Hydrogen storage properties and mechanisms of the Mg(BH4)2–NaAlH4 system

Hydrogen storage properties and mechanisms of the combined Mg(BH₄)₂–NaAlH₄ system were investigated systematically. It was found that during ball milling, the Mg(BH₄)₂–xNaAlH₄ combination converted readily to the mixture of NaBH₄ and Mg(AlH₄)₂ with a metathesis reaction. The post-milled samples exhibited an apparent discrepancy in the hydrogen desorption behavior with respect to the pristine Mg(BH₄)₂ and NaAlH₄. Approximately 9.1 wt% of hydrogen was released from the Mg(BH₄)₂–2NaAlH₄ composite milled for 24 h with an onset temperature of 101 °C, which is lowered by 105 and 139 °C than that of NaAlH₄ and Mg(BH₄)₂, respectively. At initial heating stage, Mg(AlH₄)₂ decomposed first to produce MgH₂ and Al with hydrogen release. Further elevating operation temperatures gave rise to the reaction between MgH₂ and Al and the self-decomposition of MgH₂ to release more hydrogen and form the Al_0.9Mg_0.1 solid solution and Mg. Finally, NaBH₄ reacted with Mg and partial Al_0.9Mg_0.1 to liberate all of hydrogen and yield the resultant products of MgAlB₄, Al₃Mg₂ and Na. The dehydrogenated sample could take up ∼6.5 wt% of hydrogen at 400 °C and 100 atm of hydrogen pressure through a more complicated reaction process. The hydrogenated products consisted of NaBH₄, MgH₂ and Al, indicating that the presence of Mg(AlH₄)₂ is significantly favorable for reversible hydrogen storage in NaBH₄ at moderate temperature and hydrogen pressure.     

Destabilization effects of Mg(AlH4)2 on MgH2: Improved desorption performances and its reaction mechanism

Both kinetics and thermodynamics properties of MgH₂ are significantly improved by the addition of Mg(AlH₄)₂. The as-prepared MgH₂–Mg(AlH₄)₂ composite displays superior hydrogen desorption performances, which starts to desorb hydrogen at 90 °C, and a total amount of 7.76 wt% hydrogen is released during its decomposition. The enthalpy of MgH₂-relevant desorption is 32.3 kJ mol⁻¹ H₂ in the MgH₂–Mg(AlH₄)₂ composite, obviously decreased than that of pure MgH₂. The dehydriding mechanism of MgH₂–Mg(AlH₄)₂ composite is systematically investigated by using x-ray diffraction and differential scanning calorimetry. Firstly, Mg(AlH₄)₂ decomposes and produces active Al^∗. Subsequently, the in-situ formed Al^∗ reacts with MgH₂ and forms Mg–Al alloys. For its reversibility, the products are fully re-hydrogenated into MgH₂ and Al^∗, under 3 MPa H₂ pressure at 300 °C for 5 h.     

Influence of titanium and nickel dopants on the dehydrogenation properties of Mg(AlH4)2: Electronic structure mechanisms

The structures and dehydrogenation properties of pure and Ti/Ni-doped Mg(AlH₄)₂ were investigated using the first-principles calculations. The dopants mainly affect the geometric and electronic structures of their vicinal AlH₄ units. Ti and Ni dopants improve the dehydrogenation of Mg(AlH₄)₂ in different mechanisms. In the Ti-doped case, Ti prefers to occupy the 13-hedral interstice (Ti_iA) and substitute for the Al atom (Ti_Al), to form a high-coordination structure TiH_n (n = 6, 7). The Ti 3d electrons hybridize markedly with the H 1s electrons in Ti_Al and with the Al 3p electrons in Ti_iA, which weakens the Al–H bond of adjacent AlH₄ units and facilitates the hydrogen dissociation. A TiAl₃H₁₃ intermediate in Ti_iA is inferred as the precursor of Mg(AlH₄)₂ dehydrogenation. In contrast, Ni tends to occupy the octahedral interstice to form the NiH₄ tetrahedron. The tight bind of the Ni with its surrounding H atoms inhibits their dissociation though the nearby Al–H bond also becomes weak. Therefore, Ti is the better dopant candidate than Ni for improving the dehydrogenation properties of Mg(AlH₄)₂ because of its abundant activated hydrogen atoms and low hydrogen removal energy.     

