorporation of anionic hydrogen into these systems expands the potential number of viable complexes, while varying the countercation allows for optimisation of their thermodynamic stability. In this study, the optimised synthesis of Na2Mg2TH8 (T = Fe, Ru) has been achieved and their thermal decomposition properties studied by ex situ Powder X-ray Diffraction, Gas Chromatography and Pressure-Composition Isotherm measurements. The temperature and pathway of decomposition of these isostructural compounds differs considerably, with Na2Mg2FeH8 proceeding via NaMgH3 in a three-step process, while Na2Mg2RuH8 decomposes via Mg2RuH4 in a two-step process. The first desorption maxima of Na2Mg2FeH8 occurs at ca. 400 °C, while Na2Mg2RuH8 has its first maxima at 420 °C. The enthalpy and entropy of desorption for Na2Mg2TH8 (T = Fe, Ru) has been established by PCI measurements, with the ΔHdes for Na2Mg2FeH8 being 94.5 kJ mol(-1) H2 and 125 kJ mol(-1) H2 for Na2Mg2RuH8.

  3. A direct electrochemical route from oxides to TiMn2 hydrogen storage alloy☆

    Institute of Scientific and Technical Information of China (English)

    Jing Zhu; Lei Dai; Yao Yu; Jilin Cao; Ling Wang

    2015-01-01

    This study is for investigating the direct electro-deoxidation of mixed TiO2–MnO2 powder to prepare TiMn2 al oy in molten calcium chloride. The influences of process parameters, such as sintering temperature, cell voltage, and electrolysis time, on the electrolysis process were examined to investigate the mechanism of al oy formation. The composition and morphology of the products were analyzed by XRD and SEM, respectively. The electrochemical property of TiMn2 al oy was investigated by cyclic voltammetry measurements. The results show that pure TiMn2 can be prepared by direct electrochemical reduction of mixed TiO2/MnO2 pellets at a voltage of 3.1 V in molten calcium chloride of 900 °C for 7 h. The electro-deoxidation proceeds from the reduction of manganese oxides to Mn, which is reduced by TiO2 or CaTiO3 to form TiMn2 al oy. The cyclic voltammetry measurements using pow-der microelectrode show that the prepared TiMn2 al oy has good electrochemical hydrogen storage property. © 2015 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. Al rights reserved.

  4. Recent advances in graphene-based nanomaterials for fabricating electrochemical hydrogen peroxide sensors.

    Science.gov (United States)

    Zhang, Ruizhong; Chen, Wei

    2017-03-15

    Due to the large specific surface area, extraordinary mechanical flexibility, chemical stability, and superior electrical and thermal conductivities, graphene (G)-based materials have recently opened up an exciting field in the science and technology of two-dimensional (2D) nanomaterials with continuously growing academic and technological impetus. In the past several years, graphene-based materials have been well designed, synthesized, and investigated for sensing applications. In this review, we discuss the synthesis and application of graphene-based 2D nanomaterials for the fabrication of hydrogen peroxide (H2O2) electrochemical sensors. In particular, graphene-based nanomaterials as immobilization matrix of heme proteins for the fabrication of enzymatic H2O2 electrochemical biosensors is first summarized. Then, the application of graphene-based electrocatalysts (metal-free, noble-metals and non-noble metals) in constructing non-enzymatic H2O2 electrochemical sensors is discussed in detail. We hope that this review is helpful to push forward the advancement of this academic issue (189 references).

  5. Copper complexes as catalyst precursors in the electrochemical hydrogen evolution reaction.

    Science.gov (United States)

    Kügler, Merle; Scholz, Julius; Kronz, Andreas; Siewert, Inke

    2016-04-28

    Herein, we report the synthesis and species distribution of copper(ii) complexes based on two different ligand scaffolds and the application of the two complexes in the electrochemical proton reduction catalysis. The ligands bind to one or two copper(II) ions and the pH-dependent mono/dinuclear equilibrium depends on the steric bulk of the ligands. The two water soluble copper(II) complexes were investigated for their activities in the electrochemical hydrogen evolution reaction (HER). In both complexes the copper(ii) ions have a N4-coordination environment composed of N-heterocycles, although in different coordination geometries (SPY-5 and TBPY-5). The solutions of the complexes were highly active catalysts in water at acidic pH but the complexes decompose under catalytic conditions. They act as precursors for highly active copper(0) and Cu2O deposits at the electrode surface, which are in turn the active catalysts. The absence or presence of the ligands has neither an influence on the catalytic activity of the solutions nor an influence on the activity of the deposit formed during controlled potential electrolysis. Finally, we can draw some conclusions on the stability of copper catalysts in the aqueous electrochemical HER.

  6. Performance of alternative oxide anodes for the electrochemical oxidation of hydrogen and methane in solid oxide fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Tu, H.; Apfel, H.; Stimming, U. [Department of Physics E19, Technical University of Munich, James-Franck-Strasse 1, D-85748 Garching (Germany)

    2006-07-15

    The electrode performances of the alternative oxides: La{sub 0.05}Ca{sub 0.95}Cr{sub 0.05}Ti{sub 0.95}O{sub 3-{delta}}-8YSZ and Ce{sub 0.8}TM{sub 0.2}O{sub 2-{delta}}(TM=Mn, Co) for the direct electrochemical oxidation of methane are investigated to assess their potential as anode materials for efficient methane conversion in a SOFC. The electrochemical oxidation of hydrogen was also studied, for comparison. The oxides are characterised electrochemically with impedance spectroscopy in the frequency range from 10 mHz to 1MHz, using a three-electrode geometry. They are compared to a standard Ni/8YSZ anode for the electrochemical oxidation of hydrogen. It is found that La{sub 0.05}Ca{sub 0.95}Cr{sub 0.05}Ti{sub 0.95}O{sub 3-{delta}}-8YSZ demonstrates a poor electrochemical activity in both hydrogen and methane. However, the electrochemical activity of Ce{sub 0.8}Mn{sub 0.2}O{sub 2-{delta}} is promising, but the electronic conductivity needs to be increased, e.g., by adding a conducting oxide, before it can be used as an anode material in a SOFC. (Abstract Copyright [2006], Wiley Periodicals, Inc.)

  7. Application of an electrochemical hydrogen meter for studying reactions in liquid sodium

    Science.gov (United States)

    Gnanasekaran, T.; Ganesan, V.; Periaswami, G.; Mathews, C. K.; Borgstedt, H. U.

    1990-05-01

    An electrochemical hydrogen meter based on a CaCl2- CaH2 solid electrolyte was used to study the reactions of rust (FeOOH) and hydrocarbon based oil with liquid sodium in the temperature range of 623 to 748 K. The results indicated that the reaction between FeOOH and sodium is slow at 623 K and fast at 723 K. The hydrogen concentration in sodium is increased due to the reaction. Similarly, the reaction between oil and sodium proceeds slowly at 623 K whereas above 673 K, it takes place rapidly. The gaseous products released during sodium-oil reactions were analysed by means of the gas Chromatographie technique. It was found that methane was the major gaseous product formed and its formation obeyed a parabolic rate law. The response of the meter for the liberation of hydrogen in both reactions was found to be fast, qualifying the meter for detecting the ingress of hydrogen bearing compounds into sodium.

  8. Electrochemical performances of hydrogen storage alloys treated using a new milling technique

    Institute of Scientific and Technical Information of China (English)

    LIU Kaiyu; ZHANG Ying; ZHANG Wei; HE Yuehui

    2008-01-01

    A new self-made additive of amidocyanogen-acetic salt was used in wet bail-grind technique (WBGT) for preparing hydrogen storage alloys, and the effect on the electrochemical performance of the alloy electrode was investigated in detail. It was found that the prepared electrode had perfect electrochemical performances, such as rapid activation, high capability, high-rate discharge (HRD) ability, and good stability. The first discharge capacitance at 0.2 C (throughout this study, n C rate means that the rated capacity of a hydrogen storage alloy (full capacity) is charged or discharged completely in 1/n h) reached 278mAh.g-1 and the discharge capacitance reached the maximum of 322mAh·g-1 only after two charge-discharge cycles. For the dry method, wet method, and WBGT, the high rate discharge (HRD) values (C5C/C0.2C ratio) were approximately 0.59, 0.76, and 0.83, respectively. The stable discharge capacity at 3 C increased from 275mAh·g-1 (dry method) to 295mAh·g-1 (WBGT).

  9. Phase Structure and Electrochemical Properties of RE-Mg Based Composite Hydrogen Storage Alloys

    Institute of Scientific and Technical Information of China (English)

    韩树民; 刘宝忠; 张忠; 朱惜林; 王晓铁; 荆天辅

    2004-01-01

    A new type of AB5-x%LaMg3(x=2, 3, 4, 5, 6, 7, 8)composite hydrogen storage alloys were prepared by sintering the powder mixtures of a commercial AB5 alloy and LaMg3 alloy. The phase structure and electrochemical characteristics of the composite hydrogen storage alloys were also studied. It is shown that AB5-x%LaMg3(x=2, 3, 4, 5, 6, 7, 8)composites have mult; phase structure. The matrix phase has CaCu5 structure, the second phase is LaNi3 phase. The maximum discharge capacity, discharge capacity at low temperature and HRD of AB5 alloy electrodes are greatly improved after the composite. The maximum discharge capacity of the composite electrodes increases from 325 mAh·g-1 for x=0 to 358 mAh·g-1 for x=5, and the HRD of the composites for x=5 at the current density of 1200 mA·g-130% of that of the alloy at 60 mA·g-1. The discharge capacity of AB5-x%LaMg3 composite alloy electrode at 233 K is up to 174 mAh·g-1. The improvement of the electrochemical characteristics of the composite electrodes seems to be related with formation of the LaNi3 second phase.

