Development of metal borohydrides for hydrogen storage

A metal borohydride M(BH₄)_n is a potential candidate for hydrogen storage materials because of its high gravimetric hydrogen density. The important research issues for M(BH₄)_n are to control the thermodynamic stability and to achieve the faster reaction kinetics. To clarify the thermodynamic stability, M(BH₄)_n (M=Mg, Ca∼Mn, Zn, Al, Y, Zr and Hf; n=2-4) were synthesized by mechanical milling and its thermal desorption properties were investigated. The hydrogen desorption temperature T_d of M(BH₄)_n decreases with increasing Pauling's electronegativities χ_P of M. Because Mn, Zn, and Al borohydrides (χ_P?1.5) desorb borane, they are too unstable for hydrogen storage applications. The enthalpy changes of desorption reaction ΔH_des can be estimated by using our predicted heat of formation of M(BH₄)_n ΔH_boro and reported data for decomposed products ΔH_prod, which are useful indicators for searching M(BH₄)_n with appropriate stability for hydrogen storage material. In the latter case, microwave processing was adopted for achieving fast reaction kinetics. Among metal borohydrides, LiBH₄ was rapidly heated above 380 K by microwave irradiation, 13.7 mass% of hydrogen was desorbed by microwave irradiation. The composites of LiBH₄ with B or C desorbed hydrogen within 3 min. Microwave heating aids in realizing faster kinetics of the hydrogen desorption reaction.     

Hydrogen desorption processes in Li-Mg-N-H systems

Li-Mg-N-H systems composed of Mg(NH₂)₂ and LiH with various ratios can reversibly store a large amount of hydrogen under the temperature condition above 150 °C. These composites with 3:6, 3:8 and 3:12 ratio of Mg(NH₂)₂ and LiH have been independently reported by four groups as promising candidates of high performance hydrogen storage materials possessing the reversibility and the high capacity. In any cases, an interaction between NH₃ and LiH plays an important role for the progress of hydrogen desorbing and absorbing reactions. For the hydrogen desorption process, the NH₃ molecule generated from Mg(NH₂)₂ reacts with LiH, forming LiNH₂ and H₂. Especially, under an equilibrium condition, in situ diffraction results indicated that the single phase of LiNH₂·MgNH (LiMgN₂H₃) could be generated other than the separated two phases. As a next step, the NH₃ molecule generated from LiNH₂ reacts with LiH, desorbing H₂. As a result, the dehydrogenated phase was evaluated to be Li₂NH·MgNH (Li₂MgN₂H₂) or separated two phases, in which the final phase should depend on the experimental conditions. Thus, if the amount of LiH is enough to react with NH₃, the hydrogen desorption processes are described by the NH₃ generation from the corresponding amides and the imide.     

Nitric acid oxidation method to form SiO2/3C-SiC structure at 120 °C

3C-SiC(0 0 1) surfaces are considerably rough with the roughness root mean square value (R_ms) of 1.3 nm, but the surfaces become considerably smooth (i.e., R_ms of 0.5 nm) by heat treatment in pure hydrogen at 400 °C. Two-step nitric acid (HNO₃) oxidation (i.e., immersion in ∼40 wt% HNO₃ followed by that in 68 wt% HNO₃) performed after the hydrogen treatment can oxidize 3C-SiC at extremely low temperature of ∼120 °C, forming thick SiO₂ (e.g., 21 nm) layers. With no hydrogen treatment, the leakage current density of the 〈Al/SiO₂/3C-SiC〉 metal-oxide-semiconductor (MOS) diodes is high, while that for the MOS diodes with the hydrogen treatment is considerably low (e.g., ∼10⁻⁶ A/cm² at the forward gate bias of 1 V) due to the formation of uniform thickness SiO₂ layers. The MOS diodes with the hydrogen treatment show capacitance-voltage curves with accumulation, depletion, and deep-depletion characteristics.     