TiF4-doped Mg(AlH4)2 with significantly improved dehydrogenation properties

A significant decrease in the dehydrogenation temperature of Mg(AlH₄)₂ was achieved by low-energy ball milling with TiF₄. Approximately 8.0 wt% of hydrogen was released from the Mg(AlH₄)₂-0.025TiF₄ sample with an on-set temperature of 40 °C, which represents a decrease of 75 °C relative to pristine Mg(AlH₄)₂. In contrast to the three-step reaction for pristine Mg(AlH₄)₂, hydrogen desorption from the TiF₄-doped sample involves a two-step process because the Ti-based species participates in the dehydrogenation reaction. The presence of TiF₄ alters the nucleation and growth of the dehydrogenation product, significantly decreasing the activation energy barrier of the first step in the dehydrogenation of Mg(AlH₄)₂. Further hydrogenation measurements revealed that the presence of the Ti-based species was also advantageous for hydrogen uptake, as the on-set hydrogenation temperature was only 100 °C for the dehydrogenated TiF₄-doped sample, compared with 130 °C for the additive-free sample.     

The hydrogen storage properties and reaction mechanism of the MgH2-NaAlH4 composite system

In this study, we report the hydrogen absorption/desorption properties and reaction mechanism of the MgH₂-NaAlH₄ (4:1) composite system. This composite system showed improved dehydrogenation performance compared with that of as-milled NaAlH₄ and MgH₂ alone. The dehydrogenation process in the MgH₂-NaAlH₄ composite can be divided into four stages: NaAlH₄ is first reacted with MgH₂ to form a perovskite-type hydride, NaMgH₃ and Al. In the second dehydrogenation stage, the Al phase reacts with MgH₂ to form Mg₁₇Al₁₂ phase accompanied with the self-decomposition of the excessive MgH₂. NaMgH₃ goes on to decompose to NaH during the third dehydrogenation stage, and the last stage is the decomposition of NaH. Kissinger analysis indicated that the apparent activation energy, E_A, for the MgH₂-relevent decomposition in MgH₂-NaAlH₄ composite was 148 kJ/mol, which is 20 kJ/mol less than for as-milled MgH₂ (168 kJ/mol). X-ray diffraction patterns indicate that the second, third, and fourth stages are fully reversible. It is believed that the formation of Al₁₂Mg₁₇ phase during the dehydrogenation process alters the reaction pathway of the MgH₂-NaAlH₄ (4:1) composite system and improves its thermodynamic properties.     

Effect of Al on the hydrogen storage properties of Mg(BH4)2

The various Mg–B–Al–H systems composed of Mg(BH₄)₂ and different Al-sources (metallic Al, LiAlH₄ and its decomposition products) have been investigated as potential hydrogen storage materials. The role of Al was studied on the dehydrogenation and the rehydrogenation of the systems. The results indicate that the different Al-sources exhibit a similar improving effect on the dehydrogenation properties of Mg(BH₄)₂. Taking the Mg(BH₄)₂ + LiAlH₄ system as an example, at first LiAlH₄ rapidly decomposes into LiH and Al, then Mg(BH₄)₂ decomposes into MgH₂ and B, finally the MgH₂ reacts with Al, LiH and B, which forms Mg₃Al₂ and MgAlB₄. The system starts to desorb H₂ at 140 °C and desorbs 3.6 wt.% H₂ below 300 °C, while individual Mg(BH₄)₂ starts to desorb H₂ at 250 °C and desorbs only 1.3 wt.% H₂ below 300 °C. The isothermal desorption kinetics of the Mg–B–Al–H systems is about 40% faster than that of Mg(BH₄)₂ at the hydrogen desorption ratio of 90%. In addition, the Mg–B–Al–H systems show partial reversibility at moderate temperature and pressure. For Al-added system, the product of rehydrogenation is MgH₂, while for LiAlH₄-added system the product is composed of LiBH₄ and MgH₂.     

