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.     

Fabrication of zinc‐loaded hollow glass microspheres (HGMs) for hydrogen storage

The greatest challenge for a feasible hydrogen economy lies on the production of pure hydrogen and the materials for its storage with controlled release at ambient conditions. Hydrogen with its great abundance, high energy density and clean exhaust is a promising candidate to meet the current global challenges of fossil fuel depletion and green house gases emissions. Extensive research on hollow glass microspheres (HGMs) for hydrogen storage is being carried out world‐wide, but the right material for hydrogen storage is yet underway. But many other characteristics, such as the poor thermal conductivity etc. of the HGMs, restrict the hydrogen storage capacity. In this work, we have attempted to increase the thermal conductivity of HGMs by ZnO doping. The HGMs with Zn weight percentage from 0 to 10 were prepared by flame spheroidization of amber‐colored glass powder impregnated with the required amount of zinc acetate. The prepared HGMs samples were characterized using field emission‐scanning electron microscope (FE‐SEM), environmental SEM (ESEM), high‐resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy and X‐ray diffraction (XRD) techniques. The deposition of ZnO on the microsphere walls was observed using FE‐SEM, ESEM and HRTEM which was further confirmed using the XRD and ultraviolet–visible absorption data. The hydrogen storage studies done on these samples at 200 °C and 10‐bar pressure for 5 h showed that the hydrogen storage increased when the Zn percentage in the sample increased from 0 to 2%. The percentage of zinc beyond 2, in the microspheres, showed a decline in the hydrogen storage capacity. The closure of the nanopores due to the ZnO nanocrystal deposition on the microsphere surface reduced the hydrogen storage capacity. The hydrogen storage capacity of HAZn2 was found 3.26 wt% for 10‐bar pressure at 200 °C. Copyright © 2015 John Wiley & Sons, Ltd.     

Production and characterization of hollow glass microspheres with high diffusivity for hydrogen storage

A process is developed to produce high diffusivity hollow glass microspheres (HGMs) with high concentration of silica for applications in hydrogen storage by volatilizing alkali and boron oxides in shell-forming process. We investigate the effects of the initial glass compositions of gel particles, the pressure and composition of furnace atmosphere, the temperature and length of refining zone on the diffusivity, quality and yield of the resulting HGMs. The results show that with the preferred total contents of alkali oxides and the ratios of potassium to sodium in the initial glass compositions, the ultimate concentrations of SiO₂ in the resulting HGMs can be up to 95%, with most alkali and boron oxides being volatilized in the refining process. The quality and yield of the high silica HGMs change significantly with the initial glass compositions of the gel particles. The total alkali oxide concentrations ranging from 15% to 20% in the initial glass compositions are preferred to obtain high silica HGMs with high quality and yield. The permeability coefficients of the resulting HGMs can be improved remarkably by increasing the temperature and length of the refining zone. The permeability coefficients of the high silica HGMs to hydrogen gas at ambient temperature are between 3 and 4 × 10⁻²⁰ (mol·m)/(m²·s·Pa).     

Hexagonal boron nitride (h-BN) nanoparticles decorated multi-walled carbon nanotubes (MWCNT) for hydrogen storage

Hydrogen is considered as the most promising clean energy carrier because of its abundance, environmental friendliness and high conversion efficiency. However, developing safe, compact, light weight and cost-effective hydrogen storage materials is one of the most technically challenging barriers to the widespread use of hydrogen as fuel. The present work reports the hydrogen storage performance of multi-walled carbon nanotubes (MWCNT)/hexagonal boron nitride (h-BN) nanocomposites (MWCNT/h-BN), where ultrasonication method is adopted for the synthesis of the MWCNT/h-BN nanocomposites. Hydrogenation process was carried out using Seiverts-like hydrogenation setup. Characterization techniques such as X-ray Diffraction (XRD), Micro-Raman Spectroscopy, Fourier Transform Infrared (FTIR) Spectroscopy, Scanning Electron Microscopy (SEM), Energy Dispersive X-Ray Spectroscopy (EDX), Nitrogen adsorption–desorption isothermal studies (BET), CHN-elemental analysis and Thermogravimetric Analysis (TGA) were used to analyze the samples at various stages of the experiment. A maximum of 2.3 wt% hydrogen storage is achieved in the case of acid treated MWCNTs (A-MWCNT) with 5 wt% of h-BN nanoparticles compared to pure MWCNTs that could store 0.15 wt% only. Moreover the calculated binding energy (0.42 eV) of stored hydrogen of A-MWCNT with 5 wt% of h-BN nanocomposite lies in the recommended range of binding energy (0.2–0.6 eV) for fuel cell applications. The TG study shows that 100% desorption is achieved at the temperature range of 120–410 °C and confirms that the prepared hydrogen storage medium will serve effectively in the realm of hydrogen fuel economy in near future.     