Acoustic characteristics of Ni–Nb–Zr–H glassy alloys by ultrasonic shear waves

The propagation characteristics of shear horizontally polarized (SH) waves passing through (Ni₄₂Nb₂₈Zr₃₀)_100–x H_x (x = 0–15.2) glassy alloys were investigated as a function of hydrogen content. With an increase in hydrogen content, the propagation time and main frequency of the receiving waves show increase and decrease, respectively, indicating expan‐ sion in average atomic distance which comes from solution of hydrogen. In sharp contrast to crystalline alloys, the decrease in damping ratio and the delay in phase with increasing hydrogen suggest a strong settlement of hydrogen into four‐coordination sites surrounded tetrahedrally by four Zr atoms and the resulting increase in dynamic elasticity, respectively. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Tuning hydrogen storage properties and reactivity: Investigation of the LiBH4-NaAlH4 system

Tuning the hydrogen storage properties of complex metal hydrides is of vast interest. Here, we investigate the hydrogen release and uptake pathways for a reactive hydride composite, LiBH₄−NaAlH₄ utilizing in situ synchrotron radiation powder X-ray diffraction experiments. Sodium alanate transforms to sodium borohydride via a metathesis reaction during ball milling or by heating at T∼95 °C. NaBH₄ decomposes at ∼340 °C in dynamic vacuum, apparently directly to solid amorphous boron and hydrogen and sodium gas and the latter two elements are lost from the sample. Under other conditions, T=400 °C and p(H₂)=∼1 bar, NaBH₄ only partly decomposes to B and NaH. On the other hand, formation of LiAl is facilitated by dynamic vacuum conditions, which gives access to the full hydrogen contents in the LiBH₄−NaAlH₄ system. Formation of AlB₂ is observed (T∼450 °C) and other phases, possibly AlB_x or Al_1−xLi_xB₂, were observed for the more Li-rich samples. This may open new routes to the stabilization of boron in the solid state in the dehydrogenated state, which is a challenging and important issue for hydrogen storage systems based on borohydrides.     

Site dependent hardening of the lanthanum metal lattice by hydrogen absorption

The compressibility of lanthanum (La) metal and its hydrides were measured at room temperature by high pressure synchrotron X-ray diffraction. La metal pressurized in a hydrogen medium forms a hydride with an fcc metal lattice, which likely contains hydrogen at a concentration close to 3.0 and persists over the measured pressure span up to 21 GPa. Equations of state have been determined by helium compression experiments for LaH₂ with tetrahedral interstitial sites fully occupied with hydrogen atoms and for LaH_2.46 with octahedral interstitial sites partially occupied with hydrogen atoms and tetrahedral sites fully occupied. Both hydrides possess fcc metal lattices. The bulk modulus values B₀ are 66.7 ± 1.2 GPa for LaH₂ and 68.4±1.0 GPa for LaH_2.46. These values are three times larger than that of La metal and are very close to each other despite the difference in hydrogen occupation states. The hardening of the metal lattice by hydrogenation is attributed predominantly to hydrogen-metal interactions at the tetrahedral sites and is most pronounced for La, which has the largest ionic radius among rare-earth metals.     

Development of catalytically enhanced sodium aluminum hydride as a hydrogen-storage material

The dehydriding of sodium aluminum hydride, NaAlH₄, is kinetically enhanced and rendered reversible in the solid state upon doping with selected titanium compounds. Following the initial reports of this catalytic effect, further kinetic improvement and stabilization of the cyclable hydrogen capacity have been achieved upon variation in the method of the introduction of titanium and particle-size reduction. Rapid evolution of 4.0-wt % hydrogen at 100 °C has been consistently achieved for several dehydriding/rehydriding cycles. An improved, 4.8-wt % cyclable capacity has been observed in the material doped with a combination of Ti and Zr alkoxide complexes. Doping the hydride with Ti(OBuⁿ)₄ and Fe(OEt)₂ also produces a synergistic effect, resulting in materials that can be rehydrided to 4 wt % at 104 °C and 87 atm of hydrogen within 17 h. The improved kinetics allowed us to carry out constant-temperature, equilibrium-pressure studies of NaAlH₄ that extended to temperatures well below the melting point of the hydride. The 37-kJ/mol value determined for enthalpy of the dehydriding of NaAlH₄(s) to Na₃AlH₆ and Al and the hydrogen plateau pressure of 7 atm at 80 °C are in line with the predictions of earlier studies. The nature of the active catalyst and the mechanism of catalytic action are unknown. The catalytically enhanced hydrides appear to be strong candidates for development as hydrogen carriers for onboard proton exchange membran (PEM) fuel cells. However, further research and development in the areas of rehydriding catalysts, large-scale, long-term cycling, safety and adjustment of the plateau hydrogen pressure associated with dehydriding of AlH₆ ^- are required before these materials can be utilized in commercial onboard hydrogen-storage systems. Received: 7 September 2000 / Accepted: 14 November 2000 / Published online: 9 February 2001     

