Effect of additive distribution in H2 absorption and desorption kinetics in MgH2 milled with NbH0.9 or NbF5

This paper presents a comparative study of H₂ absorption and desorption in MgH₂ milled with NbF₅ or NbH_0.9. The addition of NbF₅ or NbH_0.9 greatly improves hydriding and dehydriding kinetics. After 80 h of milling the mixture of MgH₂ with 7 mol.% of NbF₅ absorbs 60% of its hydrogen capacity at 250 °C in 30 s, whereas the mixture with 7 mol.% of NbH_0.9 takes up 48%, and MgH₂ milled without additive only absorbs 2%. At the same temperature, hydrogen desorption in the mixture with NbF₅ finishes in 10 min, whereas the mixture with NbH_0.9 only desorbs 50% of its hydrogen content, and MgH₂ without additive practically does not releases hydrogen. The kinetic improvement is attributed to NbH_0.9, a phase observed in the hydrogen cycled MgH₂ + NbF₅ and MgH₂ + NbH_0.9 materials, either hydrided or dehydrided. The better kinetic performance of the NbF₅-added material is attributed to the combination of smaller size and enhanced distribution of NbH_0.9 with more favorable microstructural characteristics. The addition of NbF₅ also produces the formation of Mg(H_xF_1-x)₂ solid solutions that limit the practically achievable hydrogen storage capacity of the material. These undesired effects are discussed.     

Synthesis of BaFe12O19 by solid state method and its effect on hydrogen storage properties of MgH2

Previous studies have shown that ferrites give a positive effect in improving the hydrogen sorption properties of magnesium hydride (MgH₂). In this study, another ferrite, i.e., BaFe₁₂O₁₉, has been successfully synthesised via the solid state method, and it was milled with MgH₂ to enhance the sorption kinetics. The result showed that the MgH₂ + 10 wt% BaFe₁₂O₁₉ sample started to release hydrogen at about 270 °C which is about 70 °C lower than the as-milled MgH₂. The doped sample was able to absorb hydrogen for 4.3 wt% in 10 min at 150 °C, while as-milled MgH₂ only absorbed 3.5 wt% of hydrogen under similar conditions. The desorption kinetic results showed that the doped sample released about 3.5 wt% of hydrogen in 15 min at 320 °C, while the as-milled MgH₂ only released about 1.5 wt% of hydrogen. From the Kissinger plot, the apparent activation energy of the BaFe₁₂O₁₉-doped MgH₂ sample was 115 kJ/mol which was lower than the milled MgH₂ (141 kJ/mol)_. Further analyses demonstrated that MgO, Fe and Ba or Ba-containing contribute to the improvement by serving as active species, thus enhancing the MgH₂ for hydrogen storage.     

Synergistic catalytic effect of SrTiO3 and Ni on the hydrogen storage properties of MgH2

Study on the synergistic catalytic effect of the SrTiO₃ and Ni on the improvement of the hydrogen storage properties of the MgH₂ system has been carried out. The composites have been prepared using ball milling method and comparisons on the hydrogen storage properties of the MgH₂ – Ni and MgH₂ – SrTiO₃ composites have been presented. The MgH₂ – 10 wt% SrTiO₃ – 5 wt% Ni composite is found to has a decomposition temperature of 260 °C with a total decomposition capacity of 6 wt% of hydrogen. The composite is able to absorb 6.1 wt% of hydrogen in 1.3 min (320 °C, 27 atm of hydrogen). At 150 °C, the composite is able to absorb 2.9 wt% of hydrogen in 10 min under the pressure of 27 atm of hydrogen. The composite has successfully released 6.1 wt% of hydrogen in 13.1 min with a total dehydrogenation of 6.6 wt% of hydrogen (320 °C). The apparent activation energy, E_a, for decomposition of SrTiO₃-doped MgH₂ reduced from 109.0 kJ/mol to 98.6 kJ/mol after the addition of 5 wt% Ni. The formation of Mg₂Ni and Mg₂NiH₄ as the active species help to boost the performance of the hydrogen storage properties of the MgH₂ system. Observation of the scanning electron microscopy images suggested the catalytic role of the SrTiO₃ additive is based on the modification of composite microstructure.     