  10. Electrochemical investigation on the hydrogen permeation behavior of 7075-T6 Al alloy and its influence on stress corrosion cracking

    Science.gov (United States)

    Zheng, Chuan-bo; Yan, Bing-hao; Zhang, Ke; Yi, Guo

    2015-07-01

    The hydrogen permeation behavior and stress corrosion cracking (SCC) susceptibility of precharged 7075-T6 Al alloy were investigated in this paper. Devanthan-Stachurski (D-S) cell tests were used to measure the apparent hydrogen diffusivity and hydrogen permeation current density of specimens immersed in 3.5wt% NaCl solution. Electrochemical experiment results show that the SCC susceptibility is low during anodic polarization. Both corrosion pits and hydrogen-induced cracking are evident in scanning electron microscope images after the specimens have been charging for 24 h.

  11. Electrochemical cell

    Energy Technology Data Exchange (ETDEWEB)

    Heuts, J.J.F.G.; Willems, J.J.G.S.A.

    1987-10-13

    An electrochemical cell is described comprising a negative electrode. The electrochemically active material of which consists of an intermetallic compound forming a hydride with hydrogen, which compound has the CaCu/sub 5/-structure and the compositional formula AB/sub m/C/sub n/, where m+n is between 4.8 and 5.4, where n is between 0.05 and 0.6, in which A consists of Misch-metal or of one or more elements selected from the group consisting of Y, Ti, Hf, Zr, Ca, Th, La and the remaining rare earth metals, in which the total atomic quantities of the elements Y, Ti, Hf and Zr may not be more than 40% of A. B consists of two or more elements selected from the group formed by Ni, Co, Cu, Fe and Mn, where the maximum atomic quantity per gram atom of A is for Ni: 3.5, for Co:3.5, for Cu:3.5, for Fe:2.0 and for Mn:1.0, and C consists of one or more elements selected from the group formed by Al, Cr and Si in the indicated atomic quantities: Al:0.05-0.6, Cr:0.05-0.5 and Si:0.05-0.5, characterized in that the electrochemically active material additionally comprises one or more metals selected from the group formed by Pd, Pt, Ir and Rh, the atomic quantity per gram atom of A being from 0.001 to 0.5.

  12. Destabilization of magnesium hydride through interface engineering

    NARCIS (Netherlands)

    Mooij, L.P.A.

    2013-01-01

    The aim of this thesis is to study the thermodynamics of hydrogenation of nanoconfined magnesium within a thin film multilayer model system. Magnesium hydride is a potential material for hydrogen storage, which is a key component in a renewable energy system based on hydrogen. In bulk form,

  13. Destabilization of magnesium hydride through interface engineering

    NARCIS (Netherlands)

    Mooij, L.P.A.

    2013-01-01

    The aim of this thesis is to study the thermodynamics of hydrogenation of nanoconfined magnesium within a thin film multilayer model system. Magnesium hydride is a potential material for hydrogen storage, which is a key component in a renewable energy system based on hydrogen. In bulk form, magnesiu

  14. Destabilization of magnesium hydride through interface engineering

    NARCIS (Netherlands)

    Mooij, L.P.A.

    2013-01-01

    The aim of this thesis is to study the thermodynamics of hydrogenation of nanoconfined magnesium within a thin film multilayer model system. Magnesium hydride is a potential material for hydrogen storage, which is a key component in a renewable energy system based on hydrogen. In bulk form, magnesiu

  15. Structural and kinetic investigation of the hydride composite Ca(BH4)2 + MgH2 system doped with NbF5 for solid-state hydrogen storage.

    Science.gov (United States)

    Karimi, Fahim; Pranzas, P Klaus; Pistidda, Claudio; Puszkiel, Julián A; Milanese, Chiara; Vainio, Ulla; Paskevicius, Mark; Emmler, Thomas; Santoru, Antonio; Utke, Rapee; Tolkiehn, Martin; Minella, Christian B; Chaudhary, Anna-Lisa; Boerries, Stefan; Buckley, Craig E; Enzo, Stefano; Schreyer, Andreas; Klassen, Thomas; Dornheim, Martin

    2015-11-07

    Designing safe, compact and high capacity hydrogen storage systems is the key step towards introducing a pollutant free hydrogen technology into a broad field of applications. Due to the chemical bonds of hydrogen-metal atoms, metal hydrides provide high energy density in safe hydrogen storage media. Reactive hydride composites (RHCs) are a promising class of high capacity solid state hydrogen storage systems. Ca(BH4)2 + MgH2 with a hydrogen content of 8.4 wt% is one of the most promising members of the RHCs. However, its relatively high desorption temperature of ∼350 °C is a major drawback to meeting the requirements for practical application. In this work, by using NbF5 as an additive, the dehydrogenation temperature of this RHC was significantly decreased. To elucidate the role of NbF5 in enhancing the desorption properties of the Ca(BH4)2 + MgH2 (Ca-RHC), a comprehensive investigation was carried out via manometric measurements, mass spectrometry, Differential Scanning Calorimetry (DSC), in situ Synchrotron Radiation-Powder X-ray Diffraction (SR-PXD), X-ray Absorption Spectroscopy (XAS), Anomalous Small-Angle X-ray Scattering (ASAXS), Scanning and Transmission Electron Microscopy (SEM, TEM) and Nuclear Magnetic Resonance (NMR) techniques.

  16. Influence of experimental conditions upon the measurements of hydrogen diffusion in palladium by electrochemical permeation methods

    Energy Technology Data Exchange (ETDEWEB)

    Bucur, R.V.

    1985-01-01

    Influences of electrical parameters, surface roughness, controlled surface contamination and concentration of the electrolyte (NaOH- and H/sub 2/SO/sub 4/-solutions) upon the permeation rate of hydrogen through a palladium membrane (thickness: 5x10/sup -3/ cm) are reported. Diffusion measurements were carried out with an electrochemical permeation cell under transient conditions. The cathodic side of the membrane was subjected either to a constant hydrogen-concentration or hydrogen-flux, while the anodic side was permanently kept at negligibly low hydrogen-concentration. The diffusion coefficient was calculated from the charging and stripping current vs. time curves, by semi-log plots. Reliable and reproducible diffusion coefficient values were obtained both from the charging and stripping curves, under galvanostatic charging conditions. By contrast, reliable values were obtained only from the stripping curves, under potentiostatic charging conditions. Within the temperature range from 5 to 50/sup 0/C the following values have been calculated for hydrogen and deuterium: Dsub(H)/sup 0/=(2.48+-0.40)x10/sup -3/ cm/sup 2/s/sup -1/; Dsub(H)/sup 298/=3.8 . 10/sup -7/ cm/sup 2/s/sup -1/; Esub(H)=5210+-70 cal/mol; Dsub(D)/sup 0/=(1.67+-0.28)x10/sup -3/ cm/sup 2/s/sup -1/; Dsub(D)/sup 298/=4.8 . 10/sup -7/ cm/sup 2/s/sup -1/; Esub(D)=4830+-70 cal/mol. These values agree well with those obtained by non-electrolytical methods.

  17. Detecting proton exchange membrane fuel cell hydrogen leak using electrochemical impedance spectroscopy method

    Science.gov (United States)

    Mousa, Ghassan; Golnaraghi, Farid; DeVaal, Jake; Young, Alan

    2014-01-01

    When a proton exchange membrane (PEM) fuel cell runs short of hydrogen, it suffers from a reverse potential fault that, when driven by neighboring cells, can lead to anode catalyst degradation and holes in the membrane due to local heat generation. As a result, hydrogen leaks through the electrically-shorted membrane-electrode assembly (MEA) without being reacted, and a reduction in fuel cell voltage is noticed. Such voltage reduction can be detected by using electrochemical impedance spectroscopy (EIS). To fully understand the reverse potential fault, the effect of hydrogen crossover leakage in a commercial MEA is measured by EIS at different differential pressures between the anode and cathode. Then the signatures of these leaky cells were compared with the signatures of a no-leaky cells at different oxygen concentrations with the same current densities. The eventual intent of this early stage work is to develop an on-board diagnostics system that can be used to detect and possibly prevent cell reversal failures, and to permit understanding the status of crossover or transfer leaks versus time in operation.

  18. Contamination Effects on Improving the Hydrogenation/Dehydrogenation Kinetics of Binary Magnesium Hydride/Titanium Carbide Systems Prepared by Reactive Ball Milling.