Improved dehydrogenation of MgH2-Li3AlH6 mixture with TiF3 addition

MgH₂-Li₃AlH₆ mixture shows a mutual activation effect between the components. But the dehydrogenation kinetics is still slow, especially at temperature as low as 250 °C. Hereby, an additive (TiF₃) was introduced into the mixture in the present study. The reaction mechanisms were studied by the combined analyses of X-ray diffraction (XRD), thermogravimetric analysis (TGA), as well as thermodynamic calculations. A two-step ball milling method could reduce the mechanical decomposition of Li₃AlH₆ effectively and was adopted. During milling, Li₃AlH₆ reacts with TiF₃ and produces Al₃Ti while MgH₂ remains stable. All the species are well mixed after milling and the grain size is as small as 100 nm. During TGA test, all the reactions occur at lower temperatures compared with undoped mixture, especially the dehydrogenation of MgH₂, which shows a decrease of 60 °C. Its activation energy is reduced by 32.0 kJ mol⁻¹. The first three isothermal (250 °C) cycles indicate that the kinetics of dehydrogenation has been greatly enhanced, showing a reversible capacity of 4.5 wt.% H₂. The time needed for the 1st dehydrogenation has been shortened to 3600 s from 8000 s for the undoped mixture. These improvements are mainly attributed to the catalytic effect of the in-situ formed Al₃Ti. But there is no influence on the rehydrogenation kinetics and the enthalpy of the dehydrogenation of MgH₂ is unchanged.     

Mg/MgH2 hydrogen storage system destabilized by recyclable AlH3–NaBH4 composite

While borohydrides, such as NaBH₄, were often used as supplements to improve hydrogen storage properties of Mg/MgH₂ systems, they have long suffered from high decomposition temperature and irreversible dehydrogenation process. Here, we report that NaBH₄ can reversibly serve as a hydrogen storage host and reactant for Mg/MgH₂ systems under mild reaction conditions with the help of Al/AlH₃. 90 wt%MgH₂–5 wt.%AlH₃–5 wt.%NaBH₄ (M-5AB) has been successfully synthesized using the conventional mechanical alloying technique. The dehydrogenation activation energy and enthalpy are 20% and 9% reduced than those of pure Mg/MgH₂. After 10 hydrogen absorption and desorption cycles, the hydrogen storage capacity of M-5AB can reach 6.35 wt%. The X-ray diffraction (XRD) and the transmission electron microscope (TEM) measurements revealed that the interface of additives and Mg/MgH₂ decompose to Mg₁₇Al₁₂, MgAlB₄ and NaH phases. The Mg₁₇Al₁₂ and MgAlB₄ phases reduces the barrier of free energies of hydrogenated and dehydrogenated states, helping NaBH₄ to recover after rehydrogenation. These discoveries indicate that Al species can boost the decomposition and reformation of NaBH₄, providing a wider degree of freedom for the material design of Mg-based hydrogen storage materials.     

Improving the hydrogen storage properties of MgH2 by reversibly forming Mg–Al solid solution alloys

Supersaturated Mg(Al) solid solutions with reduced lattice constants were successfully prepared by ball milling Mg and Al powder mixtures. The microstructure and phase transition were investigated by XRD. The results indicated that disproportionation of supersaturated Mg(Al) solid solution to MgH₂ and Al was caused by hydrogenation, then equilibrium Mg(Al) solid solution formed after dehydrogenation, while the intermetallic compound Mg₁₇Al₁₂ reversibly decomposed to MgH₂ and intermediate phase Al₃Mg₂ which could further decompose to MgH₂ and Al by hydriding. These reversible phase transitions make Mg–Al alloys show an observably lowered de/hydriding enthalpy and activation energy in comparison with pure Mg.     