Influence of K2TiF6 additive on the hydrogen sorption properties of MgH2

In this study, the hydrogen storage properties of MgH₂ with the addition of K₂TiF₆ were investigated for the first time. The temperature-programmed desorption results showed that the addition of 10 wt% K₂TiF₆ to the MgH₂ exhibited a lower onset desorption temperature of 245 °C, which was a decrease of about 105 °C and 205 °C compared with the as-milled and as-received MgH₂, respectively. The dehydrogenation and rehydrogenation kinetics of 10 wt% K₂TiF₆-doped MgH₂ were also significantly improved compared to the un-doped MgH₂. The results of the Arrhenius plot showed that the activation energy for the hydrogen desorption of MgH₂ was reduced from 164 kJ/mol to 132 kJ/mol after the addition of 10 wt% K₂TiF₆. Meanwhile, the X-ray diffraction analysis showed the formation of a new phase of potassium hydride and titanium hydride together with magnesium fluoride and titanium in the doped MgH₂ after the dehydrogenation and rehydrogenation process. It is reasonable to conclude that the K₂TiF₆ additive doped with MgH₂ played a catalytic role through the formation of active species of KH, TiH₂, MgF₂ and Ti during the ball milling or heating process. It is therefore proposed that this newly developed product works as a real catalyst for improving the hydrogen sorption properties of MgH₂.     

A novel complex oxide TiVO3.5 as a highly active catalytic precursor for improving the hydrogen storage properties of MgH2

Herein, we demonstrate the successful preparation of a novel complex transition metal oxide (TiVO_3.5) by oxidizing a solid-solution MXene (Ti_0.5V_0.5)₃C₂ at 300 °C and its high activity as a catalyst precursor in the hydrogen storage reaction of MgH₂. The prepared TiVO_3.5 inherits the layered morphology of its MXene precursor, but the layer surface becomes very coarse because of the presence of numerous nanoparticles. Adding a minor amount of TiVO_3.5 remarkably reduces the dehydrogenation and hydrogenation temperatures of MgH₂ and enhances the reaction kinetics. The 10 wt% TiVO_3.5-containing sample exhibits optimal hydrogen storage properties, as it desorbs approximately 5.0 wt% H₂ in 10 min at 250 °C and re-absorbs 3.9 wt% H₂ in 5 s at 100 °C and under 50 bar of hydrogen pressure. The apparent activation energy is calculated to be approximately 62.4 kJ/mol for the MgH₂-10 wt% TiVO_3.5 sample, representing a 59% reduction in comparison with pristine MgH₂ (153.8 kJ/mol), which reasonably explains the remarkably reduced dehydrogenation operating temperature. Metallic Ti and V are detected after ball milling with MgH₂; they are uniformly dispersed on the MgH₂ matrix and act as actual catalytic species for the improvement of the hydrogen storage properties of MgH₂.     

MnFe2O4 nanopowder synthesised via a simple hydrothermal method for promoting hydrogen sorption from MgH2