    Science.gov (United States)

    El-Eskandarany, M Sherif; Shaban, Ehab

    2015-10-10

    Ultrafine MgH₂ nanocrystalline powders were prepared by reactive ball milling of elemental Mg powders after 200 h of high-energy ball milling under a hydrogen gas pressure of 50 bar. The as-prepared metal hydride powders were contaminated with 2.2 wt. % of FeCr-stainless steel that was introduced to the powders upon using stainless steel milling tools made of the same alloy. The as-synthesized MgH₂ was doped with previously prepared TiC nanopowders, which were contaminated with 2.4 wt. % FeCr (materials of the milling media), and then ball milled under hydrogen gas atmosphere for 50 h. The results related to the morphological examinations of the fabricated nanocomposite powders beyond the micro-and nano-levels showed excellent distributions of 5.2 wt. % TiC/4.6 wt. % FeCr dispersoids embedded into the fine host matrix of MgH₂ powders. The as-fabricated nanocomposite MgH₂/5.2 wt. % TiC/4.6 wt. % FeCr powders possessed superior hydrogenation/dehydrogenation characteristics, suggested by the low value of the activation energy (97.74 kJ/mol), and the short time required for achieving a complete absorption (6.6 min) and desorption (8.4 min) of 5.51 wt. % H₂ at a moderate temperature of 275 °C under a hydrogen gas pressure ranging from 100 mbar to 8 bar. van't Hoff approach was used to calculate the enthalpy (DH) and entropy (DS) of hydrogenation for MgH₂, which was found to be -72.74 kJ/mol and 112.79 J/mol H₂/K, respectively. Moreover, van't Hoff method was employed to calculate the DH and DS of dehydrogenation, which was found to be 76.76 kJ/mol and 119.15 J/mol H₂/K, respectively. This new nanocomposite system possessed excellent absorption/desorption cyclability of 696 complete cycles, achieved in a cyclic-life-time of 682 h.

  19. Contamination Effects on Improving the Hydrogenation/Dehydrogenation Kinetics of Binary Magnesium Hydride/Titanium Carbide Systems Prepared by Reactive Ball Milling

    Science.gov (United States)

    El-Eskandarany, M. Sherif; Shaban, Ehab

    2015-01-01

    Ultrafine MgH2 nanocrystalline powders were prepared by reactive ball milling of elemental Mg powders after 200 h of high-energy ball milling under a hydrogen gas pressure of 50 bar. The as-prepared metal hydride powders were contaminated with 2.2 wt. % of FeCr-stainless steel that was introduced to the powders upon using stainless steel milling tools made of the same alloy. The as-synthesized MgH2 was doped with previously prepared TiC nanopowders, which were contaminated with 2.4 wt. % FeCr (materials of the milling media), and then ball milled under hydrogen gas atmosphere for 50 h. The results related to the morphological examinations of the fabricated nanocomposite powders beyond the micro-and nano-levels showed excellent distributions of 5.2 wt. % TiC/4.6 wt. % FeCr dispersoids embedded into the fine host matrix of MgH2 powders. The as-fabricated nanocomposite MgH2/5.2 wt. % TiC/4.6 wt. % FeCr powders possessed superior hydrogenation/dehydrogenation characteristics, suggested by the low value of the activation energy (97.74 kJ/mol), and the short time required for achieving a complete absorption (6.6 min) and desorption (8.4 min) of 5.51 wt. % H2 at a moderate temperature of 275 °C under a hydrogen gas pressure ranging from 100 mbar to 8 bar. van’t Hoff approach was used to calculate the enthalpy (∆H) and entropy (∆S) of hydrogenation for MgH2, which was found to be −72.74 kJ/mol and 112.79 J/mol H2/K, respectively. Moreover, van’t Hoff method was employed to calculate the ΔH and ΔS of dehydrogenation, which was found to be 76.76 kJ/mol and 119.15 J/mol H2/K, respectively. This new nanocomposite system possessed excellent absorption/desorption cyclability of 696 complete cycles, achieved in a cyclic-life-time of 682 h. PMID:28793606

  20. Contamination Effects on Improving the Hydrogenation/Dehydrogenation Kinetics of Binary Magnesium Hydride/Titanium Carbide Systems Prepared by Reactive Ball Milling

    Directory of Open Access Journals (Sweden)

    M. Sherif El-Eskandarany

    2015-10-01

    Full Text Available Ultrafine MgH2 nanocrystalline powders were prepared by reactive ball milling of elemental Mg powders after 200 h of high-energy ball milling under a hydrogen gas pressure of 50 bar. The as-prepared metal hydride powders were contaminated with 2.2 wt. % of FeCr-stainless steel that was introduced to the powders upon using stainless steel milling tools made of the same alloy. The as-synthesized MgH2 was doped with previously prepared TiC nanopowders, which were contaminated with 2.4 wt. % FeCr (materials of the milling media, and then ball milled under hydrogen gas atmosphere for 50 h. The results related to the morphological examinations of the fabricated nanocomposite powders beyond the micro-and nano-levels showed excellent distributions of 5.2 wt. % TiC/4.6 wt. % FeCr dispersoids embedded into the fine host matrix of MgH2 powders. The as-fabricated nanocomposite MgH2/5.2 wt. % TiC/4.6 wt. % FeCr powders possessed superior hydrogenation/dehydrogenation characteristics, suggested by the low value of the activation energy (97.74 kJ/mol, and the short time required for achieving a complete absorption (6.6 min and desorption (8.4 min of 5.51 wt. % H2 at a moderate temperature of 275 C under a hydrogen gas pressure ranging from 100 mbar to 8 bar. van’t Hoff approach was used to calculate the enthalpy (DH and entropy (DS of hydrogenation for MgH2, which was found to be 72.74 kJ/mol and 112.79 J/mol H2/K, respectively. Moreover, van’t Hoff method was employed to calculate the DH and DS of dehydrogenation, which was found to be 76.76 kJ/mol and 119.15 J/mol H2/K, respectively. This new nanocomposite system possessed excellent absorption/desorption cyclability of 696 complete cycles, achieved in a cyclic-life-time of 682 h.

  1. Thermodynamic Hydricity of Transition Metal Hydrides.

    Science.gov (United States)

    Wiedner, Eric S; Chambers, Matthew B; Pitman, Catherine L; Bullock, R Morris; Miller, Alexander J M; Appel, Aaron M

    2016-08-10

    Transition metal hydrides play a critical role in stoichiometric and catalytic transformations. Knowledge of free energies for cleaving metal hydride bonds enables the prediction of chemical reactivity, such as for the bond-forming and bond-breaking events that occur in a catalytic reaction. Thermodynamic hydricity is the free energy required to cleave an M-H bond to generate a hydride ion (H(-)). Three primary methods have been developed for hydricity determination: the hydride transfer method establishes hydride transfer equilibrium with a hydride donor/acceptor pair of known hydricity, the H2 heterolysis method involves measuring the equilibrium of heterolytic cleavage of H2 in the presence of a base, and the potential-pKa method considers stepwise transfer of a proton and two electrons to give a net hydride transfer. Using these methods, over 100 thermodynamic hydricity values for transition metal hydrides have been determined in acetonitrile or water. In acetonitrile, the hydricity of metal hydrides spans a range of more than 50 kcal/mol. Methods for using hydricity values to predict chemical reactivity are also discussed, including organic transformations, the reduction of CO2, and the production and oxidation of hydrogen.

  2. Electrochemical Peltier heat for the adsorption and desorption of hydrogen on a platinized platinum electrode in sulfuric acid solution

    Energy Technology Data Exchange (ETDEWEB)

    Shibata, Shigeo; Sumino, M.P.

    1985-01-01

    The electrochemical Peltier heat for the surface hydrogen process at a pt-Pt electrode in 0.5 M H/sub 2/SO/sub 4/ solution was measured under controlled-potential and controlled-current polarizations using a thick film thermistor electrode. The observed Peltier heat is related to the entropy change of the reversible hydrogen process. In the hydrogen potential region, four stepwise heat changes were observed. These heat changes correspond to the adsorptions of four hydrogen species with different adsorption strengths, respectively. The most weakly bonded hydrogen species Hsub(w) exhibited the largest Peltier heat. This is possibly due to the strong interaction of Hsub(w) with the water molecules of the solvent. Peltier effects for the other three adsorption species are explained in terms of the nature of the adsorption sites where hydrogen atoms adsorb with a different mobility or vibrational movement, resulting in a different entropy. (orig.).

  3. Metal hydride air conditioner

    Institute of Scientific and Technical Information of China (English)

    YANG; Ke; DU; Ping; LU; Man-qi

    2005-01-01

    The relationship among the hydrogen storage properties, cycling characteristics and thermal parameters of the metal hydride air conditioning systems was investigated. Based on a new alloy selection model, three pairs of hydrogen storage alloys, LaNi4.4 Mn0.26 Al0.34 / La0.6 Nd0.4 Ni4.8 Mn0.2 Cu0. 1, LaNi4.61Mn0. 26 Al0.13/La0.6 Nd0.4 Ni4.8 Mn0.2 Cu0. 1 and LaNi4.61 Mn0.26 Al0.13/La0.6 Y0.4 Ni4.8 Mn0. 2, were selected as the working materials for the metal hydride air conditioning system. Studies on the factors affecting the COP of the system showed that higher COP and available hydrogen content need the proper operating temperature and cycling time,large hydrogen storage capacity, flat plateau and small hysterisis of hydrogen alloys, proper original input hydrogen content and mass ratio of the pair of alloys. It also needs small conditioning system was established by using LaNi4.61 Mn0.26 Al0. 13/La0.6 Y0.4 Ni4.8 Mn0.2 alloys as the working materials, which showed that under the operating temperature of 180℃/40℃, a low temperature of 13℃ was reached, with COP =0.38 and Wnet =0.09 kW/kg.

