Hydriding and dehydriding characteristics of nanocrystalline and amorphous Mg20Ni10−xCox (x = 0–4) alloys prepared by melt-spinning

In order to improve the hydriding and dehydriding performances of the Mg₂Ni-type alloys, Ni in the alloy was partially substituted by element Co, and melt-spinning technology was used for the preparation of the Mg₂₀Ni_10−xCo_x (x = 0–4) hydrogen storage alloys. The structures of the as-cast and spun alloys were studied by XRD, SEM and HRTEM. Thermal stability of the as-spun alloys was researched by DSC. The hydrogen absorption and desorption kinetics of the alloys were measured using an automatically controlled Sieverts apparatus. The results showed that no amorphous phase formed in the as-spun Co-free alloy, but the as-spun alloys containing Co showed certain amount of amorphous phase. The hydrogen absorption capacities of the as-cast alloys first increase and then decrease with the variety of Co content. The hydrogen desorption capacities of as-cast and spun alloys rise with increasing Co content. The rapid quenching significantly improved the hydrogenation and dehydrogenation capacities and the kinetics of the alloys. When the quenching rate increased from 0 (as-cast was defined as spinning rate of 0 m/s) to 30 m/s, the hydrogen absorption capacity of the alloys (x = 0) at 200 °C and 1.5 MPa in 20 min rose from 1.39 to 3.12 wt%, and from 1.91 to 2.96 wt% for the alloy (x = 4). The hydrogen desorption capacity of the alloy (x = 0) in 20 min increased from 0.19 to 0.89 wt%, and from 1.39 to 2.15 wt% for the alloy (x = 4).     

Investigations on hydrogenation behaviour of CNT admixed Mg2Ni

The aim of the present paper is to report results on hydrogenation behaviour of the new composite material Mg₂Ni: CNT. Admixing of carbon nanotubes (CNT) in storage material Mg₂Ni leads to noticeable enhancement in desorption kinetics as well as storage capacity. We have found that the composite material Mg₂Ni–2 mole% CNT is the optimum material. The Mg₂Ni–CNT composite exhibits hydrogen desorption rate of 5.7 cc/g/min as against 3.0 cc/g/min for Mg₂Ni alone (enhancement of ∼ 90%) and storage capacity of ∼ 4.20 wt% in contrast to ∼3.20 wt% for Mg₂Ni alone (increase of ∼ 31%). Feasible mechanisms for the enhancement of hydrogen desorption kinetics and storage capacity have been put forward.     

Enhanced hydrogen storage properties of LiBH4-MgH2 composite by the catalytic effect of MoCl3

Though LiBH₄-MgH₂ system exhibits an excellent hydrogen storage property, it still presents high decomposition temperature over 350 °C and sluggish hydrogen absorption/desorption kinetics. In order to improve the hydrogen storage properties, the influence of MoCl₃ as an additive on the hydrogenation and dehydrogenation properties of LiBH₄-MgH₂ system is investigated. The reversible hydrogen storage performance is significantly improved, which leads to a capacity of about 7 wt.% hydrogen at 300 °C. XRD analysis reveals that the metallic Mo is formed by the reaction between LiBH₄ and MoCl₃, which is highly dispersed in the sample and results in improved dehydrogenation and hydrogenation performance of LiBH₄-MgH₂ system. From Kissinger plot, the activation energy for hydrogen desorption of LiBH₄-MgH₂ system with additive MoCl₃ is estimated to be ∼43 kJ mol⁻¹ H₂, 10 kJ mol⁻¹ lower than that for the pure LiBH₄-MgH₂ system indicating that the kinetics of LiBH₄-MgH₂ composite is significantly improved by the introduction of Mo.     

Hydrogenation properties of pure magnesium and magnesium–aluminium thin films

We have studied the hydrogenation/dehydrogenation behaviour of multilayered stacks of Pd/Mg/Pd and Pd–Fe(Ti)–Mg–Al–Mg–Fe(Ti)–Pd grown by electron beam physical vapour deposition. The palladium coating was deposited at both sides of the structure to ensure a fast dissociation rate and good transport properties for hydrogen as well as to avoid oxidation of magnesium either from atmosphere as from the substrate surface. Fe and Ti layers were included in the stack composition in order to assess their possible catalyst effect as well as to prevent the formation of Mg_xPd_y intermetallics during the thermal treatments. We have studied the structure evolution after thermal treatments as well as after the hydrogenation and dehydrogenation processes using XRD. We have also followed the reactions kinetics by resistometry and differential scanning calorimetry. The nanostructured Mg films have been hydrogenated at temperature as low as 50 °C in few minutes. Adding aluminium to magnesium has improved its hydrogenation capacity. We have also observed that the formation of an Mg_xAl_y intermetallic before hydrogenation improves the storage capacity. We have confirmed that titanium is a better catalyst for the hydrogenation/dehydrogenation of the Mg films.     