Effect of Gd2O3 on the hydrogen evolution property of nickel–cobalt coatings electrodeposited on titanium substrate

The effect of rare earth compound, Gd₂O₃, on the microstructure and the hydrogen evolution property of Ni–Co alloy electrode was studied. The morphology and microstructure were characterized by SEM and XRD, respectively, and the electrocatalytic efficiency was evaluated on the basis of electrochemical data obtained from steady-state polarization curves, Tafel curves and electrochemical impedance spectroscopy measurements carried out in 0.50 M Na₂SO₄+0.10 M H₂SO₄ solution. It was found that the embedded Gd₂O₃ particles largely enhanced the electrocatalytic activity of Ni–Co alloy electrode to hydrogen evolution reaction.     

Influence of hydrogen distribution on magnetic properties of amorphous samples

We have studied the effect of the homogeneity of hydrogen distribution on magnetic properties of hydrogen charged amorphous samples (Metglass 2826MB: Fe₄₀Ni₄₀Mo₄B₁₈). The results suggest that, in high magnetostrictive samples, the induced internal stresses and hence the magnetic anisotropy are related to the hydrogen distribution and not to the total quantity of hydrogen inside the sample. To perform this study, the homogeneity of hydrogen distribution in the sample was improved by using a very low rate of hydrogen charging by means of a pulsed electrolytic current. Furthermore, this pulsed electrolytic current allows us to introduce a high quantity of hydrogen without breaking the sample. Received 7 May 1999 and Received in final form 11 October 1999     

Magnetic properties and stress distribution in hydrogenated FeCrB amorphous ribbons

Amorphous Fe₈₅${}_{85}$B₁₅${}_{15}$ and Fe₈₀${}_{80}$Cr_4.3${}_{4.3}$B_15.7${}_{15.7}$ ribbons were hydrogenated from air side. During spontaneous ribbon dehydrogenation, the hydrogen concentration and the constant of anisotropy induced by internal stress were measured and the ribbon bending, characterized by curvature, was recorded. The results obtained indicate that internal stresses in samples under study are proportional to the hydrogen concentration, and hydrogen distribution is not homogeneous in the cross-section of sample. The hydrogen concentration is the largest in the region close to hydrogenated surface. The hydrogen release from this region is very fast and corresponds to the curvature decrease, and it can be, similar to the decrease of total hydrogen concentration, fitted by exponential function.     

Stoichiometrically controlled direct solid-state synthesis of C60H2

The direct solid-state synthesis of C₆₀H₂ has been demonstrated by controlling the amount of hydrogen introduced into the reaction with C₆₀. Palladium hydride has been used as the source of hydrogen. The main product 1,2-C₆₀ is the isomer predicted to have the lowest energy of the possible 23 isomers; in addition, small amounts of the thermodynamically most stable isomer of C₆₀H₄, 1,2,3,4-C₆₀H₄, have also been obtained.     

