Addition of transition metals to lithium intercalated fullerides enhances hydrogen storage properties

We report an innovative synthetic strategy based on the solid state reaction of fullerene C₆₀ with lithium-transition metals alloys (platinum and palladium), which provides transition metal-decorated lithium intercalated fullerides, with improved hydrogen storage properties. Compounds with Li₆Pt_0.11C₆₀ and Li₆Pd_0.07C₆₀ stoichiometry were obtained and investigated with manometric/calorimetric techniques which showed an 18% increase of the final H₂ absorbed amount with respect to pure Li₆C₆₀ (5.9 wt% H₂) and an improved absorption process kinetic. The absorption mechanism was investigated with X-rays diffraction which allowed to identify the formation of the hydrofullerides. Scanning Electron Microscopy was applied to gain information on transition metal distribution and detected the presence of platinum and palladium aggregates which are shown to perform a surface catalytic activity towards hydrogen molecule dissociation process.     

Synthesis and hydrogen storage capacity of exfoliated turbostratic carbon nanofibers

Turbostratic carbon nanofibers (CNFs) with a rough surface, open pore walls, and a defect structure were continuously produced by the thermal decomposition of alcohol in the presence of an iron catalyst and a sulfur promoter at 1100 °C under a nitrogen atmosphere in a vertical chemical vapor deposition reactor. A graphite exfoliation technique using intercalation and thermal shock was employed to expand the graphene layers of the as-produced turbostratic CNFs. The hydrogen storage capacity of the turbostratic CNF samples was measured using the volumetric method with a pressure of up to 1 MPa at 77 K. The hydrogen storage capacities of the as-produced and exfoliated turbostratic CNFs were 1.5 and 5 wt%, respectively. The defects on the surface and expandable graphitic structure are considered important keys to increasing the hydrogen uptake in turbostratic CNFs.     

Improving hydrogen storage in Ni-doped carbon nanospheres

The effect of nickel distribution and content in Ni-doped carbon nanospheres on hydrogen storage capacity under conditions of moderate temperature and pressure was studied. It was found that the nickel distribution, obtained by using different doping techniques and conditions, has a noticeable influence on hydrogen storage capacity. The samples with the most homogeneous nickel distribution, obtained by pre-oxidising the carbon nanospheres, displayed the highest storage capacity. In addition, storage capacity is influenced by the amount of nickel. It was found a higher storage capacity in samples containing 5 wt.% of Ni. This is due to the greater interactions between the nickel and the support that produce a higher activation of the solid through a spillover effect.     

Synthesis and hydrogen storage properties of lithium borohydride amidoborane complex

A series of mixtures of LiAB/LiBH₄ with different molar ratios were prepared and their hydrogen storage properties were investigated in this study. Among them, a new structure was found in the LiAB/LiBH₄ sample with a molar ratio of 1/1. It is of orthorhombic structure and composed of alternative layers of LiAB and LiBH₄. It shows similar hydrogen desorption behaviors of LiAB–LiBH₄ and LiAB–0.5LiBH₄. For use in hydrogen storage, high hydrogen capacity and low operation temperature are demanded, thus, the dehydrogenation properties of LiAB–0.5LiBH₄ were subsequently measured. Three steps of desorption were observed during the heating process, with a total release of 11.5 wt% H₂ at 500 °C. The reaction path was identified using a combined investigation of XRD and ¹¹B solid state NMR. Dehydrogenation kinetic analyses show that the complex has lower activation energy (61 ± 4 kJ mol⁻¹ H₂) than that of LiAB (71 ± 5 kJ mol⁻¹ H₂). It is likely that dehydrogenation process was promoted due to the presence of LiBH₄.     

Synthesis and characterisation of a mesoporous carbon/calcium borohydride nanocomposite for hydrogen storage

Borohydrides with high hydrogen content are being extensively studied as potential hydrogen storage systems placing particular emphasis on upturning their unfavourable kinetic and thermodynamic properties which give rise to significantly high dehydrogenation temperatures and slow hydrogen release far away from the desired application window. In this work the encapsulation of Ca(BH₄)₂ particles in the pores of a CMK-3 type ordered mesoporous carbon scaffold by wet chemistry routes, also employing the use of TiCl₃ as a catalyst, is shown to have a beneficial effect on the hydrogen desorption profile of the bulk hydride by shifting its decomposition to noticeable lower temperatures.     

A search for new Mg- and K-containing alanates for hydrogen storage

In this work Mg- and K-containing alanates have been investigated as possible hydrogen storage materials. Ball milling was carried out under argon or at moderate/high hydrogen pressure in order to obtain an improved driving force for the formation of potential new alanate phases. Powder X-ray diffraction and volumetric measurements were used in order to identify reaction mechanisms and phases forming in these systems. New unidentified peaks were detected for the mixtures 2MgH₂ + 3Al + KH and 2CaH₂ + Al + 2KH. However, they do not seem to belong to reversible hydride phases.     

