Efficient and highly rapid hydrogen release from ball-milled 3NH3BH3/MMgH3 (M = Na,K, Rb) mixtures at low temperatures

The stoichiometric reactions of ammonia borane (NH₃BH₃, AB) and selected alkali or alkaline-earth metal hydrides produce metal amidoboranes, which possess dehydrogenation property advantages over their parent AB. However, the losses of hydrogen capacity and chemical energy in the preparation process make metal amidoboranes less energy-effective for hydrogen storage application. In the present study, by combining the M⁺–Mg²⁺ double cations remarkably lowers the reactivity of the alkali metal hydrides toward AB. As a result, the starting Mg-based ternary hydrides MMgH₃ (M = Na, K, Rb) and AB phases are largely stable in the mechanical milling process, but transform to the corresponding mixed-cation amidoboranes in the subsequent heating process. Importantly, when the post-milled 3AB/MMgH₃ mixtures are isothermally heated at above 60 °C using water bath, the formation and decomposition processes of the mixed-cation amidoboranes can be favorably combined, giving rise to rapid and efficient dehydrogenation performances at the mild temperatures (60–80 °C). The results acquired may provide a generalized reactions coupling strategy for designing and synthesis other potentially efficient hydrogen storage system.     

Mg2FeH6–LiBH4 and Mg2FeH6–LiNH2 composite materials for hydrogen storage

Two composite hydrogen storage materials based on Mg₂FeH₆ were investigated for the first time. The Mg₂FeH₆–LiBH₄ composite of molar ratio 1:5 showed a hydrogen desorption capacity of 5.6 wt.% at 370 °C, and could be rehydrogenated to 3.6 wt.% with the formation of MgH₂, as the material was heated to 445 °C and held at this temperature. The Mg₂FeH₆–LiNH₂ composite of 3:10 molar ratio exhibited a hydrogen desorption capacity of 4.3 wt.% and released hydrogen at 100 °C lower then the Mg₂FeH₆–LiBH₄ composite, but this mixture could not be rehydrogenated. Compared to neat Mg₂FeH₆, both composites show enhanced hydrogen storage properties in terms of desorption kinetics and capacity at these low temperatures. In particular, Mg₂FeH₆–LiNH₂ exhibits a much lower desorption temperature than neat Mg₂FeH₆, but only Mg₂FeH₆–LiBH₄ re-absorbs hydrogen.     

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.     

Effective synthesis of Mg2CoH5 by reactive mechanical milling and its hydrogen sorption behavior after cycling

Mg₂CoH₅ was synthesized by reactive mechanical milling (RMM) under hydrogen atmosphere (0.5 MPa) from 2MgH₂–Co and 3MgH₂–Co mixtures, with a yield >80%. The microstructure, structure and thermal behavior of the phases formed during the processing were investigated by transmission electron microscopy, X-ray diffraction and differential scanning calorimetry. Kinetic properties of the reaction with hydrogen of the 2MgH₂–Co and 3MgH₂–Co mixtures after RMM were evaluated using modified Sieverts-type equipment. The 3MgH₂–Co mixture showed better properties for storage applications, with its highest rate of hydrogen absorption and desorption at 300 °C, its storage capacity of about 3.7 wt% in less than 100 s, and good stability after cycling. Although the starting material presents Mg₂CoH₅ as majority phase, the cycling leads to disproportion between Mg and Co. We obtained a mixture of Mg₂CoH₅, Mg₆Co₂H₁₁ and MgH₂ hydrides, as well as other phases such as Co and/or Mg, depending on experimental conditions.     

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.     

