Hydrogen generation from hydrolysis of aluminum/graphite composites with a core–shell structure

Hydrogen generated by hydrolysis of metal aluminum with water is promising for portable fuel cell applications. However aluminum would not react with water to yield hydrogen at ordinary conditions due to the passive oxide film formed on its surface. In the present investigation, the aluminum/graphite composite were prepared by a ball milling process in an attempt to improve the reactivity of aluminum, using sphere-shape aluminum particles and laminate graphite as the initial materials and 2 wt% NaCl as the milling-assisted agent. The TEM observation showed that the Al particles are covered by graphite to form a core–shell structure. Such a Al/graphite composite material exhibited a pronounced hydrolysis reactivity with tap water to generate hydrogen while Al alone did not react with water. The presence of graphite could lower the hydrogen generation reaction temperature below 45 °C. Increasing the reaction temperature could obtain an increased hydrogen generation rate and the maximum hydrogen generation rate of 40 cm³ min⁻¹ g⁻¹ Al was obtained when the reaction temperature was increased to 75 °C. Prolonging milling time could also improve the Al hydrolysis reactivity in the composite particularly at a relatively low temperature. The XRD results identified that the hydrolysis byproducts are bayerite (Al(OH)₃) and boehmite (AlOOH). The microstructure-related hydrolysis reaction mechanism was finally proposed.     

Cobalt–iron–boron catalyst-induced aluminum–water reaction

Hydrogen generation based on the corrosion of aluminum has been evaluated with regard to its possible application in on-board mobile and portable power sources. In this study, the aluminum–water reaction induced by Co–Fe–B has been examined. SEM results have shown that the chain-like Co–Fe–B catalyst forms a network structure under the influence of an external magnetic field. Co–Fe–B is actually a mixture of cubic Fe and amorphous Co–Fe–B. The Fe content in Co–Fe–B increases with increasing mass of FeCl₃ used in its synthesis. An increase in the Fe content in Co–Fe–B shortens the induction time and improves the amount of hydrogen generated owing to the formation of Fe/Al, Co–Fe–B/Al, and Co–Fe–B/Fe micro galvanic cells. However, an increase in the Co–Fe–B content slightly decreases the amount of hydrogen generated owing to its agglomeration and oxidation. With increasing temperature, both the reaction rate and the amount of hydrogen generated are improved. The activation energy of this reaction, calculated from the maximum reaction rates at different temperatures, is 40 kJ mol⁻¹. Hydrogen is rapidly generated, without an induction time, upon the addition of consecutive batches of Al, because the occurrence of the high concentration of OH⁻ ions effectively accelerates the corrosion of Al.     

First principles study to identify the reversible reaction step of a multinary hydrogen storage “Li–Mg–B–N–H” system

A density functional theory study with the generalized gradient approximation (GGA) and projected augmented wave (PAW) method is performed for the hydrogen storage properties of the complex multinary storage Li–Mg–B–N–H system. Using ab initio methods, stability of the structures at finite temperatures is confirmed via. phonon spectrum calculations. Thermodynamic properties such as heat of reaction, and Gibbs energy for each reactant and product in the reaction steps in different temperature zones are calculated. It is found that reversibility occurs in the temperature range of 160–225 °C with approximately 4.38 wt % hydrogen storage capacity. The enthalpy of reversible re-/de-hydrogenation is found to be 55.17 kJ/mol H₂, which is supported by experimental data. The total hydrogen storage capacity of this material is calculated to be 8.76 wt% from the desorption behavior observed at different temperatures up to 350 °C. These theoretically established reactions are validated with the suggested mechanism from experimental observations for the dehydrogenation reaction of this Li–Mg–B–N–H multinary system. These efforts are expected to contribute toward identification of suitable hydrogen storage materials.     