Hydrogenation and dehydrogenation behaviours of nanocrystalline Mg20Ni10−xCux (x = 0−4) alloys prepared by melt spinning

In order to improve the hydriding and dehydriding kinetics of the Mg₂Ni-type alloys, Ni in the alloy was partially substituted by element Cu, and the nanocrystalline Mg₂Ni-type Mg₂₀Ni_10−xCu_x (x = 0, 1, 2, 3, 4) alloys were synthesized by melt-spinning technique. The structures of the as-cast and spun alloys were studied by XRD, SEM and HRTEM. The hydrogen absorption and desorption kinetics of the alloys were measured using an automatically controlled Sieverts apparatus. The results show that the substitution of Cu for Ni does not change the major phase Mg₂Ni. The hydrogen absorption capacity of the alloys first increases and then decreases with rising Cu content, but the hydrogen desorption capacity of the alloys grows with increasing Cu content. The melt spinning significantly improves the hydrogenation and dehydrogenation capacity and kinetics of the alloys.     

Facilitating de/hydrogenation by long-period stacking ordered structure in Mg based alloys

We propose a simple strategy to effectively improve the hydrogenation and dehydrogenation kinetics of Mg based hydrogen storage alloys. We designed and prepared an Mg_91.9Ni_4.3Y_3.8 alloy consisting of a large quantity of long-period stacking ordered (LPSO) phases. A type of highly dispersed multiphase nanostructure, which can markedly promote the de/hydrogenation kinetics, has been obtained utilizing the decomposition of LPSO phases at first a few of hydrogenation reactions. The fine structures of LPSO phases and the microstructural evolutions of the alloy during hydrogenation and dehydrogenation reactions were in detail characterized by means of transmission electron microscopy (TEM). The LPSO phases transformed to MgH₂, Mg₂NiH₄, and YH₃ after the first hydrogenation. The highly dispersed nanostructure at macro and micro (nano) scale range remains even after several de/hydrogenation cycles. The alloy shows excellent hydrogen storage properties and its reversible hydrogen absorption/desorption capacities are about 5.8 wt% at 300 °C. Particularly, the alloy exhibits very fast dehydrogenation kinetics. The dehydrogenated sample can release approximately 5 wt% hydrogen at 300 °C within 200 s and 5.5 wt% within 600 s. We elucidate the structural mechanism of the alloy with outstanding hydrogen storage performance.     

Role of MgCo compound on the sorption properties of the Mg-Co milled mixtures

The influence of MgCo on the reaction paths during hydriding and dehydriding processes of Mg-Co mixtures was studied using a combined HP-DSC and XRD approach. Mg-Co mixtures with different compositions were mechanically milled under argon to prepare Mg-Co nanocomposites and then submitted to thermal treatment at 300 °C for 5 days to induce MgCo formation. The local Mg-Co composition in the milled and milled-heated samples determines the nature of the phases obtained after hydriding/dehydriding cycling. The formation of Mg₆Co₂H₁₁, Mg₂CoH₅ and MgH₂ hydrides occurs after the first hydriding stage of the 2Mg-Co and Mg-Co milled mixtures due to kinetic restrictions. On the contrary, Mg-Co milled-heated mixture exhibits the selective formation of Mg₂CoH₅ during first hydriding via two-step reaction. In the first one, MgCo disproportion to MgH₂ and Co takes place simultaneously with Mg hydriding (<200 °C). The second step involves MgCo hydriding to Mg₂CoH₅ through MgH₂ as intermediate phase (>200 °C). Dehydriding reaction is enhanced by dispersion of Co into Mg-matrix, which reduces more than 100 °C the hydrogen desorption temperature when compared with the Mg-Co milled sample without previous heating.     

The effects of Co and Ni addition on the hydrogen storage properties of Mg3Mm

The effects of Ni and Co addition on the hydrogen storage properties of Mg₃Mm alloy was studied by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX) and pressure-composition isotherm (PCI) measurement. The hydrogen absorption kinetics and the thermodynamic parameters (apparent ΔH, ΔS) for Mg₃Mm dehydrogenation reactions in Mg₃Mm, Mg₃MmNi_0.1 and Mg₃MmNi_0.1Co_0.1 alloys have been also investigated. The maximum hydrogen storage content of Mg₃Mm, Mg₃MmNi_0.1 and Mg₃MmNi_0.1Co_0.1 alloys was improved due to that the addition of Ni and/or Co further spurred the MmH₃ phase transforming to MmH₂ phase. On the other side, the kinetics curves show the addition of Co could enhance hydrogen absorption rate while the addition of Ni change the hydrogenation reaction mechanism.     

