Hydrogen storage properties of various carbon supported NaBH4 prepared via metathesis

Sodium borohydride nanoparticles prepared via the metathesis reaction between LiBH₄ and NaCl were successfully deposited on various carbon supporting materials such as graphite, graphene oxide and carbon nanotubes. The X-ray diffraction analyses were conducted to identify the phase of NaBH₄ deposited on various carbon supporting materials. The transmittance electron micrograph analyses were also conducted to investigate the particle size and dispersion of NaBH₄ within carbon supporting materials. The particle size and size distribution of NaBH₄ on graphite were observed to be larger and broader than of other two supporting materials, graphene oxide and CNT due to the lower surface energy as compared to GO and CNT. The bonding state of NaBH₄ was confirmed by the Fourier-transformed infrared spectroscopy analysis. The TG and PCT results show that the hydrogen desorption of the NaBH₄ deposited on carbon supports takes place at temperature (130 °C～) significantly lower than that of pure NaBH₄ (above 500 °C) and the amount of desorption was in the order of graphene oxide (12.3 mass %) > CNT (9.8 mass %) > graphite (5.7 mass %). The reversibility of hydrogen adsorption after five cycles of adsorption-desorption showed that NaBH₄/GO and NaBH₄/CNT were much better than that of pure NaBH₄ due to excellent structural stability.     

Hydrogen storage properties of nanostructured MgH2/TiH2 composite prepared by ball milling under high hydrogen pressure

Nanostructured MgH₂/0.1TiH₂ composite was synthesized directly from Mg and Ti metal by ball milling under an initial hydrogen pressure of 30 MPa. The synthesized composite shows interesting hydrogen storage properties. The desorption temperature is more than 100 °C lower compared to commercial MgH₂ from TG-DSC measurements. After desorption, the composite sample absorbs hydrogen at 100 °C to a capacity of 4 mass% in 4 h and may even absorb hydrogen at 40 °C. The improved properties are due to the catalyst and nanostructure introduced during high pressure ball milling. From the PCI results at 269, 280, 289 and 301 °C, the enthalpy change and entropy change during the desorption can be determined according to the van’t Hoff equation. The values for the MgH₂/0.1TiH₂ nano-composite system are 77.4 kJ mol⁻¹ H₂ and 137.5 J K⁻¹ mol⁻¹ H₂, respectively. These values are in agreement with those obtained for a commercial MgH₂ system measured under the same conditions. Nanostructure and catalyst may greatly improve the kinetics, but do not change the thermodynamics of the materials.     

Hydrogen isotope effects on the structural phase transition of NH3BH3

A systematic study of the structural phase transition of NH₃BH₃ and of its fully deuterated analogue was performed combining DSC and anelastic spectroscopy measurements. The transition is accompanied by a latent heat, and therefore is of the 1st order. On the deuterated sample the enthalpy variation is reduced of more than 20%, from 1.29 to 1.01 kJ/mol and the transition is shifted by ∼1.5 K toward higher temperatures. Both NH₃BH₃ and ND₃BD₃ display a temperature hysteresis between cooling and heating, thus denoting that the phase transition is of first-order. In addition, this hysteresis is extremely small (∼0.5 K) indicating that the coexistence region between the two phases is very narrow. During isothermal ageing, the transformation of the low-temperature orthorhombic phase into the high-temperature tetragonal one occurs with a time constant of ∼16 min in NH₃BH₃ and ∼64 min in ND₃BD₃, evidencing a drastic slowing down of kinetics in the deuterated compound.     

Preparation and dehydrogenation properties of two cobalt-based ammine borohydrides: CoCl3·3NH3/3LiBH4 and CoCl2·3NH3/2LiBH4

Two new cobalt-based ammine borohydrides were prepared via ball milling of LiBH₄ and CoCl_n·3NH₃ (n = 3, 2) with molar ratios of 3:1 and 2:1, respectively. X-ray diffraction (XRD) results revealed the as-prepared composites having amorphous state. Thermogravimetric analysis-mass spectrometry (TG-MS) measurements showed that the two composites mainly release H₂, concurrent with the evolution of a small amount of NH₃. Further results showed that the excessive addition of LiBH₄ can suppress the liberation of NH₃, resulting in the release of H₂ with a high purity (>99 mol.%). By combination with the temperature-programmed-desorption (TPD) results, the CoCl₃·3NH₃/4LiBH₄ and CoCl₂·3NH₃/3LiBH₄composites can release 7.3 wt.% (4.2 wt.% including LiCl) and 4.2 wt.% (2.0 wt.% including LiCl) pure hydrogen, respectively, in the temperature range of 25–300 °C. Isothermal dehydrogenation results reveal that CoCl₃·3NH₃/3LiBH₄ shows favorable dehydrogenation rate at low temperatures, releasing about 5.2 wt.% (2.9 wt.% including LiCl) of hydrogen within 45 min at 80 °C.     