Fabrication of AlLi and Al2Li3/Al4Li9 intermetallic compounds by molten salt electrolysis and their application for hydrogen generation from water

The concept of “hydrogen on demand” has been widely publicized. More importantly, the materials used to produce hydrogen on demand should be in themselves safe to handle. In present work, Al–Li intermetallic compounds (IMC) were fabricated in air by electrolysis from LiCl–KCl molten salt at 480 ± 25 °C. Bulk AlLi IMC and the bulk compound with mixture of Al₂Li₃ and Al₄Li₉ (Al₂Li₃/Al₄Li₉ IMC) were not pyrophoric and can be safely handled in air. When both compounds in contact with water, vigorous reaction occurred and H₂ was directly produced. The by-products after H₂ generation from AlLi IMC were a mixture of Li-containing α-Al and Li–Al hydrotalcite (hereafter referred to as Li–Al LDH). The by-product after H₂ generation from Al₂Li₃/Al₄Li₉ compound was a mixture of LiOH·H₂O and Li–Al LDH. Those by-products can be easily separated from water and may be reused as a resource. Approximately 500–860 ml of H₂ per weight (g) of the IMC compounds was generated in deionized water at room temperature. Experimentally, AlLi IMC powder and Al₂Li₃/Al₄Li₉ compound exhibit gravimetric hydrogen capacity of 7.0 wt.% and 5.4 wt.%, respectively. Although the energy consumed for fabricating Al–Li IMC compounds is a little larger than the energy provided by the generated H₂, the Al–Li IMC compounds are promising materials for producing hydrogen on demand without the necessity of hydrogen storage.     

Enhancement of hydrogen generation rate in reaction of aluminum with water

The aim of this investigation is to enhance hydrogen generation rate in aluminum–water reaction by improving the activity of aluminum particles and using the heat released during the reaction. This was accomplished by developing fresh surfaces by milling aluminum particles together with salt. Salt particles not only serve as nano-millers, but also surround activated particles and prevent re-oxidation of bare surfaces in the air. Therefore, the activated powder can be easily stored for a long time. Immersing the powder in warm water, the salt covers are washed away and hydrogen begins to release at a high rate until efficiency of 100% is achieved. The rate of reaction depends crucially on initial temperature of water. Hence, the mass of water was reduced to employ released energy to increase water temperature and, consequently, to increase hydrogen production rate. The optimum value of salt-to-aluminum mole ratio for achieving high activation, air-storage capability and 100% efficiency was obtained to be 2. When immersed in water, at initial temperatures of 55 and 70 °C, the powder lead to average hydrogen generation rate of ∼101 and ∼210 ml/min per 1 g of Al, respectively. To increase the rate of corrosion, three different alloys/composites of aluminum were prepared by mechanical alloying and activated with optimum salt-to-aluminum mole ratio. The alloys/composites formed galvanic cells after being immersed in water. In the case of aluminum–bismuth alloy, the average hydrogen generation rate increased to ∼287 and ∼713 ml/min per 1 g of Al, respectively.     

Preparation of Pt supported on mesoporous Mg–Al oxide catalysts for efficient dehydrogenation of methylcyclohexane

Hydrogen energy, characterizing by high-energy density, non-pollution and renewability, is regarded as an ideal clean green energy, and the chemical hydrogen storage is an optimal strategy to realize its large-scale utilization. In this study, to enhance the hydrogen evolution rate in the dehydrogenation of methylcyclohexane (MCH), Pt supported on Mg–Al oxide catalysts were prepared and the effects of the co-precipitation reaction time during the preparation of Mg–Al hydrotalcite on their structural properties were studied in detail. The results showed that both the pore diameter and Pt dispersion were increased after prolonging the precipitation reaction time. During the dehydrogenation of MCH, these resultant catalysts presented high activity and good stability: hydrogen evolution rate reached up to 1892 mmol·g_Pt^?1 min^?1 at 623 K and the conversion was still held at 92% after 218 h. Of course, a slight decrease on the conversion during the dehydrogenation reaction was also observed, which was mainly attributed to the aggregation of Pt particles at high temperature.     

A hybrid aluminum/hydrogen/air cell system

A hybrid aluminum/hydrogen/air cell system is developed to solve the parasitic hydrogen-generating problem in an alkaline aluminum/air battery. A H₂/air fuel cell is integrated into an Al/air battery so that the hydrogen generated by the parasitic reaction is utilized rather than wasted. A systematic study is conducted to investigate how the parasitic reaction and the added H₂/air cell affect the performance of the aluminum/air battery. The aluminum/air sub-cell has an open circuit voltage of 1.45 V and the hydrogen/air sub-cell of 1.05 V. The maximum power density of the entire hybrid system increases significantly by ∼20% after incorporating a H₂/air sub-cell. The system maximum power density ranges from 23 to 45 mW cm⁻² in 1–5 M NaOH electrolyte. The hybrid system is adaptable in concentrated alkaline electrolyte with significantly improved power output at no sacrifice of its overall efficiency.     