Fabrication of Pt-doped carbon aerogels for hydrogen storage by radiation method

A radiation method was investigated to fabricate Pt-doped carbon aerogels (CAsPt). The physicochemical properties of the pristine CAs and CAsPt were systematically characterized by X-ray diffraction, scanning electron microscope, transmission electron microscopy, and nitrogen adsorption measurements. The results showed that not only a great number of Pt nanospheres but also many Pt nanoparticles presented in the network of CAs after radiation. The influence of Pt doping on the hydrogen uptake capacity of CAs was studied. In comparison with the pristine CAs, it was remarkable that the hydrogen uptake capacity of the CAsPt had been significantly enhanced, which was contributed by the hydrogen spillover of Pt.     

Synthesis and characterization of porous HKUST-1 metal organic frameworks for hydrogen storage

Hydrogen storage capacity has been investigated on a copper-based metal organic framework named HKUST-1 with fine structural analyses. The crystalline structure of HKUST-1 MOF has been confirmed from the powder X-ray diffraction and the average particle diameter has been found about 15–20 μm identified by FE-SEM. Nitrogen adsorption isotherms show that HKUST-1 MOF has approximately type-I isotherm with a BET specific surface area of 1055 m²g⁻¹. Hydrogen adsorption study shows that this material can store 0.47 wt.% of H₂ at 303 K and 35 bar. The existence of Cu (II) in crystalline framework of HKUST-1 MOF has been confirmed by pre-edge XANES spectra. The sharp feature at 8985.8 eV in XANES spectra represents the dipole-allowed electron transition from 1s to 4p_xy. In addition, EXAFS spectra indicate that HKUST-1 MOF structure has the Cu–O bond distance of 1.95 Å with a coordination number of 4.2.     

Synthesis and hydrogen storage properties of ultrafine Mg-Zn particles

Mg-6.9 at.% Zn ultrafine particles (UFPs) were prepared by hydrogen plasma-metal reaction (HPMR) method. The electron microscopy study revealed that they were spherical in shape with particle size in the range 100-700 nm. Each fine particle was composed of single crystal structure of α-Mg(Zn) solid solution and amorphous structure of Mg-Zn alloy. After one absorption and desorption cycle, these UFPs transformed from the single crystal into the nanocrystalline structure and the mean particle size changed from 400 to 250 nm. It was found that the Mg-Zn UFPs could absorb 5.0 wt.% hydrogen in 20 min at 573 K and accomplish a high hydrogen storage capacity of 6.1 wt.% at 573 K. The fine particle size, nanocrystalline structure and the low oxide content of the obtained sample promoted the hydrogen sorption process with low hydrogen absorption activation energy of 56.3 kJ/mol. The enhanced hydrogen sorption properties of high absorbing rate and high storage capacity were due to the improved kinetics rather than the change in enthalpy.     

Macroscopic kinetics of hydrate formation of mixed hydrates of hydrogen/tetrahydrofuran for hydrogen storage

Hydrogen/Tetrahydrofuran mixed hydrate formation studies were conducted in a stirred tank reactor. Hydrate formation kinetics at driving forces of 2 MPa, 5 MPa and 7 MPa were studied. Tetrahydrofuran (THF) concentration was varied between 1 mol% and 5 mol% and its effect on hydrate formation kinetics was investigated. With an increase in the driving force there was an increase in gas uptake till super saturation. However, the increased driving force had little effect on the reduction of induction time even at high promoter (THF) concentration. 5 mol% THF solutions behave distinctly exhibiting an increased hydrate growth compared to low promoter concentrations due to the occurrence of multiple nucleation events (observed based on temperature spikes and gas uptake). Rate of hydrate formation increased with an increase in driving force for a given concentration of THF promoter. Water conversion to hydrates in the range of 2.8–10.8% was achieved for all the experiments. Addition of Sodium Dodecyl Sulphate (SDS) surfactant had no effect in improving the kinetics of mixed hydrogen/THF hydrates. This study highlights the kinetic challenges that need to be overcome in storing hydrogen as clathrate hydrates.     