Effects of nano additives on hydrogen storage behavior of the multinary complex hydride LiBH4/LiNH2/MgH2

Multinary complex hydrides comprised of borohydrides, amides and metal hydrides have been synthesized using the solid state mechano-chemical process. After the optimization of the system, it was found that LiBH₄/LiNH₂/MgH₂ exhibits potential reversible hydrogen storage behavior (>6 wt.%) at temperatures of 125–175 °C. To further improve the hydrogen performance of the system, various nano additives namely, nickel, cobalt, iron, copper, and manganese were investigated. It was observed that some of these additives (Co, Ni) lowered the hydrogen release temperature at least 75–100 °C in the major hydrogen decomposition step. While other additives acted as catalysts and increased the rate at which hydrogen was released. Combinatorial addition of selected materials were also investigated and found to have both a positive effect on kinetics and reduction in hydrogen desorption temperature.     

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.     

Thermochemical recycling of hydrolyzed NaBH4. Part I: In-situ and ex-situ evaluations

This paper presents a combined application of in-situ and ex-situ evaluations of products obtained by thermochemical recycling process of NaBH₄ from NaBO₂–Mg–H₂ ternary system. In-situ yield evaluation according to on-line pressure measurements of hydrogen gas, although already applied by some authors, is presented here with an innovative analysis which offers a thorough comprehension of the NaBH₄ regeneration process making feasible the qualitative and quantitative estimations of product and by-product. On the basis of in-situ observations, NaBH₄ formation in presence of NaBO₂–Mg–H₂ ternary system initiates slowly from 400 °C and accelerates above 550 °C to the melting point of Mg at 650 °C. MgH₂ is significantly produced between 370 °C and 450 °C in both heating and cooling. The amounts of these products produced at the different temperatures are clearly detectable by hydrogen pressure drops. Additionally, ex-situ evaluations by titration of NaBH₄ have also been performed in order to confirm the correct interpretation of the experimental data.     

Processing analysis of the ternary LiNH2–MgH2–LiBH4 system for hydrogen storage

In this article, we investigate the ternary LiNH₂–MgH₂–LiBH₄ hydrogen storage system by adopting various processing reaction pathways. The stoichiometric ratio of LiNH₂:MgH₂:LiBH₄ is kept constant with a 2:1:1 molar ratio. All samples are prepared using solid-state mechano-chemical synthesis with a constant rotational speed, but with varying milling duration. Furthermore, the order of addition of parent compounds as well as the crystallite size of MgH₂ are varied before milling. All samples are intimate mixtures of Li–B–N–H quaternary hydride phase with MgH₂, as evidenced by XRD and FTIR measurements. It is found that the samples with MgH₂ crystallite sizes of approximately 10 nm exhibit lower initial hydrogen release at a temperature of 150 °C. Furthermore, it is observed that the crystallite size of Li–B–N–H has a significant effect on the amount of hydrogen release with an optimum size of 28 nm. The as-synthesized hydrides exhibit two main hydrogen release temperatures, one around 160 °C and the other around 300 °C. The main hydrogen release temperature is reduced from 310 °C to 270 °C, while hydrogen is first reversibly released at temperatures as low as 150 °C with a total hydrogen capacity of ∼6 wt.%. Detailed thermal, capacity, structural and microstructural properties are discussed and correlated with the activation energies of these materials.     

Cycle life and hydrogen storage properties of mechanical alloyed Ca1−xZrxNi5−yCry; (x = 0, 0.05 and y = 0, 0.1)

CaNi₅–based alloys have been synthesized by mechanical alloying followed by isothermal annealing. The formation of the CaNi₅ structure occurred when the milled powders were heated at 800 °C under vacuum for 3 h. The abundance of CaNi₅ phase in the alloys ranges from 60 to 70 wt.%. Replacement of Zr into the Ca site reduces the unit cell volume of CaNi₅ whilst replacement of Cr into the Ni site slightly increases the unit cell volume. The hydrogen storage capacity of all substituted alloys is decreased and the hydrogen sorption plateau regions are narrowed compared to those of pure CaNi₅. Substitution of Zr into the Ca site extinguishes the flat plateau region unlike replacement of Cr into the Ni site where a flat plateau is maintained. The reaction enthalpy ΔH for both absorption and desorption are directly proportional to the unit cell volume of the alloys. The hydrogen storage capacity of all alloys rapidly decays for the first 50 cycles at 85 °C followed by a more gradual decline after 50 further cycles. The hydrogen storage capacity of the alloys after 200 cycles is in the range of 65–75% of the initial capacity.     