  4. Studies in hydride generation atomic fluorescence determination of selenium and tellurium. Part 1 — self interference effect in hydrogen telluride generation and the effect of KI

    Science.gov (United States)

    D'Ulivo, A.; Marcucci, K.; Bramanti, E.; Lampugnani, L.; Zamboni, R.

    2000-08-01

    The effects of tetrahydroborate (0.02-1%) and iodide (0-3 M) were investigated in determination of tellurium and selenium by hydride generation atomic fluorescence spectrometry. The effect of tetrahydroborate and iodide concentration were tested on the shape of calibration curves in concentration range of 1-1000 ng ml -1 analyte. Reductant deficiency resulted in a moderate sensitivity depression for tellurium but dramatically reduced the useful dynamic range down to 50 ng ml -1. On the contrary, selenium calibration curves retained a linear character even under conditions generating strong sensitivity depression. Curvature and rollover of tellurium calibration curves has been addressed to a self-interference effect caused by the formation of finely dispersed elemental tellurium. Iodide ions were found to have beneficial or no negative effects in the hydrogen telluride generation. Addition of iodide on-line to the sample has been proved effective in the control of the self-interference effect and allows to work in mild reaction conditions. Moreover, it allows a good control of Cu(II) interference and eliminates Ni(II) and Co(II) interferences. The method has been successfully applied to determination of tellurium in copper and lead ores certified reference materials.

  5. An electrochemical investigation of mechanical alloying of MgNi-based hydrogen storage alloys

    Science.gov (United States)

    Jiang, Jian-Jun; Gasik, Michael

    The electrochemical properties of amorphous MgNi-based hydrogen storage alloys synthesized by mechanical alloying (MA) were evaluated. The results show that these amorphous Mg 50Ni 50 alloys exhibit a higher discharge capacity and relatively good rate capacity at a suitable grinding time while their cycle life is very poor. In order to improve the cycle life, the surface of the amorphous Mg 50Ni 50 alloy was coated with Ti, Al and Zr in Spex 8000 mill/mixer and the coating effects were further investigated. Based on experimental results, two kinds of MgNi-based amorphous alloys are designed by substituting part of Mg in MgNi-based alloys by suitable elements. These alloys are then composed of four components. Thus, the cycle life of electrodes consisting of these quaternary amorphous alloys is greatly improved.

  6. Scalable and efficient separation of hydrogen isotopes using graphene-based electrochemical pumping

    Science.gov (United States)

    Lozada-Hidalgo, M.; Zhang, S.; Hu, S.; Esfandiar, A.; Grigorieva, I. V.; Geim, A. K.

    2017-05-01

    Thousands of tons of isotopic mixtures are processed annually for heavy-water production and tritium decontamination. The existing technologies remain extremely energy intensive and require large capital investments. New approaches are needed to reduce the industry's footprint. Recently, micrometre-size crystals of graphene are shown to act as efficient sieves for hydrogen isotopes pumped through graphene electrochemically. Here we report a fully-scalable approach, using graphene obtained by chemical vapour deposition, which allows a proton-deuteron separation factor of around 8, despite cracks and imperfections. The energy consumption is projected to be orders of magnitude smaller with respect to existing technologies. A membrane based on 30 m2 of graphene, a readily accessible amount, could provide a heavy-water output comparable to that of modern plants. Even higher efficiency is expected for tritium separation. With no fundamental obstacles for scaling up, the technology's simplicity, efficiency and green credentials call for consideration by the nuclear and related industries.

  7. Novel Electrochemical Synthesis of Polypyrrole/Ag Nanocomposite and Its Electrocatalytic Performance towards Hydrogen Peroxide Reduction

    Directory of Open Access Journals (Sweden)

    Ruma Gupta

    2015-01-01

    Full Text Available A simple electrochemical method of synthesis of polypyrrole/silver (PPy/Ag nanocomposite is presented. The method is based on potentiodynamic polymerization of pyrrole followed by electrodeposition of silver employing a single potentiostatic pulse. The synthesized PPy film has embedded Ag nanocubes. The morphology and structure of the resulting nanocomposite were characterized by field emission scanning electron microscopy and X-ray diffraction. Electron paramagnetic resonance studies showed that silver nanoparticle deposition on polypyrrole leads to an increase in carrier density, indicative of enhanced conductivity of the resulting composite. Electrocatalytic performance of the prepared composite was examined for reduction of hydrogen peroxide and was compared with corresponding PPy film and bare glassy carbon electrode.

  8. Electrochemical studies of hydrogen chloride gas in several room temperature ionic liquids: mechanism and sensing.

    Science.gov (United States)

    Murugappan, Krishnan; Silvester, Debbie S

    2016-01-28

    The electrochemical behaviour of highly toxic hydrogen chloride (HCl) gas has been investigated in six room temperature ionic liquids (RTILs) containing imidazolium/pyrrolidinium cations and range of anions on a Pt microelectrode using cyclic voltammetry (CV). HCl gas exists in a dissociated form of H(+) and [HCl2](-) in RTILs. A peak corresponding to the oxidation of [HCl2](-) was observed, resulting in the formation of Cl2 and H(+). These species were reversibly reduced to H2 and Cl(-), respectively, on the cathodic CV scan. The H(+) reduction peak is also present initially when scanned only in the cathodic direction. In the RTILs with a tetrafluoroborate or hexafluorophosphate anion, CVs indicated a reaction of the RTIL with the analyte/electrogenerated products, suggesting that these RTILs might not be suitable solvents for the detection of HCl gas. This was supported by NMR spectroscopy experiments, which showed that the hexafluorophosphate ionic liquid underwent structural changes after HCl gas electrochemical experiments. The analytical utility was then studied in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][NTf2]) by utilising both peaks (oxidation of [HCl2](-) and reduction of protons) and linear calibration graphs for current vs. concentration for the two processes were obtained. The reactive behaviour of some ionic liquids clearly shows that the choice of the ionic liquid is very important if employing RTILs as solvents for HCl gas detection.

  9. Production of bioelectricity, bio-hydrogen, high value chemicals and bioinspired nanomaterials by electrochemically active biofilms.

    Science.gov (United States)

    Kalathil, Shafeer; Khan, Mohammad Mansoob; Lee, Jintae; Cho, Moo Hwan

    2013-11-01

    Microorganisms naturally form biofilms on solid surfaces for their mutual benefits including protection from environmental stresses caused by contaminants, nutritional depletion or imbalances. The biofilms are normally dangerous to human health due to their inherited robustness. On the other hand, a recent study suggested that electrochemically active biofilms (EABs) generated by electrically active microorganisms have properties that can be used to catalyze or control the electrochemical reactions in a range of fields, such as bioenergy production, bioremediation, chemical/biological synthesis, bio-corrosion mitigation and biosensor development. EABs have attracted considerable attraction in bioelectrochemical systems (BESs), such as microbial fuel cells and microbial electrolysis cells, where they act as living bioanode or biocathode catalysts. Recently, it was reported that EABs can be used to synthesize metal nanoparticles and metal nanocomposites. The EAB-mediated synthesis of metal and metal-semiconductor nanocomposites is expected to provide a new avenue for the greener synthesis of nanomaterials with high efficiency and speed than other synthetic methods. This review covers the general introduction of EABs, as well as the applications of EABs in BESs, and the production of bio-hydrogen, high value chemicals and bio-inspired nanomaterials.

  10. Reduced hydrogen sulfide from crude oil using metal nanoparticles produced by electrochemical deposition

    Directory of Open Access Journals (Sweden)

    Sahar Safarkhani

    2016-06-01

    Full Text Available Hydrogen sulfide is one of the most dangerous contaminants in crude oil and natural gas that must be removed before transport and refining. It has multiple effects on the environment and the industry is bad that these effects include acid rain, cancer, corrosion of pipelines, poison catalytic converters in car exhaust. In this study, to eliminate H2S crude oil Nano emulsion used ionic liquid. Ionic liquids also with metal nanoparticles (MNPs have been modified. Improve and reform the electrochemical deposition of metal salts is done. Ionic liquid 1 - Hydro One Atyl2- methyl imidazolium de cyanimide [HEMIM] [DCA] is inherently hydrophilic as Scavenger H2S was added to the crude oil. Two types of metal salts of Fe (acac 3 and Cu (SO4 electrochemical deposition method for producing metal nanoparticles in the ionic liquid [HEMIM] [DCA] was used. Suitable concentrations of ionic liquids for the complete removal of hydrogen sulfide from crude oil were determined by two methods: static and dynamic methods. Dynamic method to determine the required dose used to remove H2S. Static method using response surface and through statistical experimental design for modeling and assessment CCD H2S was removed parameters. Three factors, namely Scavengerdose, contact time and the reaction temperature were studied. The interaction between these factors on the concentration of H2S in the crude oil was studied. 3 important statistical models for ionic liquids and ionic liquid containing two types of metal nanoparticles were developed. This model has an index of noncompliance was not important. The ionic liquid modified with nanoparticles , activity and H2S removal capacity is significantly increased , to the extent that the effect of one or two major factors were considered too small or unimportant . Copper metal nanoparticles showed better performance for the removal of H2S to iron

  11. Properties of nanoscale metal hydrides.

    Science.gov (United States)

    Fichtner, Maximilian

    2009-05-20

    Nanoscale hydride particles may exhibit chemical stabilities which differ from those of a macroscopic system. The stabilities are mainly influenced by a surface energy term which contains size-dependent values of the surface tension, the molar volume and an additional term which takes into account a potential reduction of the excess surface energy. Thus, the equilibrium of a nanoparticular hydride system may be shifted to the hydrogenated or to the dehydrogenated side, depending on the size and on the prefix of the surface energy term of the hydrogenated and dehydrogenated material. Additional complexity appears when solid-state reactions of complex hydrides are considered and phase segregation has to be taken into account. In such a case the reversibility of complex hydrides may be reduced if the nanoparticles are free standing on a surface. However, it may be enhanced if the system is enclosed by a nanoscale void which prevents the reaction partners on the dehydrogenated side from diffusing away from each other. Moreover, the generally enhanced diffusivity in nanocrystalline systems may lower the kinetic barriers for the material's transformation and, thus, facilitate hydrogen absorption and desorption.