Hydrogen storage properties of the novel crosslinked UiO-66-(OH)2

Metal organic frameworks (MOF) are a type of nanoporous materials with large specific surface area, which are especially suitable for gas separation and storage. In this work, we report a new approach of crosslinking UiO-66-(OH)₂ to enhance its hydrogen storage capacity. UiO-66-(OH)₂ was synthesized using hafnium tetrachloride (HfCl₄) and 2, 5-dihydroxyterephthalic acid (DTPA) through a canonical modulated hydrothermal method (MHT), followed by a post-synthesis modification, which is to form a crosslinking structure inside the porous structure of UiO-66-(OH)₂. During the modification process, the phenolic hydroxyl groups on the UiO-66-(OH)₂ reacted with methanal, and HCl aqueous solution and triethylamine served as catalyst (the products denoted as UiO-66-H and UiO-66-T, respectively). Powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FT-IR), ¹³C nuclear magnetic resonance spectroscopy (¹³C NMR) proved that the crosslinking was formed. The BET specific surface area and the average adsorption pore size of UiO-66-H and UiO-66-T significantly increased after modification. The hydrogen storage capacity of UiO-66-H reached a maximum of 3.37 wt% (16.87 mmol/g) at 77 K, 2 MPa. Hydrogen adsorption enthalpy of UiO-66-T was 0.986 kJ/mol, which was higher than that of UiO-66-(OH)₂ (0.695 kJ/mol). This work shows that UiO-66-(OH)₂ is a promising candidate for potential application in high-performance hydrogen storage.     

Hydrogen production from solid reactions between MAlH4 and NH4Cl

Solid reactions between alkali aluminum hydrides (MAlH₄, M = Li or Na) and NH₄Cl (at mole ratio 1:1) at 170 °C were investigated quantitatively using temperature programmed reaction (TPR), thermo-gravimetric analysis (TGA), differential scanning calorimetry (DSC) and x-ray diffraction (XRD). The release of 3 mol of H₂ from per mole of MAlH₄ was measured, corresponding to 5.6 wt.% H₂ capacity for the NaAlH₄/NH₄Cl system and 6.6 wt.% for LiAlH₄/NH₄Cl, respectively. By ball milling of the precursor compounds prior to the mixing, the reaction proceeded fast and NH₃ production as the by-product could be avoided. The quick solid reactions may be attributed to the low melting temperatures of MAlH₄ and the exothermic nature of the reactions. The reaction mechanism was also discussed.     

LiBH4·NH3BH3: A new lithium borohydride ammonia borane compound with a novel structure and favorable hydrogen storage properties

Mechanically milling ammonia borane and lithium borohydride in equivalent molar ratio results in the formation of a new complex, LiBH₄·NH₃BH₃. Its structure was successfully determined using combined X-ray diffraction and first-principles calculations. LiBH₄·NH₃BH₃ was carefully studied in terms of its decomposition behavior and reversible dehydrogenation property, particularly in comparison with the component phases. In parallel to the property examination, X-ray diffraction and Fourier transformation infrared spectroscopy techniques were employed to monitor the phase evolution and bonding structure changes in the reaction process. Our study found that LiBH₄·NH₃BH₃ first disproportionates into (LiBH₄)₂·NH₃BH₃ and NH₃BH₃, and the resulting mixture exhibits a three-step decomposition behavior upon heating to 450 °C, totally yielding ∼15.7 wt% hydrogen. Interestingly, it was found that h-BN was formed at such a moderate temperature. And owing to the in situ formation of h-BN, LiBH₄·NH₃BH₃ exhibits significantly improved reversible dehydrogenation properties in comparison with the LiBH₄ phase.     