Effect of metal atom substitutions in Li based hydrides for hydrogen storage

By using density functional theory and the full-potential linearised augmented plane wave method, the effect of alkali (AM) and transition metal (TM) atom substitutions in Li based hydrides (Li₇XH₈ X (AM) = Na, K, Rb and X (TM) = Ti, V, Cr) was investigated, by studying their formation energies and electron properties, aiming at improving hydrogen storage performance. The calculated formation energy values indicate that there is a gradual degradation in stability due to alkali substitutions from Na to Rb and to transition metal substitutions from Ti to Cr in Li₇XH₈. The found degradations of stability in Li₇XH₈ were better compared concomitantly with corresponding gravimetric hydrogen storage variations. The less stable phase with least variation in gravimetric hydrogen storage was found to be Li₇CrH₈ among all alkali and transition metal atom substitutions. The density of states and the electron density support our observations.     

Measurement and analysis of reaction kinetics of La – based hydride pairs suitable for metal hydride – based cooling systems

The reaction kinetics of metal hydride pairs consisting of La_0.9Ce_0.1Ni₅, La_0.8Ce_0.2Ni₅, LaNi_4.7Al_0.3 and LaNi_4.6Al_0.4 were measured at different temperatures to determine their suitability for metal hydride – based cooling systems (MHCSs). The effect of operating conditions and compositional changes on driving potential and reaction rates during cooling and regeneration processes was studied. The reaction rates were increased with Ce content and decreased with Al content. The cooling and regeneration time of MHCS, for working temperature range of 140 °C (heat source), 25 °C (heat sink) and 10 °C (cooling), were measured for each pair. The estimated cycle time took the following trend (La_0.8Ce_0.2Ni₅ – LaNi_4.7Al_0.3) < (La_0.9Ce_0.1Ni₅ – LaNi_4.7Al_0.3) < (La_0.8Ce_0.2Ni₅ – LaNi_4.6Al_0.4) < (La_0.9Ce_0.1Ni₅ – LaNi_4.6Al_0.4). Two reaction kinetics models namely Jander diffusion model (JDM) and Park – Lee model (PLM) were studied and employed for reaction kinetics analyses. The activation energies (E) of these hydrides were calculated using the Arrhenius plot. Estimated values of activation energies from these models were compared by substituting in the hydriding expression and accurate values of activation energies established for these hydrides.     

Ternary compounds in the magnesium–titanium hydrogen storage system

Mg–Ti–H samples were mechano-chemically synthesized by ball milling in argon atmosphere or under elevated hydrogen pressure. The detailed reaction mechanism during hydrogen release and uptake during continuous cycling was investigated by in-situ synchrotron radiation powder X-ray diffraction (SR-PXD) experiments. The thermal behaviour of the samples and hydrogen desorption properties were examined by simultaneous thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and mass spectrometry (MS) measurements. A ternary Ti–Mg–H compound with a fcc lattice form during mechano-chemical sample preparation in hydrogen atmosphere using metal powders, but not using metal hydrides as reactants. The amount of β-MgH₂ increases during the first hydrogen absorption cycle at 300 °C at the expense of the high-pressure polymorph, γ-MgH₂ and the amount of β-MgH₂ remain constant during the following hydrogenations. This study reveals that the ternary compound tends to absorb increasing amounts of magnesium in the dehydrogenated state during cycling. A strong coupling between the amounts of magnesium in the ternary Ti–Mg–H phase and the formation of magnesium and magnesium hydride during hydrogen release and uptake at 300 °C is observed. The composition and the amount of the Ti–Mg–H phase appear to be similar in the hydrogenated state. Fast absorption–desorption kinetics at 300 °C and lower onset temperatures for hydrogen release is observed for all investigated samples (lowest onset temperature of desorption T_on = 217 °C).     