The effects of MnFe₂O₄ nanopowder synthesised via a simple ‘hydrothermal’ method on the hydrogen storage properties of MgH₂ are investigated for the first time. The particle size of the as-synthesised MnFe₂O₄ nanoparticles is determined to be about 10 nm. We observe that MnFe₂O₄ catalyst decreases the decomposition temperature of MgH₂ and enhances the sorption kinetics. Interestingly, the onset hydrogen desorption temperature of 10 wt% MnFe₂O₄-doped MgH₂ sample gets lowered from 350 °C to 240 °C with faster kinetics, and the sample shows an average dehydrogenation rate 8–9 times faster than that of the as-milled MgH₂ sample. By adding 10 wt% of as-prepared MnFe₂O₄ to MgH₂, approximately 5.5 wt% hydrogen can be absorbed in 10 min at 200 °C. In contrast, the un-doped MgH₂ sample absorbed only 4.0 wt% hydrogen in the same period of time. From the Kissinger analysis, the apparent activation energy for hydrogen released in the MnFe₂O₄-added MgH₂ composite is found to be 108.42 kJ/mol, which is much lower than the activation energy for hydrogen released in the as-milled MgH₂ (146.57 kJ/mol). It is believed that the in situ formed Fe particle and Mn-containing phases together play a synergistic role in remarkably improving MgH₂ storage properties.     

Synthesis of low-cost biomass charcoal-based Ni nanocatalyst and evaluation of their kinetic enhancement of MgH2

In this study, a low-cost biomass charcoal (BC)-based nickel catalyst (Ni/BC) was introduced into the MgH₂ system by ball-milling. The study demonstrated that the Ni/BC catalyst significantly improved the hydrogen desorption and absorption kinetics of MgH₂. The MgH₂ + 10 wt% Ni/BC-3 composite starts to release hydrogen at 187.8 °C, which is 162.2 °C lower than the initial dehydrogenation temperature of pure MgH₂. Besides, 6.04 wt% dehydrogenation can be achieved within 3.5 min at 300 °C. After the dehydrogenation is completed, MgH₂ + 10 wt% Ni/BC-3 can start to absorb hydrogen even at 30 °C, which achieved the absorption of 5 wt% H₂ in 60 min under the condition of 3 MPa hydrogen pressure and 125 °C. The apparent activation energies of dehydrogenation and hydrogen absorption of MgH₂ + 10 wt% Ni/BC-3 composites were 82.49 kJ/mol and 23.87 kJ/mol lower than those of pure MgH₂, respectively, which indicated that the carbon layer wrapped around MgH₂ effectively improved the cycle stability of hydrogen storage materials. Moreover, MgH₂ + 10 wt% Ni/BC-3 can still maintain 99% hydrogen storage capacity after 20 cycles. XRD, EDS, SEM and TEM revealed that the Ni/BC catalyst evenly distributed around MgH₂ formed Mg₂Ni/Mg₂NiH₄ in situ, which act as a “hydrogen pump” to boost the diffusion of hydrogen along with the Mg/MgH₂ interface. Meanwhile, the carbon layer with fantastic conductivity enormously accelerated the electron transfer. Consequently, there is no denying that the synergistic effect extremely facilitated the hydrogen absorption and desorption kinetic performance of MgH₂.     

Dual-cation K2TaF7 catalyst improves high-capacity hydrogen storage behavior of MgH2

MgH₂ has been extensively regarded as a low-cost hydrogen storage material with high gravimetric hydrogen capacity of approximately 7.6 wt%. However, the hydrogen release and absorption kinetics in MgH₂ still needs further improving. For the first time, the catalytic impacts of a new dual-cation metal fluoride K₂TaF₇ upon the hydrogen storage characteristics of MgH₂ have been investigated in this work. With only 1 wt% K₂TaF₇ dopant, the initial dehydrogenation temperature of MgH₂ was lowered by about 130 °C, releasing more than 7.3 wt% hydrogen totally. The desorption activation energy of MgH₂ + 1 wt% K₂TaF₇ composite was decreased to 107.2 ± 1.2 kJ mol^?1. Besides, at 190 °C, the dehydrogenated MgH₂ + 1 wt% K₂TaF₇ sample could absorb 6.56 wt% H₂, while pristine MgH₂ re-absorbed only 3.45 wt% H₂. Further studies revealed that K₂TaF₇ could react with MgH₂ during dehydrogenation and produce symbiotic hydrides KMgH₃ and TaH_0.8, which could play the role of hydrogen pumps during hydrogen release and uptake. The cooperative catalysis between the hydrogen pump effect and the active interface in the multi-hydride area significantly enhanced the reversible hydrogen storage in the MgH₂+1 wt% K₂TaF₇ composite. This study provides new thinking for novel catalysts to elevate the hydrogen storage performance of MgH₂.     