  12. Iron Group Hydrides in Noyori Bifunctional Catalysis.

    Science.gov (United States)

    Morris, Robert H

    2016-12-01

    This is an overview of the hydride-containing catalysts prepared in the Morris group for the efficient hydrogenation of simple ketones, imines, nitriles and esters and the asymmetric hydrogenation and transfer hydrogenation of prochiral ketones and imines. The work was inspired by and makes use of Noyori metal-ligand bifunctional concepts involving the hydride-ruthenium amine-hydrogen HRuNH design. It describes the synthesis and some catalytic properties of hydridochloro, dihydride and amide complexes of ruthenium and in one case, osmium, with monodentate, bidentate and tetradentate phosphorus and nitrogen donor ligands. The iron hydride that has been identified in a very effective asymmetric transfer hydrogenation process is also mentioned. The link between the HMNH structure and the sense of enantioinduction is demonstrated by use of simple transition state models.

  13. Influence of hydrogen electrosorption on surface oxidation of Pd and Pd-noble metal alloys

    Energy Technology Data Exchange (ETDEWEB)

    Lukaszewski, M.; Kedra, T.; Czerwinski, A. [Warsaw University, Department of Chemistry, Laboratory of Electrochemical Power Sources, Pasteura 1, 02-093 Warsaw (Poland)

    2009-05-15

    Electrochemical oxidation of freshly deposited Pd and its alloys with other noble metals (Au, Pt, Rh) was compared with the behavior of samples subjected to prior hydrogen absorption/desorption procedure. It was found that surface oxidation of hydrogen-treated Pd and Pd-Pt-Au deposits starts at lower potentials than on non-hydrided electrodes and is accompanied by a negative shift of surface oxide reduction peak. Pd and its alloys with Au, Pt and Rh after hydrogen treatment are also more resistant to electrochemical dissolution than freshly deposited samples. (author)

  14. Physics of hydride fueled PWR

    Science.gov (United States)

    Ganda, Francesco

    The first part of the work presents the neutronic results of a detailed and comprehensive study of the feasibility of using hydride fuel in pressurized water reactors (PWR). The primary hydride fuel examined is U-ZrH1.6 having 45w/o uranium: two acceptable design approaches were identified: (1) use of erbium as a burnable poison; (2) replacement of a fraction of the ZrH1.6 by thorium hydride along with addition of some IFBA. The replacement of 25 v/o of ZrH 1.6 by ThH2 along with use of IFBA was identified as the preferred design approach as it gives a slight cycle length gain whereas use of erbium burnable poison results in a cycle length penalty. The feasibility of a single recycling plutonium in PWR in the form of U-PuH2-ZrH1.6 has also been assessed. This fuel was found superior to MOX in terms of the TRU fractional transmutation---53% for U-PuH2-ZrH1.6 versus 29% for MOX---and proliferation resistance. A thorough investigation of physics characteristics of hydride fuels has been performed to understand the reasons of the trends in the reactivity coefficients. The second part of this work assessed the feasibility of multi-recycling plutonium in PWR using hydride fuel. It was found that the fertile-free hydride fuel PuH2-ZrH1.6, enables multi-recycling of Pu in PWR an unlimited number of times. This unique feature of hydride fuels is due to the incorporation of a significant fraction of the hydrogen moderator in the fuel, thereby mitigating the effect of spectrum hardening due to coolant voiding accidents. An equivalent oxide fuel PuO2-ZrO2 was investigated as well and found to enable up to 10 recycles. The feasibility of recycling Pu and all the TRU using hydride fuels were investigated as well. It was found that hydride fuels allow recycling of Pu+Np at least 6 times. If it was desired to recycle all the TRU in PWR using hydrides, the number of possible recycles is limited to 3; the limit is imposed by positive large void reactivity feedback.

  15. Estimation of the composition parameter of electrochemically colored amorphous hydrogen tungsten oxide films

    Science.gov (United States)

    Kaneko, Hiroko; Miyake, Kiyoshi

    1989-07-01

    The electrical and optical steady state observed in electrochemical coloration has been studied using asymmetric cells consisting of evaporated amorphous tungsten oxide films with 350-6000 Å thickness. The counter electrode used is indium wire, steel wire, or antimony-tin oxide film, and the electrolyte is a 1-N H2SO4 aqueous solution containing 10 vol % glycerol. The current and optical transmittance of the cells decrease with increasing time during coloration, and simultaneously reach a steady state. The optical density (λ=0.5 μm) in the steady state is proportional to the thickness of the tungsten oxide film, and the absorption coefficient at λ=0.5 μm of the colored oxide film in the state is approximately 9.0×104 cm-1. The effective charges which contribute to the coloration of films calculated from the charge injected until the electro-optical steady state were found to be 1.03-1.20×103 C/cm3. Assuming that the evaporated tungsten oxide films used have a distorted ReO3 structure, and that a hydrogen tungsten bronze HxWO3 is formed by coloration, the composition parameter x calculated from the average value of the effective charge, is 0.36, which is comparable with that of hydrogen tungsten bronze H0.33WO3 obtained for the colored crystalline WO3 films.

  16. Effect of thermal treatment on the electrochemical hydrogen absorption of ZrCrNi alloy

    Energy Technology Data Exchange (ETDEWEB)

    Ruiz, F.C.; Peretti, H.A.; Corso, H.L [Centro Atomico Bariloche, Comision Nacional de Energia Atomica, Bariloche (Argentina); Visintin, A.; Real, S.G.; Castro, E.B.; Triaca, W.E. [Univ. Nacional de La Plata, La Plata (Argentina). Inst. de Investigaciones Fisiquimicas Teoricas y Aplicadas

    2006-07-01

    The catalytic effect of the secondary phases contained in a ZrCrNi alloy on its electrochemical properties was investigated. The purpose of the study was to improve the performance of Ni-MH battery electrodes. Four samples of the alloy were given annealing treatments at T=1250 K at variable times to obtain different concentrations of the secondary phases. Phase structure, morphology, and composition were studied using X-ray diffraction; radiation; scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) microanalysis. Results of the study were compatible with the presence of a major AB{sub 2} phase of C15 structure and the co-existence of C14 and C15 structures in both the as-melted and annealed alloys. The effect of the annealing in the ZrCrNi alloy resulted in a remarkable reduction of the discharge capacity and activation that was attributed to the dissolution of the secondary phases. The major catalytic effect was associated with the Zr{sub 8}Ni{sub 21} phase, by increasing the discharge capacity and favouring the activation. It was concluded that the presence of the catalytic phase in the alloy increased the hydrogen absorption capacity of the electrode due to an enhancement of the hydrogen production by electrolysis on the metal/catalytic phase and electrolyte interface. 6 refs., 1 fig.

  17. Effect of Stoichiometry on Properties of Rare-Earth-Based Hydrogen Storage Alloy for Nickel-Metal Hydride Secondary Battery

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Effect of stoichiometry on microstructures, electrochemical properties and PCT characteristics of the alloys Ml(Ni0.71Co0.15-Al0.06Mn0.08)x (Ml=Lanthanum-rich Michmetal, x=4.6~5.2) have been investigated. The lattice constants a, c, and cellvolumes of non-stoichiometric alloys are bigger than those of the stoichiometric alloy. With the increasing stoichiometry x,the value of a decreases, and the value of c and cell volume increases except for those of the stoichiometric alloy; the plateaupressure of PCT curve, discharge capacity and cycling stability all increase. The alloy with x=5.2 shows the highest dischargecapacity and the best cycling stability among the studied alloys.

  18. Electrochemical Synthesis of Polypyrrole, Reduced Graphene Oxide, and Gold Nanoparticles Composite and Its Application to Hydrogen Peroxide Biosensor

    Directory of Open Access Journals (Sweden)

    Baoyan Wu

    2016-11-01

    Full Text Available Here we report a facile eco-friendly one-step electrochemical approach for the fabrication of a polypyrrole (PPy, reduced graphene oxide (RGO, and gold nanoparticles (nanoAu biocomposite on a glassy carbon electrode (GCE. The electrochemical behaviors of PPy–RGO–nanoAu and its application to electrochemical detection of hydrogen peroxide were investigated by cyclic voltammetry. Graphene oxide and pyrrole monomer were first mixed and casted on the surface of a cleaned GCE. After an electrochemical processing consisting of the electrooxidation of pyrrole monomer and simultaneous electroreduction of graphene oxide and auric ions (Au3+ in aqueous solution, a PPy–RGO–nanoAu biocomposite was synthesized on GCE. Each component of PPy–RGO–nanoAu is electroactive without non-electroactive substance. The obtained PPy–RGO–nanoAu/GCE exhibited high electrocatalytic activity toward hydrogen peroxide, which allows the detection of hydrogen peroxide at a negative potential of about −0.62 V vs. SCE. The amperometric responses of the biosensor displayed a sensitivity of 40 µA/mM, a linear range of 32 µM–2 mM, and a detection limit of 2.7 µM (signal-to-noise ratio = 3 with good stability and acceptable reproducibility and selectivity. The results clearly demonstrate the potential of the as-prepared PPy–RGO–nanoAu biocomposite for use as a highly electroactive matrix for an amperometric biosensor.