Improved reversible dehydrogenation of LiBH4–MgH2 composite by the synergistic effects of Al and MgO

In this paper, we report a novel method of improving the reversible dehydrogenation properties of the 2LiBH₄–MgH₂ composite. Our study found that mechanically milling with small amount of Al powder can markedly shorten or even eliminate the problematic incubation period that interrupts the dehydrogenation steps of the 2LiBH₄–MgH₂ composite. But the resulting composite showed serious kinetics degradation upon cycling. In an effort to solve this problem, we found that combined usage of small amounts of Al and MgO enabled the 2LiBH₄–MgH₂ composite to rapidly and reversibly deliver around 9 wt% hydrogen at 400 °C under 0.3 MPa H₂, which compares favorably with the dehydrogenation performance of the composites with transition-metal additives. A combination of phase/microstructural analyses and series of control experiments has been conducted to gain insight into the promoting effects of Al and MgO. It was found that Al and MgO additives act as precursor and promoter for the formation of AlB₂ heterogeneous nucleation sites, respectively.     

Reversible hydrogen storage in a 3NaBH4/YF3 composite

A 3NaBH₄/YF₃ hydrogen storage composite was prepared through ball milling and its hydrogen sorption properties were investigated. It is shown that NaBH₄ does not react with YF₃ during ball milling. The dehydrogenation of the composite starts at 423 °C, which is about 100 °C lower than the dehydrogenation temperature of pure NaBH₄, with a mass loss of 4.12 wt%. Pressure–Composition–Temperature tests reveal that the composite has reversible hydrogen sorption performance in the temperature range from 350 °C to 413 °C and under quite low hydrogenation plateau pressures (<1 MPa). Its maximum hydrogen storage capacity can reach up to 3.52 wt%. The dehydrogenated composite can absorb 3.2 wt% of hydrogen within 5 min at 400 °C. Based on the Pressure–Composition–Temperature analyses, the hydrogenation enthalpy of the composite is determined to be −46.05 kJ/mol H₂, while the dehydrogenation enthalpy is 176.76 kJ/mol H₂. The mechanism of reversible hydrogen sorption in the composite involves the decomposition and regeneration of NaBH₄ through the reaction with YF₃. Therefore, the addition of the YF₃ to NaBH₄ as a reagent forms a reversible hydrogen storage composite.     

Enhanced hydrogen storage properties of TiN–LiAlH4 composite

The hydrogen storage properties of LiAlH₄ doped efficient TiN catalyst were systematically investigated. We observe that TiN catalyst enhances the dehydrogenation kinetics and decreases the dehydrogenation temperature of LiAlH₄. The dehydrogenation behaviors of 2%TiN–LiAlH₄ are investigated using temperature programmed desorption (TPD), differential scanning calorimetry (DSC) and fourier transform infrared spectroscopy (FTIR). Interestingly, the onset hydrogen desorption temperature of 2%TiN–LiAlH₄ sample gets lowered from 151.0 °C to 90.0 °C with a faster kinetics, and the dehydrogenation rate reached a maximum value at 137.2 °C. By adding a small amount of as-prepared TiN, approximately 7.1 wt% of hydrogen can be released from the LiAlH₄ at 130 °C. Interestingly, the result of the FTIR indicates that the 2%TiN–LiAlH₄ maybe restore hydrogen under 5.5 MPa hydrogen. Moreover, 2%TiN–LiAlH₄ displayed a substantially reduced activation energy for LiAlH₄ dehydrogenation.     