Magnesium and iron loaded hollow glass microspheres (HGMs) for hydrogen storage

The development of a safe and efficient method for hydrogen storage is essential for the use of hydrogen with fuel cells for vehicular applications. Hollow glass microspheres (HGMs) have characteristics suitable for hydrogen storage and are expected to be a potential hydrogen carrier to be used for energy release applications. The HGMs with 10–100 μm diameters, 100–1000 Å pore width and 3–8 μm wall thicknesses are expected to be useful for hydrogen storage. In our research we have prepared HGMs from amber glass powder of particle size 63–75 μm using flame spheroidisation method. The HGMs samples with magnesium and iron loading were also prepared to improve the heat transfer property and thereby increase the hydrogen storage capacity of the product. The feed glass powder was impregnated with calculated amount of magnesium nitrate hexahydrate salt solution to get 0.2–3.0 wt% Mg loading on HGMs. Required amount of ferrous chloride tetrahydrate solution was mixed thoroughly with the glass feed powder to prepare 0.2–2 wt% Fe loaded HGMs. Characterizations of all the HGMs samples were done using FEG-SEM, ESEM and FTIR techniques. Adsorption of hydrogen on all the Fe and Mg loaded HGMs at 10 bar pressure was conducted at room temperature and at 200 °C, for 5 h. The hydrogen adsorption capacity of Fe loaded sample was about 0.56 and 0.21 weight percent for Fe loading 0.5 and 2.0 weight percentage respectively. The magnesium loaded samples showed an increase of hydrogen adsorption from 1.23 to 2.0 weight percentage when the magnesium loading percentage was increased from 0 to 2.0. When the magnesium loading on HGMs was increased beyond 2%, formation of nano-crystals of MgO and Mg was seen on the HGMs leading to pore closure and thereby reduction in hydrogen storage capacity.     

Hydrogen storage properties of flexible and porous La0.8Mg0.2Ni3.8/PVDF composite

A study on the hydrogen storage properties of flexible and porous La_0.8Mg_0.2Ni_3.8/PVDF (polyvinylidene fluoride) composite was reported. In this composite, PVDF acted as a binder to connect the alloy powders and (NH₄)₂CO₃ as a pore-forming agent to create void space. Increasing PVDF content, the hydrogen absorption kinetics of the composite gradually decreased. Increasing (NH₄)₂CO₃ from 1% to 5%, the capacity firstly increased and then decreased. 0.08–0.13 wt% increased capacity for the composite was observed at 70 °C by comparison with the intrinsic composite (La_0.8Mg_0.2Ni_3.8/1%PVDF). Varying temperature from 0 °C to 100 °C, 0.1–0.15 wt% increased capacity were obtained for the typical porous composite (La_0.8Mg_0.2Ni_3.8/1%PVDF/3%(NH₄)₂CO₃). The PVDF-assisted composite showed the flexible/solidified characteristic in hydriding/dehydriding, which maybe lowed down the oxidation of the alloy powders and preserved the void space. Finally, ∼0.1 wt% increased capacity remained after ten hydriding/dehydriding cycles.     

Synthesis of novel hollow microflowers (NHMF) of Nb3O7F,their optical and hydrogen storage properties

A two step, facile surfactant free hydrothermal route was adopted to synthesize Nb₃O₇F novel hollow microflowers (NHMF). Time dependent experiments were performed which suggested Nb₃O₇F-NHMF were formed due to Ostwald-ripening process. Raman spectroscopy was conducted to understand different vibrational modes of Nb₃O₇F-NHMF. Its characteristic band at 692 cm⁻¹ was observed which is associated to NbO₆ octahedron sharing. The bandgap of 3.2 eV was calculated by using UV-VIS-NIR absorption spectrum. Considering importance of layered structures in energy storage applications, hydrogen storage ability of Nb₃O₇F-NHMF were measured for the first time. The maximum values of hydrogen absorption for Nb₃O₇F-NHMF at 373 K and 473 K were 0.789 wt.% and 1.08 wt.%, respectively. The hydrogen storage measurements revealed the potential of Nb₃O₇F-NHMF as prospective material for energy storage applications.     