An investigation on the hydrogen storage properties and reaction mechanism of the destabilized MgH2–Na3AlH6 (4:1) system

A novel hydrogen storage composite system, MgH₂–Na₃AlH₆ (4:1), was prepared by mechanochemical milling, and its hydrogen storage properties and reaction mechanism were studied. Temperature-programmed desorption results showed that a mutual destabilization effect exists between the components. First, Na₃AlH₆ reacts with MgH₂ to form a perovskite-type hydride, NaMgH₃, Al, and H₂ at a temperature of about 170 °C, which is about 55 °C lower than the decomposition temperature of as-milled Na₃AlH₆. Then, at a temperature of about 275 °C, the as-formed Al can destabilize MgH₂ to form the intermetallic compound Mg₁₇Al₁₂, which is accompanied by the self-decomposition of the residual MgH₂. This temperature is about 55 °C lower than the decomposition temperature for as-milled MgH₂. Furthermore, when heated up to 345 °C, NaMgH₃ starts to decompose into NaH, Mg, and H₂, which is followed by the decomposition of NaH at a temperature of about 370 °C. Rehydrogenation processes show that Mg₁₇Al₁₂ and NaMgH₃ are fully reversible. It is believed that the Mg₁₇Al₁₂ and NaMgH₃ formed in situ provide synergetic thermodynamic and kinetic destabilization, leading to the dehydrogenation of MgH₂, which is responsible for the distinct reduction in the operating temperatures of the as-prepared MgH₂–Na₃AlH₆ (4:1) composite system.     

Direct synthesis of Mg(AlH4)2 and CaAlH5 crystalline compounds by ball milling and their potential as hydrogen storage materials

Mg(AlH₄)₂ and CaAlH₅ were synthesized by direct ball milling of AlH₃ and MgH₂ or AlH₃ and CaH₂ hydrides. The XRD profiles indicated crystalline compounds. Several ball-milling conditions were studied and the optimum parameters were found. Among these, the key parameter is the pause used to cool down the milling device, which allows reducing the temperature rise during milling. Thus, the maximum yield of complex hydrides was obtained by minimizing the desorbed alane amount. The decomposition properties were studied and were in agreement with those reported for different synthesis methods. Mg(AlH₄)₂ with a good hydrogen capacity and a decomposition reaction enthalpy close to 0 kJ/mol H₂ can be a candidate for one-way storage systems. As for CaAlH₅, it might be suitable for reversible hydrogen storage thanks to its dehydrogenation reaction enthalpy (26 kJ/mol H₂). However, rather high activation energy values were evaluated for both compounds (119 and 161 kJ/mol, respectively).     

First-principles study on the dehydrogenation properties and mechanism of Al-doped Mg2NiH4

Mg₂NiH₄, with fast sorption kinetics, is considered to be a promising hydrogen storage material. However, its hydrogen desorption enthalpy is too high for practical applications. In this paper, first-principles calculations based on density functional theory (DFT) were performed to systematically study the effects of Al doping on dehydrogenation properties of Mg₂NiH₄, and the underlying dehydrogenation mechanism was investigated. The energetic calculations reveal that partial component substitution of Mg by Al results in a stabilization of the alloy Mg₂Ni and a destabilization of the hydride Mg₂NiH₄, which significantly alters the hydrogen desorption enthalpy ΔH_des for the reaction Mg₂NiH₄ → Mg₂Ni + 2H₂. A desirable enthalpy value of ∼0.4 eV/H₂ for application can be obtained for a doping level of x ≥ 0.35 in Mg_2−xAl_xNi alloy. The stability calculations by considering possible decompositions indicate that the Al-doped Mg₂Ni and Mg₂NiH₄ exhibit thermodynamically unstable with respect to phase segregation, which explains well the experimental results that these doped materials are multiphase systems. The dehydrogenation reaction of Al-doped Mg₂NiH₄ is energetically favorable to perform from a metastable hydrogenated state to a multiphase dehydrogenated state composed of Mg₂Ni and Mg₃AlNi₂ as well as NiAl intermetallics. Further analysis of density of states (DOS) suggests the improving of dehydrogenation properties of Al-doped Mg₂NiH₄ can be attributed to the weakened Mg-Ni and Ni-H interactions and the decreasing bonding electrons number below Fermi level. The mechanistic understanding gained from this study can be applied to the selection and optimization of dopants for designing better hydrogen storage materials.     