Effects of MoS2 addition on the hydrogen storage properties of 2LiBH4–MgH2 systems

A 2LiBH₄–MgH₂–MoS₂ composite was prepared by solid-state ball milling, and the effects of MoS₂ as an additive on the hydrogen storage properties of 2LiBH₄–MgH₂ system together with the corresponding mechanism were investigated. As shown in the TG–DSC and MS results, with the addition of 20 wt.% of MoS₂, the onset dehydrogenation temperature is reduced to 206 °C, which is 113 °C lower than that of the pristine 2LiBH₄–MgH₂ system. Meanwhile, the total dehydrogenation amount can be increased from 9.26 wt.% to 10.47 wt.%, and no gas impurities such as B₂H₆ and H₂S are released. Furthermore, MoS₂ improves the dehydrogenation kinetics, and lowers the activation energy (E_a) 34.49 kJ mol⁻¹ of the dehydrogenation reaction between Mg and LiBH₄ to a value lower than that of the pristine 2LiBH₄–MgH₂ sample. According to the XRD test, Li₂S and MoB₂ are formed by the reaction between LiBH₄ and MoS₂, which act as catalysts and are responsible for the improved hydrogen storage properties of the 2LiBH₄–MgH₂ system.     

Burner-heated dehydrogenation of a liquid organic hydrogen carrier (LOHC) system

For a hydrogen-based economy, safe and efficient hydrogen storage is essential. Compared to other chemical hydrogen storage technologies, such as ammonia or methanol, liquid organic hydrogen carrier (LOHC) systems allow for a reversible storage of hydrogen while being easy to handle in a diesel-like manner. In our contribution, we describe for the first time the successful utilization of the exhaust gas enthalpy of a porous media burner to directly supply the dehydrogenation heat for a kW-scale dehydrogenation of the hydrogen-rich LOHC compound perhydro dibenzyltoluene (H18-DBT). Our setup demonstrates the dynamics of the dehydrogenation unit at a realized maximum hydrogen power of 3.9 kW_th, based on the lower heating value of the released hydrogen. For the intended applications with fluctuating hydrogen demand, e.g. a hydrogen refueling station (HRS) or stationary heating in buildings, a dynamic hydrogen supply from LOHC is important. Methane, e.g. from a biogas plant, is utilized in our scenario as a fuel source for the burner. Hydrogen is released within 30 min after cold start of the system. The dehydrogenation unit exhibits a power density relative to the reactor volume of about 0.5 kW_therm l⁻¹ based on the lower heating value of the hydrogen and a catalyst productivity of up to 0.65 g_H2 g_Pt⁻¹ min⁻¹ for hydrogen release from H18-DBT. An analysis of the by-products and reaction intermediates shows low by-product formation (e.g. maximum 0.6 wt.-% for high boilers and 0.9 wt.- % for low boilers) and uniform distribution of intermediates after the reaction. Thus, a relatively homogeneous temperature distribution and a uniform LOHC flow in the reaction zone can be assumed. Our findings illustrate the dynamics (heating rates of about 10 K min⁻¹) and performance of direct heating of a release unit with a burner and represent a significant step towards LOHC-based hydrogen provisioning systems at technically relevant scales.     

Enhancement of the H2 desorption properties of LiAlH4 doping with NiCo2O4 nanorods

Lithium aluminum hydride (LiAlH₄) is considered as an attractive candidate for hydrogen storage owing to its favorable thermodynamics and high hydrogen storage capacity. However, its reaction kinetics and thermodynamics have to be improved for the practical application. In our present work, we have systematically investigated the effect of NiCo₂O₄ (NCO) additive on the dehydrogenation properties and microstructure refinement in LiAlH₄. The dehydrogenation kinetics of LiAlH₄ can be significantly increased with the increase of NiCo₂O₄ content and dehydrogenation temperature. The 2 mol% NiCo₂O₄-doped LiAlH₄ (2% NCO–LiAlH₄) exhibits the superior dehydrogenation performances, which releases 4.95 wt% H₂ at 130 °C and 6.47 wt% H₂ at 150 °C within 150 min. In contrast, the undoped LiAlH₄ sample just releases <1 wt% H₂ after 150 min. About 3.7 wt.% of hydrogen can be released from 2% NCO–LiAlH₄ at 90 °C, where total 7.10 wt% of hydrogen is released at 150 °C. Moreover, 2% NCO–LiAlH₄ displayed remarkably reduced activation energy for the dehydrogenation of LiAlH₄.     