Ab initio characterization of Ti decorated SWCNT for hydrogen storage

Characterization has been performed on basis of several physicochemical parameters. The results indicate that the preferential adsorption is on Ti atom deposited on the top site of the (5,5) armchair SWCNT with energies (−0.44 and −0.71) eV for H₂ oriented parallel to the (x) and (y) axes respectively. The binding of H₂ is mostly dominated by the support-metal E (i)^S?Ti term. The role of the SWCNT is not restricted to support the metal. Significant reduction of the energy gap is observed when H₂ are anchored on the external surface of the SWCNT. The SWCNT?Ti?H₂(x) complex is the least reactive configuration with nucleophiles. The calculated parameters characterize H₂ that is oriented parallel to the (x)-[100] axis of the SWCNT to be the most suitable configuration for hydrogen storage based on the recommended adsorption energy range of DOE (−0.2 to −0.6) eV.     

Nitrogen-incorporated carbon nanotube derived from polystyrene and polypyrrole as hydrogen storage material

“Synthesis of nitrogen-doped carbon nanotubes from polymeric precursors (polystyrene and polypyrrole) by poly-condensation followed by carbonization under an inert atmosphere is reported. Three different carbonization temperatures (500 °C, 700 °C and 900 °C) were employed to synthesize three different carbon nanostructures with different morphologies. These were designated as NCNR-500 (nitrogen-doped carbon nanorods), NCBCT-700 (nitrogen-doped fused bead carbon nanotubes), and NCNT-900 (nitrogen-doped carbon nanotubes) according to morphology and carbonization temperature. Microstructure, morphology, porosity, and nitrogen content were characterized by several different techniques. The effects of carbonization temperature and the role of functional groups were also investigated. Total and excess hydrogen storage capacities of 2.0 wt% and 1.8 wt%, respectively, were measured at 298 K and 100 bar for the NCNT-900 material. This is higher than the capacities of the NCNR-500 and NCBCT-700 materials. NCNT-900 exhibited a porous structure with high specific surface area and total pore volume of 870 m/g and 0.62 cm³/g, respectively.     

Metal hydride hydrogen storage and compression systems for energy storage technologies

Along with a brief overview of literature data on energy storage technologies utilising hydrogen and metal hydrides, this article presents results of the related R&D activities carried out by the authors. The focus is put on proper selection of metal hydride materials on the basis of AB₅- and AB₂-type intermetallic compounds for hydrogen storage and compression applications, based on the analysis of PCT properties of the materials in systems with H₂ gas. The article also presents features of integrated energy storage systems utilising metal hydride hydrogen storage and compression, as well as their metal hydride based components developed at IPCP and HySA Systems.     

Review of hydrogen storage techniques for on board vehicle applications

Hydrogen gas is increasingly studied as a potential replacement for fossil fuels because fossil fuel supplies are depleting rapidly and the devastating environmental impacts of their use can no longer be ignored. H₂ is a promising replacement energy storage molecule because it has the highest energy density of all common fuels by weight. One area in which replacing fossil fuels will have a large impact is in automobiles, which currently operate almost exclusively on gasoline. Due to the size and weight constraints in vehicles, on board hydrogen must be stored in a small, lightweight system. This is particularly challenging for hydrogen because it has the lowest energy density of common fuels by volume. Therefore, a lot of research is invested in finding a compact, safe, reliable, inexpensive and energy efficient method of H₂ storage. Mechanical compression as well as storage in chemical hydrides and absorption to carbon substrates has been investigated. An overview of all systems including the current research and potential benefits and issue are provided in the present paper.     

Improving comparability of hydrogen storage capacities of nanoporous materials

We present results of investigations into improving methods by which gas sorption data are collected and reported. The focus is the accurate comparison of hydrogen storage capacities of different nanoporous materials. The aim is to produce a more rigorous approach to the assessment of the hydrogen storage capacities of different nanoporous materials through formulation of meticulous and systematic data collection routines for production of universally reproducible H₂ isotherms over a wide range of pressure and temperature conditions. Effects of a range of experimental variables are examined and recommendations for the optimisation of data collection routines are given.     

Catenated metal-organic frameworks: Promising hydrogen purification materials and high hydrogen storage medium with further lithium doping

Based on the first-principles derived force fields and grand canonical Monte Carlo simulations, we find that the catenated metal-organic frameworks outperform the noncatenated structures, in terms of H₂ separation from other gases (CH₄, CO and CO₂) and H₂ adsorption by Li doping. A system utilizing IRMOF-11 (or IRMOF-13) for hydrogen separation and Li-doped IRMOF-9 for hydrogen storage is therefore proposed, with hydrogen uptake of 4.91 wt% and 36.6 g/L at 243 K and 100 bar for Li-doped IRMOF-9, which is close to the 2017 DOE target. It is promising to find appropriate microporous materials for hydrogen purification and storage at ambient conditions with structure catenated.     