A hybrid hydrolytic hydrogen storage system based on catalyst‐coated hollow glass microspheres

Hydrogen‐pressurized hollow glass microspheres (HGMs) in combination with a hydride bear the potential of storing hydrogen in feasible amounts. Therefore, the approximately 20‐µm diameter spheres are heated up and pressurized with hydrogen at a pressure of 85 MPa, so hydrogen diffuses into the spheres. After the spheres are cooled down, hydrogen can be stored at room temperature without excessive security measures. To release the stored hydrogen, heat has to be applied again to reach temperatures of about 250 °C (523.15 K). To reach this temperature, it is suggested in this work to use an exothermal chemical reaction, which produces hydrogen as a by‐product. In this case, an NaBH₄–water reaction will be discussed, which has to be initialized by a catalyst deployed on the HGMs. It will be shown that hydrogen storage densities of up to 20 wt% and 50 kg/m³ can be theoretically achieved with the proposed hydrogen storage system consisting of hydrogen‐pressurized HGMs and a hydride, that is, NaBH₄. Volumetric storage density and other aspects, such as water management, temperature restriction, stoichiometric restriction and hydrogen diffusion through glass, will be discussed. Due to resulting high water vapour pressures, a pressure vessel will still be needed in the concept. This paper shall give an overview of theoretically achievable storage densities with the proposed system. Experiments were carried out regarding catalytic promoted hydrolysis with HGMs, and resulting storage densities were determined. These experiments show good agreement with theory. However, they will be addressed only briefly in the outlook of the paper because a detailed discussion would go beyond the scope of this work. Copyright © 2016 John Wiley & Sons, Ltd.     

Tests on a metal hydride based thermal energy storage system

In this paper, the performance tests on Mg + 30% MmNi₄ based thermal energy storage device is presented. Experiments were carried out at different supply pressures (10–30 bar) and absorption temperatures (120–150 °C). The effects of hydrogen supply pressure and absorption temperature on the amount of hydrogen/heat stored and thermal energy storage coefficient are presented. The maximum hydrogen storage capacity of 2.5wt% is reported at the operating conditions of 20 bar supply pressure and 150 °C absorption temperature. For a given absorption temperature of 150 °C, the thermal energy storage coefficient is found to increase from 0.5 at 10 bar to 0.74 at 30 bar supply pressure. For the given operating conditions of 20 bar supply pressure and 150 °C absorption temperature, the maximum amount of heat stored is about 0.714 MJ/kg and the corresponding thermal energy storage coefficient is 0.74.     

Development of hydrogen storage reactor using composite of metal hydride materials with ENG

Hydrogen is widely accepted as a promising energy carrier replacing fossil fuels. In this context hydrogen storage is one of the critical challenges in realizing hydrogen economy which relies on hydrogen as the commercial fuel. Due to very low volumetric energy density of pure hydrogen, it is highly compressed as a gas phase or liquified at extremely low temperature. However, chemically combined state in other materials has advantages in terms of storage conditions and associated safety concerns.The present study focuses on a development of a hydrogen storage applicable to special fuel cell (FC) mobilities such as forklift but not limited to. We adopts a solid-state storage method using metal hydride composite prepared by processing La_0.9Ce_0.1Ni₅ and extended natural graphite (ENG). The isothermal hydrogen absorption/desorption behavior of the composite is measured at 20–80 °C. The results suggest that around 10 bar is sufficient to store 1.2 wt% of hydrogen. A cylindrical reactor is manufactured and experiments are carried out with the fabricated hydrogen storage material by changing operation conditions. The results of satisfaction are obtained in terms of the amount of hydrogen storage (>83 standard liter) and the absorption time (~10 min) under relatively moderate conditions of temperature (~19 °C) and pressure (~11 bar).As for scaling-up, a reactor of 2.0 kWh is designed based on the experimental results. CFD analysis is performed based on the hottest operation conditions focusing on a cooling water flow. The flow pattern and the temperature distribution of the cooling water are expected to be adequate not deviating from the stable operating conditions. CFD would be further applied to optimize the incorporated modular reactors.     