Study on dehydrogenation and oxidation kinetics mechanisms of micron α-AlH3 in an oxidative atmosphere

Aluminum hydride (AlH₃) exhibits attractive properties, such as high hydrogen/energy storage, relatively good stability, and low dehydrogenation temperature. Thus, AlH₃ has appreciable prospects as a component in solid propellant for promoting the specific impulse of rocket engines and for effectively reducing the erosion of engine nozzles. The TG-MS, SEM, XRD, XPS, and EDS results show that the thermal reaction of AlH₃ is divided into three stages: (1) Dehydrogenation (below 210 °C, 2AlH₃→2Al+3H₂) starts from the inherent defects on the surface with an incomplete decomposition due to the passivation reaction in which an amorphous Al₂O₃ layer is formed to encapsulate the contained hydrogen. This is accompanied by nucleation and growth of Al nuclei from the outer particles to the inner particles and the formation of H₂O via oxidation of the generated hydrogen. (2) The primary oxidation of Al (210–650 °C, 4Al+3O₂→2γ-Al₂O₃) is attributed to a discontinuous layer of γ-Al₂O₃, which is transformed from amorphous Al₂O₃ that results in the reaction of naked residual Al and O₂. (3) The secondary oxidation of residual Al (above 650 °C, 4Al+3O₂→2α-Al₂O₃) occurs because of the crystal conversion from γ-Al₂O₃ to α-Al₂O₃, which leads to the shrinkage of the oxide shell and to the formation of cracks. Also, melting of residual Al breaks the shell, and this induces further oxidation. The results obtained for the microscopic kinetics mechanisms of dehydrogenation and oxidation of AlH₃, show a clear direction for research regarding modifications of AlH₃ as the theoretical foundation and are beneficial for the wide use of AlH₃ in applications such as solid propellant as an energetic material and as a hydrogen source for fuel cells.     

Study on the hydrogen storage properties and reaction mechanism of NaAlH4–MgH2–LiBH4 ternary-hydride system

In this paper, we report the hydrogen storage properties and reaction mechanism of NaAlH₄–MgH₂–LiBH₄ (1:1:1) ternary-hydride system prepared by ball milling. It was found that during ball milling, the NaAlH₄/MgH₂/LiBH₄ combination converted readily to the mixture of LiAlH₄/MgH₂/NaBH₄ and there is a mutual destabilization among the hydrides. Three major dehydrogenation steps were observed in the system, which corresponds to the decomposition of LiAlH₄, MgH₂, and NaBH₄, respectively. The onset dehydrogenation temperature of MgH₂ in this system is observed at around 275 °C, which is over 55 °C lower from that of as-milled MgH₂. Meanwhile, NaBH₄-relevant decomposition showed significant improvement, starts to release hydrogen at 370 °C, which is reduced by about 110 °C compared to the as-milled NaBH₄. The second and third steps decomposition enthalpy of the system were determined by differential scanning calorimetry measurements and the enthalpies were changed to be 61 and 100 kJ mol⁻¹ H₂ respectively, which are smaller than that of MgH₂ and NaBH₄ alone. From the Kissinger plot, the apparent activation energy, E_A, for the decomposition of MgH₂ and NaBH₄ in the composite was reduced to 96.85 and 111.74 kJ mol⁻¹ respectively. It is believed that the enhancement of the dehydrogenation properties was attributed to the formation of intermediate compounds, including Li–Mg, Mg–Al, and Mg–Al–B alloys, upon dehydrogenation, which change the thermodynamics of the reactions through altering the de/rehydrogenation pathway.     

Al–Li3AlH6: A novel composite with high activity for hydrogen generation

A novel material for hydrogen generation with high capacity of H₂ generation has been successfully prepared by ball milling the mixture of Al and home-made fresh Li₃AlH₆ powder. Its theoretical capacity of hydrogen released is higher than that of pure Al. Results obtained have shown conversion efficiency of Al–Li₃AlH₆ composite can be close to 100% by increasing the content of Li₃AlH₆. When the content of Li₃AlH₆ is 20 wt%, the maximum hydrogen generation rate and hydrogen yield are 2737.6 mL g⁻¹ min⁻¹ and 1513.1 mL g⁻¹, respectively, at room temperature. By XRD, SEM analyses and reaction heat measurements, it demonstrates that the additive Li₃AlH₆ can provide an additional source of H₂ and an alkaline environment (LiOH) as well as additional heat to promote the Al/H₂O reaction. Therefore, the Al–Li₃AlH₆ composite has a very high activity and high capacity of hydrogen released.     