Reversible hydrogen storage in LiBH4/Ca(AlH4)2 systems

To improve the hydrogen storage property of LiBH₄, the LiBH₄/Ca(AlH₄)₂ reactive systems with various ratios were constructed, and their de-/hydrogenation properties as well as the reaction mechanisms were investigated experimentally. It was found that the sample with the LiBH₄ to Ca(AlH₄)₂ molar ratio of 6:1 exhibits the best comprehensive hydrogen storage properties, desorbing hydrogen completely (8.2 wt.%) within 35 min at 450 °C and reversibly absorbing 4.5 wt.% of hydrogen at 450 °C under a hydrogen pressure as low as 4.0 MPa. During the first dehydrogenation process of the LiBH₄/Ca(AlH₄)₂ systems, the CaH₂ and Al particles were in situ precipitated via the self-decomposition of Ca(AlH₄)₂, and then reacted with LiBH₄ to form CaB₆, AlB₂ and LiH. Whereafter, the sample can cycle between LiBH₄ + Ca(BH₄)₂ + Al in the hydrogenated state and CaB₆ + AlB₂ + LiH in the dehydrogenated state.     

Electronic and dehydrogenation properties of TiB2 cluster-doped NaAlH4 (101) surface: A first-principle approach

The crystal structures, electronic and dehydrogenation properties of TiB₂ cluster-doped NaAlH₄ (101) surface have been investigated by the first-principles density functional theory method. In the TiB₂ cluster-doped NaAlH₄ (101) surface, a Ti-centered TiB₂–Al₂H₈–AlH₅–AlH₃ complex is observed, and the AlH₃ and (AlH₅)²⁻ units in the TiB₂–Al₂H₈–AlH₅–AlH₃ favor the first-step decomposition reaction of NaAlH₄. The calculated electronic properties show that B–Ti bonds are stronger than B–Al and Ti–H bonds, which demonstrates that TiB₂ does not change its configuration in catalyzing the decomposition reaction of NaAlH₄. The results of hydrogen desorption energies imply that the import of TiB₂ makes the strength of Al–H bonds decreases. Therefore, the removal of H atoms, especially the removal of H atoms in the Ti–H–Al bonds is easier in the TiB₂ cluster-doped NaAlH₄ than in pure NaAlH₄.     

Effects of helical GNF on improving the dehydrogenation behavior of LiMg(AlH4)3 and LiAlH4

The present paper reports the effect of graphitic nanofibres (GNFs) for improving the desorption kinetics of LiMg(AlH₄)₃ and LiAlH₄. LiMg(AlH₄)₃ has been synthesized by mechano-chemical metathesis reaction involving LiAlH₄ and MgCl₂. The enhancement in dehydrogenation characteristics of LiMg(AlH₄)₃ has been shown to be higher when graphitic nanofibres (GNFs) were used as catalyst. Out of two different types of nanofibres namely planar graphitic nanofibre (PGNF) and helical graphitic nanofibre (HGNF), the latter has been found to act as better catalyst. We observed that helical morphology of fibres improves the desorption kinetics and decreases the desorption temperature of both LiMg(AlH₄)₃ and LiAlH₄. The desorption temperature for 8 mol% HGNF admixed LiAlH₄ gets lowered from 159 °C to 128 °C with significantly faster kinetics. In 8 mol% HGNF admixed LiMg(AlH₄)₃ sample, the desorption temperature gets lowered from 105 °C to ∼70 °C. The activation energy calculated for the first step decomposition of LiAlH₄ admixed with 8 mol% HGNF is ∼68 kJ/mol, where as that for pristine LiAlH₄ it is 107 kJ/mol. The activation energy calculated for as synthesized LiMg(AlH₄)₃ is ∼66 kJ/mol. Since the first step decomposition of LiMg(AlH₄)₃ occurs during GNF admixing, the activation energy for initial step decomposition of GNF admixed LiMg(AlH₄)₃ could not be estimated.     