Combined effects of hydrogen back-pressure and NbF5 addition on the dehydrogenation and rehydrogenation kinetics of the LiBH4–MgH2 composite system

It is well known that the dehydrogenation pathway of the LiBH₄–MgH₂ composite system is highly reliant on whether decomposition is performed under vacuum or a hydrogen back-pressure. In this work, the effects of hydrogen back-pressure and NbF₅ addition on the dehydrogenation kinetics of the LiBH₄–MgH₂ system are studied under either vacuum or hydrogen back-pressure, as well as the subsequent rehydrogenation and cycling. For the pristine sample, faster desorption kinetics was obtained under vacuum, but the performance is compromised by slow absorption kinetics. In contrast, hydrogen back-pressure remarkably promotes the absorption kinetics and increases the reversible hydrogen storage capacity, but with the penalty of much slower desorption kinetics. These drawbacks were overcome after doping with NbF₅, with which the dehydrogenation and rehydrogenation kinetics was significantly improved. In particular, the enhanced kinetics was observed to persist well, even after 9 cycles, in the case of the NbF₅ doped sample under hydrogen back-pressure, as well as the suppression of forming Li₂B₁₂H₁₂. Furthermore, the mechanism that is behind these effects of NbF₅ additive on the reversible dehydrogenation reaction of the LiBH₄–MgH₂ system is discussed.     

The enhanced de/re‐hydrogenation performance of MgH2 with TiH2 additive

Catalytic effects of TiH₂ on hydrogenation/dehydrogenation kinetics of MgH₂ were investigated in this study. The TG analysis showed that the addition of the x wt% TiH₂ exhibited lower onset temperature of 160°C which is 100°C and 190°C lower than as‐milled and as‐received MgH₂. The dehydrogenation and hydrogenation kinetics were significantly improved compared with the pure MgH₂. The activation energy for the hydrogen desorption of MgH₂ was reduced from ?137.13 to ?77.58 kJ/mol by the addition of TiH₂. XRD and XPS results showed that the phase of TiH₂ remained same during the dehydrogenation without any intermediate formation confirming its role as catalyst.     

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.     

The hydrogen storage properties and catalytic mechanism of the CuFe2O4-doped MgH2 composite system

The influence of CuFe₂O₄ addition on the sorption performances of MgH₂ prepared by ball milling was studied for the first time. The MgH₂ + 10 wt% CuFe₂O₄ sample exhibited an enhancement in hydrogen storage performance compared to that of as-milled MgH₂, with the onset decomposition temperature decreased from 340 °C to 250 °C. Dehydrogenation kinetic result revealed that CuFe₂O₄-added MgH₂ released around 5.3 wt% H₂ within 10 min at 320 °C, while the as-milled MgH₂ released below 1.0 wt% H₂ under the same condition. Furthermore, about 5.0 wt% H₂ was absorbed at 250 °C in 30 min for the 10 wt% CuFe₂O₄-doped MgH₂ sample. In contrast, the un-doped MgH₂ only absorbed 4.0 wt% H₂ at 250 °C in 30 min. From the Kissinger analysis, the apparent activation energy of as-milled MgH₂ was 166.0 kJ/mol and this value decreased to 113.0 kJ/mol for 10 wt% CuFe₂O₄-added MgH₂. The enhanced sorption performance of MgH₂ in the presence of CuFe₂O₄ is believed to be due to the role of in situ formed Fe, Mg-Cu alloy, and MgO phases as an active species to catalyse the hydrogen storage properties of MgH₂.     