  19. Photochemistry of Transition Metal Hydrides.

    Science.gov (United States)

    Perutz, Robin N; Procacci, Barbara

    2016-08-10

    Photochemical reactivity associated with metal-hydrogen bonds is widespread among metal hydride complexes and has played a critical part in opening up C-H bond activation. It has been exploited to design different types of photocatalytic reactions and to obtain NMR spectra of dilute solutions with a single pulse of an NMR spectrometer. Because photolysis can be performed on fast time scales and at low temperature, metal-hydride photochemistry has enabled determination of the molecular structure and rates of reaction of highly reactive intermediates. We identify five characteristic photoprocesses of metal monohydride complexes associated with the M-H bond, of which the most widespread are M-H homolysis and R-H reductive elimination. For metal dihydride complexes, the dominant photoprocess is reductive elimination of H2. Dihydrogen complexes typically lose H2 photochemically. The majority of photochemical reactions are likely to be dissociative, but hydride complexes may be designed with equilibrated excited states that undergo different photochemical reactions, including proton transfer or hydride transfer. The photochemical mechanisms of a few reactions have been analyzed by computational methods, including quantum dynamics. A section on specialist methods (time-resolved spectroscopy, matrix isolation, NMR, and computational methods) and a survey of transition metal hydride photochemistry organized by transition metal group complete the Review.

  20. Boron Hydrides

    Science.gov (United States)

    1946-07-01

    of direct interest could be b.P.4d. ’Thus the discovory of a now proj.ect, since silano is probably too readily infla-zmablo for practical usc’ this...devoted, ho specc4fie compounds vhitih a’-ould be tocdte at prescnt arc: nron tiy * silano , %;2.SiFi3 , diothyl sila~no, (C2 115 )2 Si112, mono r.-rop; ! (n...Bcrohydrido or Li h.... I .A-4A- The prepuation of Silano med of Stannane by the interaction or lithium aluzirun hydride v-ithl silicon tetrtchiorido and

  1. Erbium hydride decomposition kinetics.

    Energy Technology Data Exchange (ETDEWEB)

    Ferrizz, Robert Matthew

    2006-11-01

    Thermal desorption spectroscopy (TDS) is used to study the decomposition kinetics of erbium hydride thin films. The TDS results presented in this report are analyzed quantitatively using Redhead's method to yield kinetic parameters (E{sub A} {approx} 54.2 kcal/mol), which are then utilized to predict hydrogen outgassing in vacuum for a variety of thermal treatments. Interestingly, it was found that the activation energy for desorption can vary by more than 7 kcal/mol (0.30 eV) for seemingly similar samples. In addition, small amounts of less-stable hydrogen were observed for all erbium dihydride films. A detailed explanation of several approaches for analyzing thermal desorption spectra to obtain kinetic information is included as an appendix.

  2. Sealed aerospace metal-hydride batteries

    Science.gov (United States)

    Coates, Dwaine

    1992-01-01

    Nickel metal hydride and silver metal hydride batteries are being developed for aerospace applications. There is a growing market for smaller, lower cost satellites which require higher energy density power sources than aerospace nickel-cadmium at a lower cost than space nickel-hydrogen. These include small LEO satellites, tactical military satellites and satellite constellation programs such as Iridium and Brilliant Pebbles. Small satellites typically do not have the spacecraft volume or the budget required for nickel-hydrogen batteries. NiCd's do not have adequate energy density as well as other problems such as overcharge capability and memory effort. Metal hydride batteries provide the ideal solution for these applications. Metal hydride batteries offer a number of advantages over other aerospace battery systems.

  3. A critical overview of definitions and determination techniques of the internal resistance using lithium-ion, lead-acid, nickel metal-hydride batteries and electrochemical double-layer capacitors as examples

    Science.gov (United States)

    Piłatowicz, Grzegorz; Marongiu, Andrea; Drillkens, Julia; Sinhuber, Philipp; Sauer, Dirk Uwe

    2015-11-01

    The internal resistance (Ri) is one of the key parameters that determine the current state of electrochemical storage systems (ESS). It is crucial for estimating cranking capability in conventional cars, available power in modern hybrid and electric vehicles and for determining commonly used factors such as state-of-health (SoH) and state-of-function (SoF). However, ESS are complex and non-linear systems. Their Ri depends on many parameters such as current rate, temperature, SoH and state-of-charge (SoC). It is also a fact that no standardized methodologies exist and many different definitions and ways of Ri determination are being used. Nevertheless, in many cases authors are not aware of the consequences that occur when different Ri definitions are being used, such as possible misinterpretations, doubtful comparisons and false figures of merit. This paper focuses on an application-oriented separation between various Ri definitions and highlights the differences between them. The investigation was based on the following technologies: lead-acid, lithium-ion and nickel metal-hydride batteries as well as electrochemical double-layer capacitors. It is not the target of this paper to provide a standardized definition of Ri but to give researchers, engineers and manufacturers a possibility to understand what the term Ri means in their own work.

  4. Atom probe analysis of titanium hydride precipitates.

    Science.gov (United States)

    Takahashi, J; Kawakami, K; Otsuka, H; Fujii, H

    2009-04-01

    It is expected that the three-dimensional atom probe (3DAP) will be used as a tool to visualize the atomic scale of hydrogen atoms in steel is expected, due to its high spatial resolution and very low detection limit. In this paper, the first 3DAP analysis of titanium hydride precipitates in metal titanium is reported in terms of the quantitative detection of hydrogen. FIB fabrication techniques using the lift-out method have enabled the production of needle tips of hydride precipitates, of several tens of microns in size, within a titanium matrix. The hydrogen concentration estimated from 3DAP analysis was slightly smaller than that of the hydride phase predicted from the phase diagram. We discuss the origin of the difference between the experimental and predicted values and the performance of 3DAP for the quantitative detection of hydrogen.

  5. Failure Mechanisms of Nickel/Metal Hydride Batteries with Cobalt-Substituted Superlattice Hydrogen-Absorbing Alloy Anodes at 50 °C

    Directory of Open Access Journals (Sweden)

    Tiejun Meng

    2016-06-01

    Full Text Available The incorporation of a small amount of Co in the A2B7 superlattice hydrogen absorbing alloy (HAA can benefit its electrochemical cycle life performance at both room temperature (RT and 50 °C. The electrochemical properties of the Co-substituted A2B7 and the failure mechanisms of cells using such alloys cycled at RT have been reported previously. In this paper, the failure mechanisms of the same alloys cycled at 50 °C are reported. Compared to that at RT, the trend of the cycle life at 50 °C versus the Co content in the Co-substituted A2B7 HAAs is similar, but the cycle life is significantly shorter. Failure analysis of the cells at 50 °C was performed using X-ray diffraction (XRD, scanning electron microscopy (SEM, X-ray energy dispersive spectroscopy (EDS, and inductively coupled plasma (ICP analysis. It was found that the elevated temperature accelerates electrolyte dry-out and the deterioration (both pulverization and oxidation of the A2B7 negative electrode, which are major causes of cell failure when cycling at 50 °C. Cells from HAA with higher Co-content also showed micro-shortage in the separator from the debris of the corrosion of the negative electrode.

  6. Mechanical ball-milling preparation of fullerene/cobalt core/shell nanocomposites with high electrochemical hydrogen storage ability.

    Science.gov (United States)

    Bao, Di; Gao, Peng; Shen, Xiande; Chang, Cheng; Wang, Longqiang; Wang, Ying; Chen, Yujin; Zhou, Xiaoming; Sun, Shuchao; Li, Guobao; Yang, Piaoping

    2014-02-26

    The design and synthesis of new hydrogen storage nanomaterials with high capacity at low cost is extremely desirable but remains challenging for today's development of hydrogen economy. Because of the special honeycomb structures and excellent physical and chemical characters, fullerenes have been extensively considered as ideal materials for hydrogen storage materials. To take the most advantage of its distinctive symmetrical carbon cage structure, we have uniformly coated C60's surface with metal cobalt in nanoscale to form a core/shell structure through a simple ball-milling process in this work. The X-ray diffraction (XRD), scanning electron microscope (SEM), Raman spectra, high-solution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectrometry (EDX) elemental mappings, and X-ray photoelectron spectroscopy (XPS) measurements have been conducted to evaluate the size and the composition of the composites. In addition, the blue shift of C60 pentagonal pinch mode demonstrates the formation of Co-C chemical bond, and which enhances the stability of the as-obtained nanocomposites. And their electrochemical experimental results demonstrate that the as-obtained C60/Co composites have excellent electrochemical hydrogen storage cycle reversibility and considerably high hydrogen storage capacities of 907 mAh/g (3.32 wt % hydrogen) under room temperature and ambient pressure, which is very close to the theoretical hydrogen storage capacities of individual metal Co (3.33 wt % hydrogen). Furthermore, their hydrogen storage processes and the mechanism have also been investigated, in which the quasi-reversible C60/Co↔C60/Co-Hx reaction is the dominant cycle process.