Preparation, characterization and photocatalytic activity of metal-loaded NaNbO3

Fe-, Ni-, Co- and Ag- loaded NaNbO₃ catalysts were prepared and their activities have been investigated in the reaction of photocatalytic hydrogen generation. Me/NaNbO₃ were synthesized by impregnation of NaNbO₃ in an aqueous solution of metal nitrates and then by calcination at the temperature of 400 °C. The crystallographic phases and optical and vibronic properties were examined by X-ray diffraction (XRD) and diffuse reflectance (DR) UV-vis and resonance Raman spectroscopic methods, respectively. Morphology and chemical composition of the produced samples were studied using a high-resolution transmission electron microscope (HR-TEM) and an energy dispersive X-Ray spectrometer (EDX) as its mode. The detailed analysis has revealed that all the investigated catalysts exhibit high crystallinity and the presence of Fe₂O₃, NiO, Co₃O₄ and Ag₂O oxides on Me/NaNbO₃ was confirmed. Finally, the influence of different metal loadings (Fe, Ni, Co and Ag) on the photocatalytic activity of NaNbO₃ for photocatalytic hydrogen generation has been investigated. Here we report that among all the Me/NaNbO₃ photocatalysts Ag-loaded NaNbO₃ exhibited higher photocatalytic efficiency for photocatalytic hydrogen generation than NaNbO₃.     

Hydrogen-induced magnetic and structural transformations of GdCu

The magnetization of GdCu induced by hydrogen uptake was measured within the temperature range of 4.2 to 300 K, occurring phase changes were followed by X-ray diffraction measurements at ambient temperature. The prepared GdCu powder of CsCl-type structure readily absorbed hydrogen at ambient temperature, where hydrogen pressure was below 100 kPa. Hydrogenation changed the magnetism of GdCu in a complex manner from an antiferromagnetic-like type to a paramagnetic-like one. The changes in magnetic properties of GdCu by hydrogenation are governed by hydrogen-induced disproportionation. Within the composition range 0<[H]/[GdCu]<1, GdCu disproportionated according to 2GdCu+H₂→GdH₂+GdCu₂ . The magnetization was evaluated by the expression χ_total=(1-x)χ_GdCu+(x/2)(χ_GdH2+χ_GdCu2). GdCu hydride was not observed. Hydrogenation beyond [H]/[GdCu]>1 gave rise to the disproportionation of GdCu₂ causing the change in magnetization.     

Effects of hydrogen plasma annealing on the luminescence from a-Si:H/SiO2 and nc-Si/SiO2 multilayers

Effects of post-hydrogen plasma annealing (HPA) on a-Si:H/SiO₂ and nc-Si/SiO₂ multilayers have been investigated and compared. It is found that photoluminescence (PL) from hydrogen-passivated samples was improved due to the reduction of non-radiative recombination defects. Some interesting difference is that during HPA, atomic hydrogen can directly passivate defects of a-Si:H/SiO₂, which results in the reappearance of luminescence band at 760 nm, while for nc-Si/SiO₂, hydrogen passivation requires additional thermal annealing after nc-Si/SiO₂ multilayer was treated by HPA. It is indicated that higher atomic mobility is needed to passivate defects at nc-Si/SiO₂ interface compared with a-Si:H/SiO₂ interface.     

Study of the hydrogen diffusion and segregation into Fe-C-Mo martensitic HSLA steel using electrochemical permeation test

Diffusion and trapping mechanisms are studied in order to improve Hydrogen embrittlement (HE) resistance of high yield strength steels. Investigations were carried on Fe-C-Mo model steel with a quenched and tempered martensitic microstructure. Hydrogen diffusion was studied by using the electrochemical permeation technique. The influence of the charging current densities in 1 M H₂SO₄ at ambient temperature shows a relation between the apparent diffusion coefficient D_app and the apparent subsurface concentration of hydrogen C_0app. Two domains can be separated and are mainly associated with a competition between two distinct processes: hydrogen trapping and hydrogen diffusion. These results are correlated to the quantities of reversible and irreversible traps into the membrane. Moreover, the experimental results revealed that the apparent diffusion coefficient increases and the total amount of trapped hydrogen decreases with temperature. The activation energy of the diffusion process (0.26 eV) and the trapping process (0.58 eV) are supposed to be, respectively, affiliated with lattice diffusion and with trapping on incidental dislocations and/or on martensitic lath interfaces due to misorientations (geometric necessary dislocations).     