Temperature controlled three-stage catalytic dehydrogenation and cycle performance of perhydro-9-ethylcarbazole

Organic liquid heteroaromatic compounds, e.g. 9-ethylcarbazole, are potentially promising hydrogen storage materials because they can be catalytically hydrogenated and dehydrogenated at relatively moderate temperatures. In the present work, the cyclic hydrogenation of 9-ethylcarbazole and the temperature controlled stage-wise dehydrogenation of perhydro-9-ethylcarbazole were investigated. Full hydrogenation of 9-ethylcarbazole was realized over a 5 wt% Ru/Al₂O₃ catalyst at 180 °C and 80 bar, yielding a gravimetric density of 5.79 wt%. The catalytic dehydrogenation of perhydro-9-ethylcarbazole over a 5 wt% Pd/Al₂O₃ catalyst was found to undergo a three-stage process, i.e. perhydro-9-ethylcarbazole → octahydro-9-ethylcarbazole, octahydro-9-ethylcarbazole → tetrahydro-9-ethylcarbazole, and tetrahydro-9-ethylcarbazole → 9-ethylcarbazole with the initial reaction temperatures of 128 °C, 145 °C and 178 °C, respectively. Our results indicate that 9-ethylcarbazole displays an excellent cycle performance with very little capacity degradation after 10 cycles of catalytic hydrogenation and dehydrogenation. The hydrogen gas produced from the dehydrogenation possesses a high purity of over 99.99% with no carbon monoxide or other poisonous gases for fuel cells.     

Fast hydrogen generation from NaBH4 hydrolysis catalyzed by carbon aerogels supported cobalt nanoparticles

Carbon aerogels (CAs) with oxygen-rich functional groups and high surface area are synthesized by hydrothermal treatment of glucose in the presence of boric acid, and are used as the support for loading cobalt catalysts (CAs/Co). Cobalt nanoparticles distribute uniformly on the surface of ACs, creating highly dispersed catalytic active sites for hydrolysis of alkaline sodium borohydride solution. A rapid hydrogen generation rate of 11.22 L min⁻¹ g_(cobalt)⁻¹ is achieved at 25 °C by hydrolysis of 1 wt% NaBH₄ solution containing 10 wt% NaOH and 20 mg the CAs/Co catalyst with a cobalt loading of 18.71 wt%. Furthermore, various influences are systematically investigated to reveal the hydrolysis kinetics characteristics. The activation energy is found to be 38.4 kJ mol⁻¹. Furthermore, the CAs/Co catalyst can be reusable and its activity almost remains unchanged after recycling, indicating its promising applications in fuel cell.     

Hydrogenation/dehydrogenation in MgH2-activated carbon composites prepared by ball milling

A systematic investigation was performed on the hydrogen storage behaviors of ball-milled MgH₂-activated carbon (AC) composites. Differential Scanning Calorimetry (DSC) measurement on the desorption temperature was carried out and indicated that the onset and peak temperatures both decreased with increasing AC adding amount, for example, the desorption peak temperature shifted from 349 °C for 1 wt% AC to 316 °C for 20 wt% AC. Furthermore, it is noted that the hydrogen absorption capacity and hydriding kinetics of the composites were also dependent on the adding amount of AC, and the optimum condition could be achieved by mechanical milling of MgH₂ with 5 wt% AC. The Mg-5wt%AC composite can absorb about 6.5 wt% hydrogen within 7 min at 300 °C and 6.7 wt% within 2 h at 200 °C, respectively. It is also demonstrated that MgH₂-5wt% AC exhibited good hydrogen desorption property that could release 6.5 wt% at 330 °C within 30 min. X-ray diffraction patterns (XRD) and transmission electron microscopy (TEM) observations revealed that the grain size of the synthesized composites decreased with increasing AC amount. This may contribute to the improvement of hydrogen storage in MgH₂-AC composites.     