  7. Facile Fabrication of 3D Layer-by-layer Graphene-gold Nanorod Hybrid Architecture for Hydrogen Peroxide Based Electrochemical Biosensor

    Science.gov (United States)

    2015-01-01

    Facile fabrication of 3D layer-by-layer graphene-gold nanorod hybrid architecture for hydrogen peroxide based electrochemical biosensor Chenming Xue...the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/). 1. Introduction Electrochemical biosensors are highly effective in...measurement techniques such as radioisotope tracing, NMR spectroscopy, and microfluorometry assay [12,25,18]. In recent years, electrochemical biosensors

  8. Fabrication of ZnO nanoparticles-embedded hydrogenated diamond-like carbon films by electrochemical deposition technique

    Institute of Scientific and Technical Information of China (English)

    Zhang Pei-Zeng; Li Rui-Shan; Pan Xiao-Jun; Xie Er-Qing

    2013-01-01

    ZnO nanoparticles-embedded hydrogenated diamond-like carbon (ZnO-DLC) films have been prepared by electrochemical deposition in ambient conditions.The morphology,composition,and microstructure of the films have been investigated.The results show that the resultant films are hydrogenated diamond-like carbon films embedded with ZnO nanoparticles in wurtzite structure,and the content and size of the ZnO nanoparticles increase with increasing deposition voltage,which are confirmed by X-ray photoelectron spectroscopy (XPS),Raman,and transmission electron microscope (TEM).Furthermore,a possible mechanism used to describe the growth process of ZnO-DLC films by electrochemical deposition is also discussed.

  9. Surface science and electrochemical studies of metal-modified carbides for fuel cells and hydrogen production

    Science.gov (United States)

    Kelly, Thomas Glenn

    Carbides of the early transition metals have emerged as low-cost catalysts that are active for a wide range of reactions. The surface chemistry of carbides can be altered by modifying the surface with small amounts of admetals. These metal-modified carbides can be effective replacements for Pt-based bimetallic systems, which suffer from the drawbacks of high cost and low thermal stability. In this dissertation, metal-modified carbides were studied for reactions with applications to renewable energy technologies. It is demonstrated that metal-modified carbides possess high activity for alcohol reforming and electrochemical hydrogen production. First, the surface chemistry of carbides towards alcohol decomposition is studied using density functional theory (DFT) and surface science experiments. The Vienna Ab initio Simulation Package (VASP) was used to calculate the binding energies of alcohols and decomposition intermediates on metal-modified carbides. The calculated binding energies were then correlated to reforming activity determined experimentally using temperature programmed desorption (TPD). In the case of methanol decomposition, it was found that tungsten monocarbide (WC) selectively cleaved the C-O bond to produce methane. Upon modifying the surface with a single layer of metal such as Ni, Pt, or Rh, the selectivity shifted towards scission of the C-H bonds while leaving the C-O bond intact, producing carbon monoxide (CO) and H2. High resolution energy loss spectroscopy (HREELS) was used to examine the bond breaking sequence as a function of temperature. From HREELS, it was shown that the surfaces followed an activity trend of Rh > Ni > Pt. The Au-modified WC surface possessed too low of a methanol binding energy, and molecular desorption of methanol was the most favorable pathway on this surface. Next, the ability of Rh-modified WC to break the C-C bond of C2 and C3 alcohols was demonstrated. HREELS showed that ethanol decomposed through an acetaldehyde

  10. Synthesis of tantalum carbide and nitride nanoparticles using a reactive mesoporous template for electrochemical hydrogen evolution

    KAUST Repository

    Alhajri, Nawal Saad

    2013-01-01

    Tantalum carbide and nitride nanocrystals were prepared through the reaction of a tantalum precursor with mesoporous graphitic (mpg)-C 3N4. The effects of the reaction temperature, the ratio of the Ta precursor to the reactive template (mpg-C3N4), and the selection of the carrier gas (Ar, N2 and NH3) on the resultant crystal phases and structures were investigated. The produced samples were characterized using powder X-ray diffraction (XRD), CHN elemental analyses, thermogravimetric analyses (TGA), nitrogen sorption, a temperature-programmed reaction with mass spectroscopy (MS), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The results indicate that the different tantalum phases with cubic structure, TaN, Ta2CN, and TaC, can be formed under a flow of nitrogen when formed at different temperatures. The Ta3N5 phase with a Ta5+ oxidation state was solely obtained at 1023 K under a flow of ammonia, which gasified the C 3N4 template and was confirmed by detecting the decomposed gaseous products via MS. Significantly, the formation of TaC, Ta2CN, and TaN can be controlled by altering the weight ratio of the C 3N4 template relative to the Ta precursor at 1573 K under a flow of nitrogen. The high C3N4/Ta precursor ratio generally resulted in high carbide content rather than a nitride one, consistent with the role of mpg-C3N4 as a carbon source. Electrochemical measurements revealed that the synthesized nanomaterials were consistently able to produce hydrogen under acidic conditions (pH 1). The obtained Tafel slope indicates that the rate-determining step is the Volmer discharge step, which is consistent with adsorbed hydrogen being weakly bound to the surface during electrocatalysis. © 2013 The Royal Society of Chemistry.

  11. Electrochemical determination of hydrogen peroxide using -dianisidine as substrate and hemoglobin as catalyst

    Indian Academy of Sciences (India)

    Wei Sun; Hong Jiang; Kui Jiao

    2005-07-01

    A new electrochemical method for the determination of microamounts of hydrogen peroxide utilizing -dianisidine (ODA) as substrate and hemoglobin (Hb) as catalyst is described in this paper. Hb can be used as mimetic peroxidase and it can catalyse the reduction of hydrogen peroxide with the subsequent oxidation of ODA. The oxidative reaction product is an azo compound, which is an electroactive substance and has a sensitive second-order derivative polarographic reductive peak at the potential of -0.58 V (vs. SCE) in pH 8.0 Britton-Robinson (B-R) buffer solution. The conditions of Hb-catalytic reaction and polarographic detection of the reaction product were carefully studied. By using this polarographic peak and under optimal conditions, the calibration curve for the H2O2 was constructed in the linear range of 2.0 × 10-7 ∼ 1.0 × 10-4 mol/l with the detection limit of 5.0 × 10-8 mol/l. This method can also be used to the determination of Hb content in the range of 2.0 × 10-9 ∼ 3.0 × 10-7 mol/l with a detection limit of 1.0 × 10-9 mol/l. The proposed method was further applied to the determination of the content of H2O2 in fresh rainwater with satisfactory results. The catalytic reaction mechanism and the electrode reductive process of the reaction product were carefully studied.

  12. H{sub 2} thermal desorption and hydride conversion reactions in Li cells of TiH{sub 2}/C amorphous nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Vitucci, F.M., E-mail: francesco.vitucci@roma1.infn.it [CNR-ISC, U.O.S. La Sapienza, Piazzale A. Moro 5, 00185 Roma (Italy); Paolone, A. [CNR-ISC, U.O.S. La Sapienza, Piazzale A. Moro 5, 00185 Roma (Italy); Brutti, S. [CNR-ISC, U.O.S. La Sapienza, Piazzale A. Moro 5, 00185 Roma (Italy); Dipartimento di Scienze, Univ. Basilicata, V.le Ateneo Lucano, 10, 85100 Potenza (Italy); Munaò, D.; Silvestri, L.; Panero, S. [Dipartimento di Chimica, Sapienza Univ. Roma, P.le A. Moro 5, 00185 Roma (Italy); Reale, P. [ENEA – Centro Ricerche Casaccia,via Anguillarese 301, 00100 Roma (Italy)

    2015-10-05

    Highlights: • Galvanostatic measurements on amorphous TiH{sub 2} is reported. • Variation of ball milling pre-treatment vary the first discharge capacity. • Relation between thermal H{sub 2} desorption and electrochemical properties is proposed. - Abstract: Here we investigate the properties of amorphous TiH{sub 2}/carbon nanocomposites as possible active material in lithium cells. Several TiH{sub 2}/C mixtures are prepared by a mechanochemical route, by varying the carbon/hydride ratio. Materials are tested in electrochemical cells versus lithium metal in EC:DMC LiPF{sub 6} electrolyte by galvanostatic cycling (GC) and are characterized by X-ray diffraction, transmission electron microscopy, thermogravimetry and mass spectrometry. Thermal dehydrogenation processes are altered by the mechanochemical treatment of the sample: milling decreases the hydrogen content of the hydride. On the other hand, the mechanochemical grinding increases the specific capacity delivered during the first GC discharge. We suggest that the electrochemical process is the result of a delicate balance between the absolute quantity of hydrogen and its availability for the hydride conversion reaction.

  13. Metal/graphene nanocomposites synthesized with the aid of supercritical fluid for promoting hydrogen release from complex hydrides.