Excellent catalytic effect of LaNi5 on hydrogen storage properties for aluminium hydride at mild temperature

The catalytic effect of rare-earth hydrogen storage alloy is investigated for dehydrogenation of alane, which shows a significantly reduced onset dehydrogenation temperature (86 °C) with a high-purity hydrogen storage capacity of 8.6 wt% and an improved dehydrogenation kinetics property (6.3 wt% of dehydrogenation at 100 °C within 60 min). The related mechanism is that the catalytic sites on the surface of the hydrogen storage alloy and the hydrogen storage sites of the entire bulk phase of the hydrogen storage reduce the dehydrogenation temperature of AlH₃ and improve the dehydrogenation kinetic performance of AlH₃. This facile and effective method significantly improves the dehydrogenation of AlH₃ and provides a promising strategy for metal hydride modification.     

Hydrogen generation from the reaction of Al pretreated in acidic or alkaline solution and water

Al and Al₂O₃ film react with strong acid or alkaline solution, bring the extensive corrosion. To decrease the corrosion, Al is first pretreated with a small amount of HCl, NaOH, NaAlO₂ and a mixture of NaAlO₂+Al(OH)₃ in this work. Al pretreatment allows for the rapid removal of oxide film, shortens the induction time and ensures the initial Al–H₂O reaction rate. Typically, immersion of the pretreated Al by a mixture of NaAlO₂+Al(OH)₃ into water, generates hydrogen rapidly without an induction time, and the average H₂ generation rate reaches 5.5 mL min⁻¹. As the Al–H₂O reaction proceeds, the potential changes, which is similar to hydrogen evolution of pretreated Al in water. Hydrogen generated rapidly with the consecutive addition of Al, and the initial hydrogen generation rate reaches ~37 mL min⁻¹. Therefore, Al pretreatment by a mixed alkaline solution is an effective method to accelerate hydrogen generation for the first cycle. Rapid and consecutive hydrogen generation by the Al–H₂O reaction could provide on-demand and high-purity hydrogen, meet some equipment requirements and promote the competition in renewable-energy sources.     

Reversible hydrogen storage in vapour deposited Mg-5 at.% Pd powder composites

Mg-5 at.% Pd powder composites derived from multilayered films of Mg and Pd deposited in Pd/Mg/Pd/Mg/Pd layer configuration by thermal evaporation reversibly store about 3.5 wt.% hydrogen up to 15 cycles under mild conditions of pressure and temperature. Hydrogenation takes place at 0.15 MPa hydrogen pressure while dehydrogenation occurs in a dynamic rotary vacuum. Each process is completed in about three hours. The temperature of a dehydrogenation or hydrogenation step is about 5–10 K higher than the preceding hydrogenation or dehydrogenation step. The hydrogenation temperature of the first cycle is 343 K whereas the dehydrogenation temperature of the 15th cycle is 423 K. The hydrogen storage capacity of composite is the manifestation of fine-grained microstructure of Mg and the catalytic properties of Pd. It declines beyond 423 K due to the exhaustion of metallic Pd as a result of the formation of Mg–Pd intermetallic compounds. This approach presents a simple and rapid method of preparing Mg–Pd composites for hydrogen storage applications.     

Integration of hydrogenation and dehydrogenation based on dibenzyltoluene as liquid organic hydrogen energy carrier

The heat transfer oil dibenzyltoluene (DBT) offered an intriguing approach for the scattered storage of renewable excess energy as a novel Liquid Organic Hydrogen Carrier (LOHC). The integration of hydrogenation and dehydrogenation in H0-DBT/H18-DBT pairs demonstrated that the feasibility of hydrogenation and dehydrogenation reaction conducted in one reactor with the same catalyst, which would be proposed to simplify the hydrogen storage process. The optimal reaction temperature based on the inhibition of ring opening and cracking was investigated combined with the ¹H NMR analysis. Meanwhile, the ideal catalyst 3 wt% Pt/Al₂O₃ for high hydrogen storage efficiency was screened out. Cycle tests of hydrogenation and dehydrogenation integration reaction had shown that the hydrogen storage efficiency was 84.6% after five cycle tests. The integration of hydrogenation and dehydrogenation reaction based on DBT exhibited the ideal thermal stability, which demonstrated its potential as a reversible H₂ carrier.