Effects of nano size mischmetal and its oxide on improving the hydrogen sorption behaviour of MgH2

This paper reports the catalytic effects of mischmetal (Mm) and mischmetal oxide (Mm-oxide) on improving the dehydrogenation and rehydrogenation behaviour of magnesium hydride (MgH₂). It has been found that 5 wt.% is the optimum catalyst (Mm/Mm-oxide) concentration for MgH₂. The Mm and Mm-oxide catalyzed MgH₂ exhibits hydrogen desorption at significantly lower temperature and also fast rehydrogenation kinetics compared to ball-milled MgH₂ under identical conditions of temperature and pressure. The onset desorption temperature for MgH₂ catalyzed with Mm and Mm-oxide are 323 °C and 305 °C, respectively. Whereas the onset desorption temperature for the ball-milled MgH₂ is 381 °C. Thus, there is a lowering of onset desorption temperature by 58 °C for Mm and by 76 °C for Mm-oxide. The dehydrogenation activation energy of Mm-oxide catalyzed MgH₂ is 66 kJ/mol. It is 35 kJ/mol lower than ball-milled MgH₂. Additionally, the Mm-oxide catalyzed dehydrogenated Mg exhibits faster rehydrogenation kinetics. It has been noticed that in the first 10 min, the Mm-oxide catalyzed Mg (dehydrogenated MgH₂) has absorbed up to 4.75 wt.% H₂ at 315 °C under 15 atmosphere hydrogen pressure. The activation energy determined for the rehydrogenation of Mm-oxide catalyzed Mg is ∼62 kJ/mol, whereas that for the ball-milled Mg alone is ∼91 kJ/mol. Thus, there is a decrease in absorption activation energy by ∼29 kJ/mol for the Mm-oxide catalyzed Mg. In addition, Mm-oxide is the native mixture of CeO₂ and La₂O₃ which makes the duo a better catalyst than CeO₂, which is known to be an effective catalyst for MgH₂. This takes place due to the synergistic effect of CeO₂ and La₂O₃. It can thus be said that Mm-oxide is an effective catalyst for improving the hydrogen sorption behaviour of MgH₂.     

Multi-hydride systems with enhanced hydrogen storage properties derived from Mg(BH4)2 and LiAlH4

A two-step ball-milling method has been provided to synthesize Mg(BH₄)₂ using NaBH₄ and MgCl₂ as starting materials. The method offers high yield and high purity (96%) of the compound. The as-synthesized Mg(BH₄)₂ is then combined with LiAlH₄ by ball-milling in order to form new multi-hydride systems with high hydrogen storage properties. The structure, the dehydrogenation and the reversibility of the combined systems are studied. Analyses show that a metathesis reaction takes place between Mg(BH₄)₂ and LiAlH₄ during milling, forming Mg(AlH₄)₂ and LiBH₄. Mg(BH₄)₂ is excessive and remains in the ball-milled product when the molar ratio of Mg(BH₄)₂ to LiAlH₄ is over 0.5. The onset dehydrogenation temperature of the combined systems is lowered to ca. 120 °C, which is much lower than that of either Mg(BH₄)₂ or LiAlH₄. The dehydrogenation capacities of the combined systems below 300 °C are all higher than that of both Mg(BH₄)₂ and LiAlH₄. The combined systems are reversible for hydrogen storage at moderate hydrogenation condition, and rapid hydrogenation occurred within the initial 30 min. Moreover, the remained Mg(BH₄)₂ in the combined systems is found also partially reversible. The mechanism of the enhancement of the hydrogen storage properties and the dehydrogenation/hydrogenation process of the combined systems were discussed.     