Optimization of hydrogen charging process parameters for an advanced complex hydride reactor concept

Complex hydrides are identified as promising hydrogen storage media with gravimetric capacities up to 10 wt.%. However, the high temperatures required for the initiation of their hydrogen charging process and their slow kinetics prevent their integration in many practical applications. This paper discusses the challenge of addressing these issues by combining this kind of materials with the appropriate metal hydrides. For this purpose, the complex hydride, 2LiNH₂–1.1MgH₂–0.1LiBH₄–3 wt.% ZrCoH₃ (CxH) and the metal hydride, LaNi_4.3Al_0.4Mn_0.3 (MeH) have been selected as reference materials. The studied configuration corresponds to a tubular reactor where the metal hydride and the complex hydride, separated by a gas permeable layer, are embedded respectively in the centre and the annular ring of the reactor. A 1-dimensional finite element model and a dimensionless number comparing the dominance of the kinetics and the heat transfer processes have been developed to optimize the charging process for different thicknesses and volumetric ratios of the studied materials. For the selected cases, the influence of the thermal properties of the complex hydride and the operating conditions on the charging process is assessed. A sensitivity study has shown that the thermal conductivity of the CxH is the most important parameter influencing the hydrogen storage rate if thick MeH and CxH beds are considered. In contrast, the hydrogen loading time is significantly improved by increasing the coolant temperature for small thicknesses of the two storage media. Thereafter, the gravimetric and volumetric capacities resulting from the scale up of the optimized configurations to store 1 kg of hydrogen are calculated and results are discussed taking into account the interdependence of the different studied parameters.     

Sorption behavior of the MgH2–Mg2FeH6 hydride storage system synthesized by mechanical milling followed by sintering

The hydrogen sorption behavior of the Mg₂FeH₆–MgH₂ hydride system is investigated via in-situ synchrotron and laboratory powder X-ray diffraction (SR-PXD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), particle size distribution (PSD) and volumetric techniques. The Mg₂FeH₆–MgH₂ hydride system is obtained by mechanical milling in argon atmosphere followed by sintering at high temperature and hydrogen pressure. In-situ SR-PXD results show that upon hydriding MgH₂ is a precursor for Mg₂FeH₆ formation and remained as hydrided phase in the obtained material. Diffusion constraints preclude the further formation of Mg₂FeH₆. Upon dehydriding, our results suggest that MgH₂ and Mg₂FeH₆ decompose independently in a narrow temperature range between 275 and 300 °C. Moreover, the decomposition behavior of both hydrides in the Mg₂FeH₆–MgH₂ hydride mixture is influenced by each other via dual synergetic-destabilizing effects. The final hydriding/dehydriding products and therefore the kinetic behavior of the Mg₂FeH₆–MgH₂ hydride system exhibits a strong dependence on the temperature and pressure conditions.     

Theoretical calculation of hydrogen desorption energies of calcium hydride clusters

Recently calcium hydride has attracted attention as a possible component in ternary complex hydrides such as Ca(AlH₄)₂, Ca₂SiH_x and quaternary complex hydrides of the type Li–B–Ca–H. Although in bulk form CaH₂ decomposes reversibly above 600° centigrade we were motivated to see whether calcium hydride in cluster form has properties suitable for hydrogen storage. We report here the results of DFT calculations using VASP^® package for clusters Ca_nH_2n with n = 1, 2, 3, 4, 6, 8, 10, 12, 14, 16, 20 to get the ground state geometries, energies, bond lengths, and desorption energies, after molecular dynamics optimization. The desorption energy vs. cluster size n curve showed that the desorption energy goes up sharply to ∼1.4 eV per H₂ for n up to 4, followed by a broad maximum of ∼1.8 eV per H₂ around n = 12–14, and then tapers off to a nearly constant value of 1.6 eV per H₂ approximating bulk behavior, which compares favorably with previously reported results. Comparison of these results with those of Mg_nH_2n shows that Ca_nH_2n has a lesser potential as a hydrogen storage medium.     

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.