SANS characterization of porous magnesium for hydrogen storage

Porous magnesium was produced through the thermal decomposition of various additives in an effort to increase hydrogen storage capacity. Samples were characterized using SANS and different theoretical models were applied to the results and discussed. The polydisperse self-assembled (PSA) model was found to best represent the scattering from these materials as this model incorporates the polydispersity of the pores and allows for variations in structure factor. Pure magnesium produced using the same thermal method absorbed a negligible amount of hydrogen, and hydrogen uptake was found to increase with increasing porosity as determined using the PSA model. Maximum hydrogen uptake (1.3%) was found when 0.3% Cs₂CO₃ and 0.5% Ni were combined as an additive during thermal treatment. In addition, the development of porosity was found to promote hydrogen desorption at lower temperatures. SANS represents an indispensible method by which to characterize materials and the PSA model described in this work has the potential to be extremely useful in the characterisation of porous metallic systems.     

Preparation and characterization of mica glass-ceramics as hydrogen storage materials

This work is an attempt to study storing hydrogen in safe, reliable, compact, and cost-effective glass-ceramics materials for the first time. The effect of replacing K⁺ by Na⁺ or Li⁺ in the fluorophlogopite formula KMg₃AlSi₃O₁₀F₂ was studied using DTA, XRD and SEM. Also the effect of the crystallized phases within glass-ceramics on the surface area and capacity of storing hydrogen under different pressures were studied. Replacement of K⁺ by Na⁺ or Li⁺ leads to increase the temperature of crystallization in the same order. XRD revealed crystallization of spodumene (LiAlSi₂O₆) and forsterite (Mg₂SiO₄) in GLi and Na-fluorophlogopite (NaMg₃AlSi₃O₁₀F₂) and Na-mica (NaAl₃Si₃O₁₁) in GNa while Lucite (KAlSi₂O₆) and forsterite in GK. Surface area measurements for optimum samples showed low values in the range 0.48–0.58 m²/g; also total pore volumes have low values 9.4 × 10^?4–6.99 × 10^?3 cm³/g. The hydrogen adsorption content reached 1.25, 2.5, 1.34 sand 1.9 wt% for GLi, GNa, GK and GK samples heated for 2 h at 770,1100, 1000 and 1100 °C, respectively. The results obtained that, Na-bearing samples are the proper for hydrogen storage wherein sodium mica and phlogopite with characteristic sheet structure were crystallized.     

Nanoconfined mixed Li and Mg borohydrides as materials for solid state hydrogen storage

Several mixtures of LiBH₄ and Mg(BH₄)₂ borohydrides in different stoichiometric ratios (1:0, 2:1, 1:1, 1:2, 0:1), prepared by high energy ball milling, have been investigated with X-ray powder diffraction and thermal programmed desorption (TPD) volumetric analysis to test the dehydrogenation kinetics in correlation with the physical mixture composition. Afterwards mixed and unmixed borohydrides were dispersed on high specific surface area ball milled graphite by means of the solvent infiltration technique. BET and statistical thickness methods were used to characterize the support surface properties, and SEM micrographs gave a better understanding of the preparation techniques. It has been observed by TPD volumetric measurements that the confinement of the reactive borohydrides on the nanoporous supports leads to a lower dehydrogenation temperature compared to unsupported borohydrides. Moreover, a further decrease of the dehydrogenation temperature has been observed by increasing the specific surface area of the support and the pores volume and by using the prepared mixtures instead of pure materials. The dehydrogenation process seems to be favoured by the heterogeneous nucleation on the graphite surface of decomposition products or intermediate phases from melted liquid borohydrides.     

Changes in hydrogen storage properties of carbon nano-horns submitted to thermal oxidation

The effect of thermal oxidation on the hydrogen storage properties of carbon nano-horns was investigated by gravimetric and electrochemical methods. The pristine nano-horn sample was oxidised at 673 K in air for different periods (15, 30 and 60 min) and the resulting materials were characterised. The N₂ adsorption experiments reveal a marked increase in the surface area, from 267 m² g⁻¹, for the pristine sample, up to 1360 m² g⁻¹ for the sample oxidised for the 60 min period, and a reduction in the average pore diameter. The gravimetric investigation, conducted at low temperature (77 K) showed an increase in the hydrogen storage, from 0.75 wt% for the pristine sample up to 2.60 wt% for the oxidised material. Reproducible and stable hydrogen storage was found for all the samples examined apart from the sample oxidised for 60 min. For the latter, a decrease in the amount of hydrogen stored between the first and second cycles was found. Electrochemical loading of hydrogen in the samples was performed at room temperature (298 K) in alkaline solution by the galvanostatic charge/discharge technique. The results obtained here however show a much lower hydrogen storage level by the samples as compared to the gas storage method, with a maximum value of 0.124 wt% H₂ and with very little dependence on the thermal oxidation treatment.