Study on the dehydrogenation properties and reversibility of Mg(BH4)2AlH3 composite under moderate conditions

Mg(BH₄)₂ has been considered as one of the promising light metal complex hydrides due to its high hydrogen capacity and low cost. But its higher thermal stability (dehydrogenation at above 300 °C) needs to be improved for the practical application. In this study, the aluminum hydride AlH₃ was introduced into complex borohydride Mg(BH₄)₂ to synthesize a new Mg(BH₄)₂AlH₃ composite by ball milling method. It is found that the active Al¹ formed from the self-decomposition of AlH₃ can effectively improve the dehydrogenation properties of Mg(BH₄)₂, the Mg(BH₄)₂AlH₃ composite starts to release hydrogen at 130.8 °C with a total hydrogen capacity of 11.9 wt.%. The dehydrogenated products of the composite is composed of Mg₂Al₃ and B at 350 °C, resulting in the improved hydrogen desorption properties of Mg(BH₄)₂AlH₃ composite. The Mg₂Al₃ and B products would be further transformed into MgAlB₄ and Al at 500 °C. Moreover, the Mg₂Al₃ and B dehydrogenated products show better reversible hydrogen storage property than that of the MgAlB₄ and Al products. This research shows a way to alter hydrogen de/hydrogenation route and reversibility of Mg(BH₄)₂ complex hydride by compositing with AlH₃ and controlling the dehydrogenation temperature.     

Enhanced reversible hydrogen storage properties of a Mg–In–Y ternary solid solution

A Mg(In, Y) ternary solid solution was successfully synthesized by two-step method, namely sintering the elemental powders and subsequent milling. The formation of Mg(In, Y) indicates that the solubility of Y in the Mg lattice is expanded due to the existence of In. The as-synthesized Mg₉₀In₅Y₅ solid solution transformed to MgH₂, YH₃, In₃Y and MgIn compound upon hydrogenation, the hydrogenated products except for the YH₃ recovered to Mg(In, Y) solid solution after dehydrogenation. The Mg₉₀In₅Y₅ solid solution exhibited a decreased reaction enthalpy of 62.9 kJ/(mol H₂), reduction by ca. 5 kJ/(mol H₂) or 12 kJ/(mol H₂) than the Mg₉₅In₅ binary solid solution and pure Mg, respectively. The working temperature as well as the activation energies for the hydriding and dehydriding were also decreased in comparison with those of Mg(In) binary solid solution, which are attributed to the reduced reaction enthalpy and the catalytic role of YH₃. Our work indicates that the thermodynamic and kinetic tuning of MgH₂ are realized in the Mg(In, Y) ternary solid solution.     

Comparative investigation on the hydrogenation/dehydrogenation characteristics and hydrogen storage properties of Mg3Ag and Mg3Y

The hydrogenation/dehydrogenation characteristics and hydrogen storage properties of nominal Mg₃Ag and Mg₃Y alloys prepared by induction melting were investigated. The as-melted Mg₃Ag alloy was composed of Mg₅₄Ag₁₇ phase, while Mg₃Y consisted of Mg₂₄Y₅ and Mg₂Y phases. Mg₅₄Ag₁₇ transformed into MgAg and MgH₂ during the first hydrogenation, and the phase transition of the following hy/dehydrogenation cycles was Mg₃Ag + 2H₂ ↔ MgAg + 2MgH₂. Both Mg₂₄Y₅ and Mg₂Y undertook disproportion reactions and decomposed into MgH₂ and YH₃. Experimental and calculated results demonstrated that there was no necessary relation between the thermodynamic stabilities and the size interstices in these alloys. The dehydrogenation enthalpy change (ΔH) and entropy change (ΔS) of Mg₃Ag were calculated and compared with that of pure Mg, which indicated that the increase of ΔS could counteract the stabilization effect of ΔH, which offered a method for tuning the thermodynamic properties of Mg-based alloys.