A novel cryogenic insulation system of hollow glass microspheres and self-evaporation vapor-cooled shield for liquid hydrogen storage

Liquid hydrogen (LH₂) attracts widespread attention because of its highest energy storage density. However, evaporation loss is a serious problem in LH₂ storage due to the low boiling point (20 K). Efficient insulation technology is an important issue in the study of LH₂ storage. Hollow glass microspheres (HGMs) is a potential promising thermal insulation material because of its low apparent thermal conductivity, fast installation (Compared with multi-layer insulation, it can be injected in a short time.), and easy maintenance. A novel cryogenic insulation system consisting of HGMs and a self-evaporating vapor-cooled shield (VCS) is proposed for storage of LH₂. A thermodynamic model has been established to analyze the coupled heat transfer characteristics of HGMs and VCS in the composite insulation system. The results show that the combination of HGMs and VCS can effectively reduce heat flux into the LH₂ tank. With the increase of VCS number from 1 to 3, the minimum heat flux through HGMs decreases by 57.36%, 65.29%, and 68.21%, respectively. Another significant advantage of HGMs is that their thermal insulation properties are not sensitive to ambient vacuum change. When ambient vacuum rises from 10⁻³ Pa to 1 Pa, the heat flux into the LH₂ tank increases by approximately 20%. When the vacuum rises from 10⁻³ Pa to 100 Pa, the combination of VCS and HGMs reduces the heat flux into the tank by 58.08%–69.84% compared with pure HGMs.     

Hydrogen storage capability of Se@C120 system

A single-walled, capped and selenium doped, carbon nanotube, Se@C₁₂₀, was doped endohedrally with hydrogen molecules to obtain a series of (n_H2+Se)@_C120$(n{\mathrm{H}}_2+\mathrm{Se})@{\mathrm{C}}_{120}$, (n  : 0–11) systems. Then, they were subjected to quantum chemical treatment using PM3 method at the level of RHF approach. Calculations indicated that these systems were stable but endothermic in nature. In (10_H2+Se@_C120)$(10{\mathrm{H}}_2+\mathrm{Se}@{\mathrm{C}}_{120})$ and (11_H2+Se@_C120)$(11{\mathrm{H}}_2+\mathrm{Se}@{\mathrm{C}}_{120})$ systems, the hydrogen molecule nearest to the Se atom tends to dissociate to form a quasi-_H2Se${\mathrm{H}}_2\mathrm{Se}$ structure.     

Hydrogen storage capability of carbon nanotube Be@C120

PM3 (RHF) type semiempirical quantum chemical calculations have been carried out on (nH₂+Be)@C₁₂₀ systems where C₁₂₀ is a capped tube and n15. The results indicate that all these systems are stable but endothermic in nature. (7H₂+Be)@C₁₂₀ system has the lowest heat of formation value.     

Hydrogen release by thermolysis of ammonia borane NH3BH3 and then hydrolysis of its by-product [BNHx]

Ammonia borane (AB) is one of the most attractive hydrides owing to its high hydrogen density (19.5 wt%). Stored hydrogen can be released by thermolysis or catalyzed hydrolysis, both routes having advantages and issues. The present study has envisaged for the first time the combination of thermolysis and hydrolysis, AB being first thermolyzed and then the solid by-product believed to be polyaminoborane [NH₂BH₂]_n (PAB) being hydrolyzed. Herein we report that: (i) the combination is feasible, (ii) PAB hydrolyzes in the presence of a metal catalyst (Ru) at 40 °C, (iii) a total of 3 equiv. H₂ is released from AB and PAB-H₂O, (iv) high hydrogen generation rates can be obtained through hydrolysis, and (v) the by-products stemming from the PAB hydrolysis are ammonium borates. The following reactions may be proposed: AB → PAB + H₂ and PAB + xH₂O → 2H₂ + ammonium borates. All of these aspects as well as the advantages and issues of the combination of AB thermolysis and PAB hydrolysis are discussed.     

Dehydriding and rehydriding properties of yttrium borohydride Y(BH4)3 prepared by liquid-phase synthesis

Y(BH₄)₃ was prepared by liquid-phase synthesis, and its dehydriding and rehydriding properties were systematically investigated by performing thermogravimetry and differential thermal analysis (TG-DTA) and powder X-ray diffraction (XRD) measurement. The dehydriding reaction of Y(BH₄)₃ starts at appropriately 460 K, and a total of 7.8 wt% of hydrogen is released up to 773 K. Phase transformation and melting are observed in Y(BH₄)₃ at approximately 474 K and 499 K, respectively. Both DTA and XRD measurement results indicate that the decomposition of Y(BH₄)₃ proceeds via multistep dehydriding reactions accompanied with the formation of an intermediate phase. Furthermore, Y(BH₄)₃ is proved to be partially rehydrided.     