Hydrogen implantation and diffusion in silicon and silicon dioxide

Depth profiles of hydrogen implanted into crystalline silicon in random direction at different fluences have been measured by the¹⁵N technique and by SIMS. Whereas hydrogen implanted at a fluence of 10¹⁵ ions/cm² shows some limited mobility, no such mobility is observed for higher implantation fluences. In these cases, ballistic computer codes describe the depth distributions well, within the ranges of both experimental and theoretical accuracy. Annealing up to 510 K does not change the hydrogen distributions.Furthermore, high-fluence hydrogen implantation into silicon dioxide has been examined. There is some indication for radiation-enhanced diffusion during the implantation process. Upon subsequent thermal annealing, the hydrogen is found to diffuse, probably via a trapping/detrapping mechanism associated with an OH/H₂ transformation of the hydrogen bonding.     

Plasma — Processed obliquely deposited Bi-Ge-Se and Ag/Bi-Ge-Se films as resist materials

Lithographic properties of photoexposed Bi₁₀Ge₂₀Se₇₀ and Ag/Bi₁₀Ge₂₀Se₇₀ films and hydrogen plasma exposed Ag/Bi₁₀Ge₂₀Se₇₀ films have been investigated. The asdeposited films show a positive resist behavior on exposure to photons and the silver overlayered films show a negative resisti behavior on exposure to both photons and hydrogen plasme. The contrast values are 1.25 and 2.3 for photoexposed positive and negative resists, respectively, and 5.0 for plasma-exposed negative resist. The sensitivity is 10²⁰ photons/cm² for the photoexposed positive and negative resists and 10¹⁸ ions/cm² (0.11 C/cm²) for the plasma-exposed negative resist.     

Morphology, structure and photocatalytic performance of ZnIn2S4 synthesized via a solvothermal/hydrothermal route in different solvents

Hexagonal ZnIn₂S₄ photocatalysts with different morphology and crystallinity (micro-structures) were prepared in aqueous-, methanol- and ethylene glycol-mediated conditions via a solvothermal/hydrothermal method. The aqueous- and methanol-mediated ZnIn₂S₄ presented to be Flowering-Cherry-like microsphere, while the ethylene glycol-mediated ZnIn₂S₄ presented to be micro-cluster. In comparison with two other products, aqueous-mediated ZnIn₂S₄ possessed the best crystallinity (micro-structure), which resulted in the highest photocatalytic activity for hydrogen evolution under visible-light irradiation. Additionally, aqueous-mediated ZnIn₂S₄ was found to be more stable than the other two ZnIn₂S₄ photocatalysts while undergoing the photocatalytic process. During the photocatalytic reaction, the average rates for hydrogen production over aqueous-, methanol- and ethylene glycol-mediated ZnIn₂S₄ were determined to be 27.3, 12.4 and 9.1 μmol h^-1, respectively, in the present photocatalytic systems.     

Interaction between nanobuds and hydrogen molecules: A first-principles study

Hydrogen storage materials are crucial for the wide application of hydrogen in fuel cells. In this Letter, the interaction between hydrogen molecules and nanobuds has been studied using the Dmol3 package. The results show that the adsorption energies of hydrogen molecules onto nanobuds range from 0.069 eV to 0.115 eV, and that the adsorption energies are not sensitive to the nanobuds' structures but closely related to the number of carbon atoms around H₂ molecules. The energy barrier of a hydrogen molecule entering C176 is 2.38 eV. Each C176 nanobud can accommodate four H₂ molecules. The stress existing in nanobuds induces alterative charge distribution, which can improve the hydrogen storage performance of nanobuds to a certain extent.     

Preparation and characterization of lithium niobate as a novel photocatalyst in hydrogen generation

Several chemical compounds based lithium niobate have been tested in the reaction for the photocatalytic hydrogen generation. The photocatalysts have been prepared by impregnation of Nb₂O₅ in the aqueous solution of lithium hydroxide and then the calcination at the temperature range of 400-650 °C. In this report, we present the interesting study showing that the most active catalyst for the photocatalytic generation of hydrogen is the one containing two lithium niobate phases such as LiNbO₃ and LiNb₃O₈. It means that the lithium niobates based catalyst without any further modification or doping can be applied as a novel material for this process.