Synergetic effect of reactive ball milling and cold pressing on enhancing the hydrogen storage behavior of nanocomposite MgH2/10 wt% TiMn2 binary system

Intermetallic TiMn₂ compound was employed for improving the de/rehydrogenation kinetics behaviors of MgH₂ powders. The metal hydride powders, obtained after 200 h of reactive ball milling was doped with 10 wt% TiMn₂ powders and high-energy ball milled under pressurized hydrogen of 70 bar for 50 h. The cold-pressing technique was used to consolidate them into 36-green buttons with 12 mm in diameter. During consolidation, the hard TiMn₂ spherical powders deeply embedded into MgH₂ matrix to form homogeneous nanocomposite bulk material. The apparent activation energies of hydrogenation and dehydrogenation for the fabricated buttons were 19.3 kJ/mol and 82.9 kJ/mol, respectively. The present MgH₂/10 wt% TiMn₂ nanocomposite binary system possessed superior hydrogenation/dehydrogenation kinetics at 225 °C to absorb/desorb 5.1 wt% hydrogen at 10 bar/200 mbar H₂ within 100 s and 400 s, respectively. This new system revealed good cyclability of achieving 414 cycles within 600 h continuously without degradations. For the present study, the consolidated buttons were used as solid-state hydrogen storage for feeding proton-exchange membrane fuel cell through a house made Ti-reactor at 250 °C. This nanocomposite system possessed good capability for providing the fuel cell with hydrogen flow at an average rate of 150 ml/min. The average current and voltage outputs were 3 A and 5.5 V, respectively.     

Modeling and optimization of composite thermal insulation system with HGMs and VDMLI for liquid hydrogen on orbit storage

The passive thermal insulation system for liquid hydrogen (LH₂) on orbit storage mainly consists of foam and variable density multilayer insulation (VDMLI) which have been considered as the most efficient and reliable thermal insulation system. The foam provides main heat leak protection on launch stage and the VDMLI plays a major role on orbit stage. However, compared with the extremely low thermal conductivity of VDMLI (1 × 10⁻⁵ W/(m·K)) at high vacuum, the foam was almost useless. Recently, based on hollow glass microspheres (HGMs) we have proposed the HGMs-VDMLI system which performs better than foam-VDMLI system. In order to improve insulation performance and balance weigh and environmental adaptability of passive insulation system, the HGMs-VDMLI insulation system should be configured optimally. In this paper, the thickness of HGMs and the number and arrangement of spacers of VDMLI were configured optimally by the “layer by layer” model. The effective thicknesses of HGMs were 25 mm for 60 layers MLI and 20 mm for 45 layers VDMLI. Compared with 35 mm foam and 45 layers VDMLI system, the heat flux of 20 mm HGMs and 45 layers VDMLI system was reduced by 11.97% with the same weight, or the weight of which was reduced by 9.91% with the same heat flux. Moreover, the effects of warm boundary temperature (WBT) and vacuum pressure on thermal insulation performance of the system were also discussed.     

Experimental investigation of a liquid cooled high temperature proton exchange membrane (HT-PEM) fuel cell coupled to a sodium alanate tank

In high temperature proton exchange membrane (HT-PEM) fuel cells, waste heat at approximately 160 °C is produced, which can be used for thermal integration of solid state hydrogen storage systems. In the present study, an HT-PEM fuel cell stack (400 W) with direct liquid cooling is characterized and coupled to a separately characterized sodium alanate storage tank (300 g material). The coupled system is studied in steady state for 20 min operation and all relevant heat flows are determined. Even though heat losses at that specific power and temperature level cannot be completely avoided, it is demonstrated that the amount of heat transferred from the fuel cell stack to the cooling liquid circuit is sufficient to desorb the necessary amount of hydrogen from the storage tank. Furthermore, it is shown that the reaction rate of the sodium alanate at 160 °C and 1.7 bar is adequate to provide the hydrogen to the fuel cell stack. Based on these experimental investigations, a set of recommendations is given for the future design and layout of similar coupled systems.     

Effect of ball milling on structural and hydrogen storage properties of Mg - x wt% FeTi (x=2 & 5) solid solutions

The effects of milling time on structural and hydrogen storage properties of Mg-xwt% FeTi (x = 2 & 5) solid solutions prepared by ball milling have been investigated. The solid solutions were analyzed by X-ray Diffraction (XRD) and Scanning Electron Microscope (SEM). It is shown that the application of mechanical (ball) milling is a simple technique to produce nanocrystalline powder. A clear reduction of crystallite size with an increase of microstrain is observed with increasing milling time. Hydrogen absorption isotherms have been measured at pressures up to 9 bar and in a temperature range 553 K to 583 K. After 5 h milling results show maximum hydrogen storage 5.32 wt% for Mg-2wt% FeTi while 5.21 wt% for Mg-5wt% FeTi solid solutions and also found that the hydrogen absorption pressure of the ball-milled sample is lower than that of the as-prepared (0 h milling) sample.     