Influence of different amounts of FeCl3 on decomposition and hydrogen sorption kinetics of MgH2

In the present work, the hydrogen storage properties of MgH₂-X wt.% FeCl₃ (X = 5, 10, 15 and 20) are investigated experimentally. It is found that the MgH₂ + 10 wt.% FeCl₃ sample exhibits the best comprehensive hydrogen storage properties, in terms of the onset dehydrogenation temperature, the hydrogen amounts de/reabsorbed as well as the relative de/rehydrogenation rates. The onset dehydrogenation temperature of the 10 wt.% FeCl₃-doped MgH₂ sample is reduced by about 90 °C compared to the as-milled MgH₂, and the sorption kinetics measurements indicate that the FeCl₃-doped sample displays an average dehydrogenation rate 5–6 times faster than that of the undoped MgH₂ sample. Higher levels of doping introduce negative effects, such as lower capacity and slower absorption/desorption rates compared to samples with lower FeCl₃ doping levels. The apparent activation energy for hydrogen desorption is decreased from 166 kJ•mol⁻¹ for as-milled MgH₂ to 130 kJ•mol⁻¹ by the addition of 10 wt.% FeCl₃. It is believed that the improvement of the MgH₂ sorption properties in the MgH₂/FeCl₃ composite is due to the catalytic effects of the in-situ generated Fe species and MgCl₂ that are formed during the heating process.     

CNTs decorated with CoFeB as a dopant to remarkably improve the dehydrogenation/rehydrogenation performance and cyclic stability of MgH2

The chain-like carbon nanotubes (CNTs) decorated with CoFeB (CoFeB/CNTs) prepared by oxidation-reduction method is introduced into MgH₂ to facilitate its hydrogen storage performance. The addition of CoFeB/CNTs enables MgH₂ to start desorbing hydrogen at only 177 °C. Whereas pure MgH₂ starts hydrogen desorption at 310 °C. The dehydrogenation apparent activation energy of MgH₂ in CoFeB/CNTs doped-MgH₂ composite is only 83.2 kJ/mol, and this is about 59.5 kJ/mol lower than that of pure MgH₂. In addition, the completely dehydrogenated MgH₂−10 wt% CoFeB/CNTs sample can start to absorb hydrogen at only 30 °C. At 150 °C and 5 MPa H₂, the MgH₂ in CoFeB/CNTs doped-MgH₂ composite can absorb 6.2 wt% H₂ in 10 min. The cycling kinetics can remain rather stable up to 20 cycles, and the hydrogen storage capacity retention rate is 98.5%. The in situ formation of Co₃MgC, Fe, CoFe and B caused by the introduction of CoFeB/CNTs can provide active and nucleation sites for the dehydrogenation/rehydrogenation reactions of MgH₂. Moreover, CNTs can provide hydrogen diffusion pathways while also enhancing the thermal conductivity of the sample. All of these can facilitate the dehydrogenation/rehydrogenation performance and cyclic stability of MgH₂.     

Hydrogen storage properties of nanocrystalline Mg2Ni prepared from compressed 2MgH2Ni powder

In the present work, nanocrystalline Mg₂Ni with an average size of 20–50 nm was prepared via ball milling of a 2MgH₂Ni powder followed by compression under a pressure of 280 MPa. The phase component, microstructure, and hydrogen sorption properties were characterized by using X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), pressure-composition-temperature (PCT) and synchronous thermal analyses (DSC/TG). Compared to the non-compressed 2MgH₂Ni powder, the compressed 2MgH₂Ni pellet shows lower dehydrogenation temperature (290 °C) and a single-phase Mg₂Ni is obtained after hydrogen desorption. PCT measurements show that the nanocrystalline Mg₂Ni obtained from dehydrogenated 2MgH₂Ni pellet has a single step hydrogen absorption and desorption with fairly low absorption (?57.47 kJ/mol H₂) and desorption (61.26 kJ/mol H₂) enthalpies. It has very fast hydrogen absorption kinetics at 375 °C with about 3.44 wt% hydrogen absorbed in less than 5 min. The results gathered in this study show that ball milling followed by compression is an efficient method to produce Mg-based ternary hydrides.     