Industrial scale modelling of the thermochemical energy storage system based on CO2 + 2NH3 ↔ NH2COONH4 equilibrium

The thermochemical storage of energy by the system carbon dioxide, ammonia and ammonium carbamate is studied in detail. In particular, the kinetics and the thermodynamics of the reversible reaction is studied. We give two industrial models for the operation of this system. In the first, the separation of the gases NH₃ and CO₂ is achieved by compression and liquefaction of NH₃. In the second, a method of separation of the gases is proposed which is based on the solubility of NH₃ in ethanol while CO₂ is practically insoluble. The operation of this system is examined both in closed form and in the case in which CO₂ is rejected in the atmosphere, and it is taken from alcoholic fermentation or from the combustion gases of power plants burning lignite. The mass and energy balance is given, for each case, and the amount of energy losses by the use of this storage system is calculated. Finally, we give some estimates for the area of solar collectors and the amount of chemicals which are required in order to cover the energy needs of a community.     

Li2(NH2BH3)(BH4)/LiNH2BH3: The first metal amidoborane borohydride complex with inseparable amidoborane precursor for hydrogen storage

A novel lithium amidoborane borohydride complex, Li₂(NH₂BH₃)(BH₄), was synthesized using mechanochemical method and its crystal structure was successfully determined by a combination of X-ray diffraction (XRD) analysis and first-principles calculations. Interestingly, this compound does not exist as a pure phase, but requires almost equivalent amount of amorphous LiAB as a stabilizing agent. In this paper, we report a careful study of the structure, property, and dehydrogenation mechanism of the 1:1 Li₂(NH₂BH₃)(BH₄)/LiAB composite. This composite can release ∼8 wt% H₂ at 100 °C via a two-step dehydrogenation process, with dehydrogenation kinetics better than the parenting phases. The composite and its dehydrogenation products were characterized by the combined XRD, Fourier transformation infrared (FTIR) spectroscopy, and solid-state ¹¹B MAS NMR techniques. Selective deuterium labeling was performed to elucidate a reaction sequence for the hydrogen release by analyzing the released gases.     

Enhanced hydrogen storage properties of LiBH4-MgH2 composite by the catalytic effect of MoCl3

Though LiBH₄-MgH₂ system exhibits an excellent hydrogen storage property, it still presents high decomposition temperature over 350 °C and sluggish hydrogen absorption/desorption kinetics. In order to improve the hydrogen storage properties, the influence of MoCl₃ as an additive on the hydrogenation and dehydrogenation properties of LiBH₄-MgH₂ system is investigated. The reversible hydrogen storage performance is significantly improved, which leads to a capacity of about 7 wt.% hydrogen at 300 °C. XRD analysis reveals that the metallic Mo is formed by the reaction between LiBH₄ and MoCl₃, which is highly dispersed in the sample and results in improved dehydrogenation and hydrogenation performance of LiBH₄-MgH₂ system. From Kissinger plot, the activation energy for hydrogen desorption of LiBH₄-MgH₂ system with additive MoCl₃ is estimated to be ∼43 kJ mol⁻¹ H₂, 10 kJ mol⁻¹ lower than that for the pure LiBH₄-MgH₂ system indicating that the kinetics of LiBH₄-MgH₂ composite is significantly improved by the introduction of Mo.     

Synthesis and thermal decomposition properties of a novel dual-cation/anion complex hydride Li2Mg(BH4)2(NH2)2

A novel dual-cation/anion complex hydride (Li₂Mg(BH₄)₂(NH₂)₂), which contains a theoretical hydrogen capacity of 12.1 wt%, is successfully synthesized for the first time by ball milling a mixture consisting of MgBH₄NH₂ and Li₂BH₄NH₂. The prepared Li₂Mg(BH₄)₂(NH₂)₂ crystallizes in a triclinic structure, and the [NH₂] and [BH₄] groups remain intact within the structure. Upon heating, the prepared Li₂Mg(BH₄)₂(NH₂)₂ decomposes to release approximately 8.7 wt% hydrogen in a three-step reaction at 100–450 °C. In addition, a small amount of ammonia is evolved during the first and second thermal decomposition steps as a side product. This ammonia is responsible for the lower experimental dehydrogenation amount compared to the theoretical hydrogen capacity. The XRD and FTIR results reveal that Li₂Mg(BH₄)₂(NH₂)₂ first decomposes to LiMgBN₂, LiBH₄, BN, LiH and MgBNH₈ at 100–250 °C, and then, the newly formed MgBNH₈ reacts with LiH to form Mg, LiBH₄ and BN at 250–340 °C. Finally, the decomposition of LiBH₄ releases hydrogen and generates LiH and B at 340–450 °C.