Thermal modeling of LmNi4.91Sn0.15 based solid state hydrogen storage device with embedded cooling tubes

A 2-D mathematical model is developed for predicting the minimum charging/discharging time of the metal hydride based hydrogen storage device by varying the number of cooling tubes embedded in it. This study is extended to 3-D mathematical model for predicting the hydriding and dehydriding characteristics of LmNi_4.91Sn_0.15 based hydrogen storage device with 60 embedded cooling tubes (ECT) using COMSOL Multiphysics 4.3. The performance of the hydrogen storage device during hydriding/dehydriding process is presented for different supply pressure (10–35 bar), hot fluid temperature (30–60 °C) and effective thermal conductivity of hydride bed (0.2–2.5 W/(m?K)). It is observed that the rate of heat transfer and the hydriding and dehydriding rates are enhanced when the number of ECT is increased from 24 to 70. For the reactor with 60 ECT, the rate of hydrogen absorption is rapid for the supply pressure of 35 bar and hydride bed effective thermal conductivity of 2.5 W/(m?K). The numerically predicted hydrogen storage capacity (wt%) and amount of hydrogen desorbed (wt%) are compared with experimental data and found a good accord between them.     

Metal hydride hydrogen storage tank for fuel cell utility vehicles

The “low-temperature” intermetallic hydrides with hydrogen storage capacities below 2 wt% can provide compact H₂ storage simultaneously serving as a ballast. Thus, their low weight capacity, which is usually considered as a major disadvantage to their use in vehicular H₂ storage applications, is an advantage for the heavy duty utility vehicles. Here, we present new engineering solutions of a MH hydrogen storage tank for fuel cell utility vehicles which combines compactness, adjustable high weight, as well as good dynamics of hydrogen charge/discharge. The tank is an assembly of several MH cassettes each comprising several MH containers made of stainless steel tube with embedded (pressed-in) perforated copper fins and filled with a powder of a composite MH material which contains AB₂- and AB₅-type hydride forming alloys and expanded natural graphite. The assembly of the MH containers staggered together with heating/cooling tubes in the cassette is encased in molten lead followed by the solidification of the latter. The tank can provide >2 h long H₂ supply to the fuel cell stack operated at 11 kWe (H₂ flow rate of 120 NL/min). The refuelling time of the MH tank (T = 15–20 °C, P(H₂) = 100–150 bar) is about 15–20 min.     

Different effects of temperature on supramolecular protein and non-protein materials in hydrogen storage

The storage of large quantities of hydrogen at ambient temperature is a key factor in establishing a hydrogen-based economy. One strategy for hydrogen storage is to exploit the interaction between H₂ and a solid material by physisorption of hydrogen on porous materials. However, physisorption materials containing MOF, porous carbons, zeolites, clathrates, and synthesized organic polymers physisorb only about 1 wt% of H₂ at ambient temperature. One approach to solving this problem is to prepare new classes of physisorption materials which exhibits a mechanism different from the reported materials in hydrogen storage. Here we report the synthesis of apo cross-linked ferritin supramolecules by disulfide bonds, and their holo form. Unlike non-protein adsorbents, the hydrogen storage capacity of these protein materials increases as a function of temperature over the range of 20–40 °C. The holo supramolecules enable the adsorption of hydrogen up to 3.51 wt% at 40 °C and 40 bar H₂. In contrast, non-protein physisorption materials such as activated carbon and nano Fe₂O₃ marginally adsorb hydrogen, and, as reported, their ability to adsorb hydrogen decreases with increasing temperature under the same experimental condition. These results demonstrate that protein materials have a unique hydrogen storage mechanism which offers new opportunities in exploration of physisorption materials at ambient temperature.     

Energy storage of thermally reduced graphene oxide

The energy-storage capacity of reduced graphene oxide (rGO) is investigated in this study. The rGO used here was prepared by thermal annealing under a nitrogen atmosphere at various temperatures (300, 400, 500 and 600 °C). We measured high-pressure H₂ isotherms at 77 K and the electrochemical performance of four rGO samples as anode materials in Li-ion batteries (LIBs). A maximum H₂ storage capacity of ∼5.0 wt% and a reversible charge/discharge capacity of 1220 mAh/g at a current density of 30 mA/g were achieved with rGO annealed at 400 °C with a pore size of approximately 6.7 Å. Thus, an optimal pore size exists for hydrogen and lithium storage, which is similar to the optimum interlayer distance (6.5 Å) of graphene oxide for hydrogen storage applications.