Studies on de/rehydrogenation characteristics of nanocrystalline MgH2 co-catalyzed with Ti,Fe and Ni

In the present study, we have investigated the combined effect of different transition metals such as Ti, Fe and Ni on the de/rehydrogenation characteristics of nano MgH₂. Mechanical milling of MgH₂ with 5 wt% each of Ti, Fe and Ni for 24 h at 12 atm of H₂ pressure lead to the formation of nano MgH₂-Ti5Fe5Ni5. The decomposition temperature of nano MgH₂-Ti5Fe5Ni5 is lowered by 90 °C as compared to nano MgH₂ alone. It is also found that the nano MgH₂-Ti5Fe5Ni5 absorbs 5.3 wt% within 15 min at 270 °C and 12 atm hydrogen pressures. However, nano MgH₂ reabsorbs only 4.2 wt% under identical condition. An interesting result of the present study is that mechanical milling of MgH₂ separately with Fe and Ni besides refinement in particle size also leads to the formation of alloys Mg₂NiH₄ and Mg₂FeH₆ respectively. On the other hand, when MgH₂ is mechanically milled together with Ti, Fe and Ni, the dominant result is the formation of nano particles of MgH₂. Moreover the activation energy for dehydrogenation of nano MgH₂ co-catalyzed with Ti, Fe and Ni is 45.67 kJ/mol which is 35.71 kJ/mol lower as compared to activation energy of nano MgH₂ (81.34 kJ/mol). These results are one of the most significant in regard to improvement in de/rehydrogenation characteristics of known MgH₂ catalyzed through transition metal elements.     

Synergistic effects played by CMK-3 and NbF5 co-additives on de/re-hydrogenation performances of NaAlH4

In the present work, a strategy for simultaneously reducing the thermal stability of NaAlH₄ and enhancing its dehydrogenation kinetics was suggested by means of synergistic effects from co-additives of mesoporous carbon material CMK-3 and NbF₅. The ball milled NaAlH₄ + 10 wt% (NbF₅ + CMK-3) (NbF₅: CMK-3 = 1:1 in weight ratio) composite can liberate hydrogen at an onset temperature of 358 K, which was drastically decreased by 93 K from that of pristine NaAlH₄. By means of Kissinger's method, the activation energy of NaAlH₄ + 10 wt% (NbF₅ + CMK-3) can be identified as 99.2 kJ mol^?1, which was greatly reduced from that of pristine NaAlH₄ (121 kJ mol^?1). Investigations on the dehydrogenation process revealed that CMK-3 was beneficial to reducing the particle size of NaAlH₄ during ball milling, while NbF₅ was actively involved in the decomposition of NaAlH₄ and yielded some Nb-relevant intermediate phases NbH_0.89 during the heating process. The modified dehydrogenation pathway of NaAlH₄ also results in the destabilization of dehydrogenation by 2.13 kJ mol^?1 H₂ from that of pristine NaAlH₄. During the hydrogenation process, the NbH_0.89 and the mesoporous carbon material CMK-3 played synergistic roles in improving the dehydrogenation performance of NaAlH₄.     

Reversible hydrogen sorption and kinetics of hydrogen storage tank based on MgH2 modified by TiF4 and activated carbon