    Science.gov (United States)

    Jiang, De-Hao; Yang, Cheng-Hsien; Tseng, Chuan-Ming; Lee, Sheng-Long; Chang, Jeng-Kuei

    2014-11-07

    With the aid of supercritical CO2, Fe-, Ni-, Pd-, and Au-nanoparticle-decorated nanostructured carbon materials (graphene, activated carbon, carbon black, and carbon nanotubes) are synthesized for catalyzing the dehydrogenation of LiAlH4. The effects of the metal nanoparticle size and distribution, and the type of carbon structure on the hydrogen release properties are investigated. The Fe/graphene nanocomposite, which consists of ∼2 nm Fe particles highly dispersed on graphene nanosheets, exhibits the highest catalytic performance. With this nanocomposite, the initial dehydrogenation temperature can be lowered (from ∼135 °C for pristine LiAlH4) to ∼40 °C without altering the reaction route (confirmed by in situ X-ray diffraction), and 4.5 wt% H2 can be released at 100 °C within 6 min, which is faster by more than 135-fold than the time required to release the same amount of H2 from pristine LiAlH4.

  14. Molybdenum carbide-carbon nanocomposites synthesized from a reactive template for electrochemical hydrogen evolution

    KAUST Repository

    Alhajri, Nawal Saad

    2014-01-01

    Molybdenum carbide nanocrystals (Mo2C) with sizes ranging from 3 to 20 nm were synthesized within a carbon matrix starting from a mesoporous graphitic carbon nitride (mpg-C3N4) template with confined pores. A molybdenum carbide phase (Mo2C) with a hexagonal structure was formed using a novel synthetic method involving the reaction of a molybdenum precursor with the carbon residue originating from C3N4 under nitrogen at various temperatures. The synthesized nanocomposites were characterized using powder X-ray diffraction (XRD), temperature-programmed reaction with mass spectroscopy (MS), CHN elemental analyses, thermogravimetric analyses (TGA), nitrogen sorption, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The results indicated that the synthesized samples have different surface structures and compositions, which are accordingly expected to exhibit different electrocatalytic activities toward the hydrogen evolution reaction (HER). Electrochemical measurements demonstrated that the sample synthesized at 1323 K exhibited the highest and most stable HER current in acidic media, with an onset potential of -100 mV vs. RHE, among the samples prepared in this study. This result is attributed to the sufficiently small particle size (∼8 nm on average) and accordingly high surface area (308 m2 g-1), with less oxidized surface entrapped within the graphitized carbon matrix. © 2014 the Partner Organisations.

  15. Characterization of hydrides and delayed hydride cracking in zirconium alloys

    Science.gov (United States)

    Fang, Qiang

    This thesis tries to fill some of the missing gaps in the study of zirconium hydrides with state-of-art experiments, cutting edge tomographical technique, and a novel numerical algorithm. A new hydriding procedure is proposed. The new anode material and solution combination overcomes many drawbacks of the AECLRTM hydriding method and leads to superior hydriding result compared to the AECL RTM hydriding procedure. The DHC crack growth velocity of as-received Excel alloy and Zr-2.5Nb alloy together with several different heat treated Excel alloy samples are measured. While it already known that the DHC crack growth velocity increases with the increase of base metal strength, the finding that the transverse plane is the weaker plane for fatigue crack growth despite having higher resistance to DHC crack growth was unexpected. The morphologies of hydrides in a coarse grained Zircally-2 sample have been studied using synchrotron x-rays at ESRF with a new technique called Diffraction Contrast Tomography that uses simultaneous collection of tomographic data and diffraction data to determine the crystallographic orientation of crystallites (grains) in 3D. It has been previously limited to light metals such as Al or Mg (due to the use of low energy x-rays). Here we show the first DCT measurements using high energy x-rays (60 keV), allowing measurements in zirconium. A new algorithm of a computationally effcient way to characterize distributions of hydrides - in particular their orientation and/or connectivity - has been proposed. It is a modification of the standard Hough transform, which is an extension of the Hough transform widely used in the line detection of EBSD patterns. Finally, a basic model of hydrogen migration is built using ABAQUS RTM, which is a mature finite element package with tested modeling modules of a variety of physical laws. The coupling of hydrogen diffusion, lattice expansion, matrix deformation and phase transformation is investigated under

  16. Crystal structure of gold hydride

    Energy Technology Data Exchange (ETDEWEB)

    Degtyareva, Valentina F., E-mail: degtyar@issp.ac.ru

    2015-10-05

    Highlights: • Volume expansion of metal hydrides is due to the increase in the s-band filling. • AuH structure is similar to that of Hg having one more s electron compared to Au. • Structure stability of both Hg and AuH is governed by the Hume-Rothery rule. - Abstract: A number of transition metal hydrides with close-packed metal sublattices of fcc or hcp structures with hydrogen in octahedral interstitial positions were obtained by the high-pressure-hydrogen technique described by Ponyatovskii et al. (1982). In this paper we consider volume increase of metals by hydrogenation and possible crystal structure of gold hydride in relation with the structure of mercury, the nearest neighbor of Au in the Periodic table. Suggested structure of AuH has a basic tetragonal body-centered cell that is very similar to the mercury structure Hg-t I 2. The reasons of stability for this structure are discussed within the model of Fermi sphere–Brillouin zone interactions.

  17. PEM fuel cell stack performance using dilute hydrogen mixture. Implications on electrochemical engine system performance and design

    Energy Technology Data Exchange (ETDEWEB)

    Inbody, M.A.; Vanderborgh, N.E.; Hedstrom, J.C.; Tafoya, J.I. [Los Alamos National Lab., NM (United States)

    1996-12-31

    Onboard fuel processing to generate a hydrogen-rich fuel for PEM fuel cells is being considered as an alternative to stored hydrogen fuel for transportation applications. If successful, this approach, contrasted to operating with onboard hydrogen, utilizes the existing fuels infrastructure and provides required vehicle range. One attractive, commercial liquid fuels option is steam reforming of methanol. However, expanding the liquid methanol infrastructure will take both time and capital. Consequently technology is also being developed to utilize existing transportation fuels, such as gasoline or diesel, to power PEM fuel cell systems. Steam reforming of methanol generates a mixture with a dry gas composition of 75% hydrogen and 25% carbon dioxide. Steam reforming, autothermal reforming, and partial oxidation reforming of C{sub 2} and larger hydrocarbons produces a mixture with a more dilute hydrogen concentration (65%-40%) along with carbon dioxide ({approx}20%) and nitrogen ({approx}10%-40%). Performance of PEM fuel cell stacks on these dilute hydrogen mixtures will affect the overall electrochemical engine system design as well as the overall efficiency. The Los Alamos Fuel Cell Stack Test facility was used to access the performance of a PEM Fuel cell stack over the range of gas compositions chosen to replicate anode feeds from various fuel processing options for hydrocarbon and alcohol fuels. The focus of the experiments was on the anode performance with dilute hydrogen mixtures with carbon dioxide and nitrogen diluents. Performance with other anode feed contaminants, such as carbon monoxide, are not reported here.

  18. Use of triammonium salt of aurin tricarboxylic acid as risk mitigant for aluminum hydride

    Science.gov (United States)

    Cortes-Concepcion, Jose A.; Anton, Donald L.

    2017-08-08

    A process and a resulting product by process of an aluminum hydride which is modified with by physically combining in a ball milling process an aluminum hydride with a triammonium salt of aurin tricarboxylic acid. The resulting product is an aluminum hydride which is resistant to air, ambient moisture, and liquid water while maintaining useful hydrogen storage and release kinetics.

  19. Modification of Charge Trapping at Particle/Particle Interfaces by Electrochemical Hydrogen Doping of Nanocrystalline TiO2.

    Science.gov (United States)

    Jiménez, Juan M; Bourret, Gilles R; Berger, Thomas; McKenna, Keith P

    2016-12-14

    Particle/particle interfaces play a crucial role in the functionality and performance of nanocrystalline materials such as mesoporous metal oxide electrodes. Defects at these interfaces are known to impede charge separation via slow-down of transport and increase of charge recombination, but can be passivated via electrochemical doping (i.e., incorporation of electron/proton pairs), leading to transient but large enhancement of photoelectrode performance. Although this process is technologically very relevant, it is still poorly understood. Here we report on the electrochemical characterization and the theoretical modeling of electron traps in nanocrystalline rutile TiO2 films. Significant changes in the electrochemical response of porous films consisting of a random network of TiO2 particles are observed upon the electrochemical accumulation of electron/proton pairs. The reversible shift of a capacitive peak in the voltammetric profile of the electrode is assigned to an energetic modification of trap states at particle/particle interfaces. This hypothesis is supported by first-principles theoretical calculations on a TiO2 grain boundary, providing a simple model for particle/particle interfaces. In particular, it is shown how protons readily segregate to the grain boundary (being up to 0.6 eV more stable than in the TiO2 bulk), modifying its structure and electron-trapping properties. The presence of hydrogen at the grain boundary increases the average depth of traps while at the same time reducing their number compared to the undoped situation. This provides an explanation for the transient enhancement of the photoelectrocatalytic activity toward methanol photooxidation which is observed following electrochemical hydrogen doping of rutile TiO2 nanoparticle electrodes.

  20. High energy density battery based on complex hydrides

    Science.gov (United States)

    Zidan, Ragaiy

    2016-04-26

    A battery and process of operating a battery system is provided using high hydrogen capacity complex hydrides in an organic non-aqueous solvent that allows the transport of hydride ions such as AlH.sub.4.sup.- and metal ions during respective discharging and charging steps.