By doping with 5 wt % TiF₄ and activated carbon (AC), onset and main dehydrogenation temperatures of MgH₂ significantly reduce (ΔT = 138 and 109 °C, respectively) with hydrogen capacity of 4.4 wt % H₂. Up-scaling to storage tank begins with packing volume and sample weight of 28.8 mL and ～14.5 g, respectively, and continues to 92.6 mL and ～60.5–67 g, respectively. Detailed hydrogen sorption mechanisms and kinetics of the tank tightly packed with four beds of MgH₂TiF₄-AC (～60.5 g) are investigated. De/rehydrogenation mechanisms are detected by three temperature sensors located at different positions along the tank radius, while hydrogen permeability is benefited by stainless steel mesh sheets and tube inserted in the hydride beds. Fast desorption kinetics of MgH₂TiF₄-AC tank at ～275–283 °C, approaching to onset dehydrogenation temperature of the powder sample (272 °C) suggests comparable performances of laboratory and tank scales. Hydrogen desorption (T = 300 °C and P(H₂) = 1 bar) and absorption (T = 250 °C and P(H₂) = 10–15 bar) of MgH₂TiF₄-AC tank provide gravimetric and volumetric capacities during the 1^st-2nd cycles of 4.46 wt % H₂ and 28 gH₂/L, respectively, while those during the 3^rd-15th cycles are up to 3.62 wt % H₂ and 23 gH₂/L, respectively. Due to homogeneous heat transfer along the tank radius, de/rehydrogenation kinetics superior at the tank center and degrading forward the tank wall can be due to poor hydrogen permeability. Particle sintering and/or agglomeration upon cycling yield deficient hydrogen content reproduced.     

Effects of NbF5 addition on the hydrogen storage properties of LiAlH4

We investigated the effects of NbF₅ addition by ball milling on the hydrogen storage properties of LiAlH₄. Pressure-composition-temperature (PCT) experiments showed that addition of 0.5 and 1 mol% NbF₅ in LiAlH₄ improves the onset desorption temperature and results in little decrease in hydrogen capacity, with approximately 7.0 wt% released by 188 °C. Isothermal dehydriding kinetics measurements indicated that the NbF₅-doped sample shows an average dehydrogenation rate 5–6 times faster than that of the as-received LiAlH₄ sample. In the x-ray diffraction results, there are distinct peaks of Al and LiH that appear after desorption. There is no peak of NbF₅ before or after desorption. Desorption kinetics measurements indicated that the activation energy, E_A, for LiAlH₄ + 1 mol% NbF₅ is about 67 kJ/mol for first reaction stage and about 77 kJ/mol for second reaction stage. The desorption process was further characterised by differential scanning calorimetry, and the possible mechanism of the effects of NbF₅ addition is discussed.     

Kinetic performance of hydrogen generation enhanced by AlCl3 via hydrolysis of MgH2 prepared by hydriding combustion synthesis

Magnesium hydride (MgH₂) is a very promising hydrogen storage material and it has been paid more and more attention on the application of supplying hydrogen on-board because the theoretical hydrogen yield is up to 1703 mL/g when it reacts with water. However, the hydrolysis reaction is inhibited rapidly by the passivation layer of Mg(OH)₂ formed on the surface of MgH₂. This paper reports that high purity MgH₂ (～98.7 wt%) can be readily obtained by the process of hydriding combustion synthesis (HCS) and the hydrogen generation via hydrolysis of the as-prepared HCSed MgH₂ can be dramatically enhanced by the addition of AlCl₃ in hydrolysis solutions. An excellent kinetics of hydrogen generation of 1487 mL/g in 10 min and 1683 mL/g in 17 min at 303 K was achieved for the MgH₂-0.5 M AlCl₃ system, in which the theoretical hydrogen yield (1685 mL/g) of the HCSed product was nearly reached. The mechanism of the hydrolysis kinetics enhancement was demonstrated by the generation of a large amounts of H⁺ from the Al³⁺ hydrolysis and the pitting corrosion (Cl^?) of the Mg(OH)₂ layer wrapped on the surface of MgH₂ even at a low temperature. In addition, the apparent activation energies for the MgH₂ hydrolysis in the 0.1 M AlCl₃ and 0.5 M AlCl₃ solutions are decreased to 34.68 kJ/mol and 21.64 kJ/mol, respectively, being far superior to that of reported in deionized water (58.06 kJ/mol). The results suggest that MgH₂ + AlCl₃ system may be used as a promising hydrogen generation system in practical application of supplying hydrogen on-board.