Improved hydrogen storage kinetics of Mg-based alloys by substituting La with Sm

Element substitution is an effective strategy for improving Mg-based alloys in their hydrogenation/dehydrogenation property. Thereby, in this paper, Sm was selected to partially replace La in a La–Mg-based alloy for improving its hydriding and dehydriding performance. The alloys with the compositions of Mg₈₀Ni₁₀La_10-xSm_x (x = 0–4) were manufactured through vacuum induction melting. Their microstructures and phase compositions were measured by XRD, SEM and HRTEM. The isothermal hydrogen storage property was tested through an automatic Sieverts apparatus. Non-isothermal hydrogen desorption performance was measured through TGA and DSC. Arrhenius and Kissinger methods were adopted to calculate the dehydrogenation activation energy of alloys. The results reveal that all of the experimental alloys can reversibly absorb and release a large amount of H₂ at appropriate temperatures. The substitution of Sm for La ameliorates the hydriding and dehydriding kinetics, but it results in an undesired reduction of hydrogen absorption and desorption capacities. Substituting La by Sm decreases the initial hydrogen release temperature of the hydride visibly. Furthermore, substituting Sm for La engenders the dehydrogenation activation energy decline clearly, which is considered as the main reason for the improved hydrogen desorption kinetics resulted from Sm replacing La.     

Influence of the substitution of La for Mg on the microstructure and hydrogen storage characteristics of Mg20−xLaxNi10 (x = 0–6) alloys

In order to enhance the glass forming ability of the Mg₂Ni-type hydrogen storage alloy, the Mg in the alloy was partially substituted by La. The alloys Mg_20−xLa_xNi₁₀ (x = 0, 2, 4, 6) were prepared by casting and rapid quenching. The structures and morphologies of the as-cast and the quenched alloys were studied by XRD, SEM and HRTEM. It was found that no amorphous phase was formed in the as-quenched La-free alloy. But the as-quenched alloys containing La held a major amorphous phase, confirming that the substitution of La for Mg significantly enhances the glass forming ability of the alloys. When La content x ≤ 2, the major phase in the as-cast alloys is Mg₂Ni phase, but with the further increase of La content, the major phase of the as-cast alloys changes into (La,Mg)Ni₃ + LaMg₃ phase. Thermal stability of the as-quenched alloys was studied by DSC, showing that La content engenders a negligible influence on the crystallization temperature of the amorphous phase. The hydrogen absorption and desorption kinetics of the as-cast and the quenched alloys were measured by an automatically controlled Sieverts apparatus. The results showed that the hydrogen absorption and desorption capacities and kinetics of the as-cast alloys clearly rise with increasing La content. For La content x = 2, the as-quenched alloy displays an optimal hydrogen desorption kinetics at 200 °C. The electrochemical measurement showed that the discharge capacities of the as-cast alloys rose with the increase of La content, but those of the as-quenched alloys obtained the maximum values with the variation of La content. The cycle stability of the as-cast and the quenched alloys significantly improved with increasing La content.     

Microchip power compensated calorimetry applied to metal hydride characterization

In this work, we show the suitability of the thin film membrane-based calorimetric technique to measure kinetically limited phase transitions such as the dehydrogenation of metallic hydrides. Different compounds such as Mg, Mg/Al and Mg₈₀Ti₂₀ have been deposited over the active area of the microchip by electron beam evaporation. After several hydrogenation treatments at different temperatures to induce the hydride formation, calorimetric measurements on the dehydrogenation process of those thin films, either in vacuum or in air, are performed at a heating rate of 10 °C/min. We observe a significant reduction in the onset of dehydrogenation for Mg₈₀Ti₂₀ compared with pure Mg or Mg/Al layers, which confirms the beneficial effect of Ti on dehydrogenation. We also show the suitability of the membrane-based nanocalorimeters to be used in parallel with optical methods. Quantification of the energy released during hydrogen desorption remains elusive due to the semi-insulating to metallic transition of the film which affects the calorimetric trace.     

Remarkable decrease in dehydrogenation temperature of Li–B–N–H hydrogen storage system with CoO additive

Cobalt monoxide (CoO) was introduced into the Li–B–N–H system as a catalyst precursor, and the hydrogen desorption behavior of the LiBH₄–2LiNH₂–xCoO (x = 0–0.20) composites was investigated. It was observed that the majority of hydrogen desorption from the CoO-added sample occurred simultaneously with the melting of α-Li₄BN₃H₁₀. Moreover, the 0.05CoO-added sample exhibited optimized dehydrogenation properties, desorbing 9.9 wt% hydrogen completely with an onset temperature of 100 °C and exhibiting a decrease of more than 120 °C in the onset dehydrogenation temperature with respect to that of the additive-free sample. The activation energy of hydrogen desorption for the 0.05CoO-added sample was reduced by 30%. XAFS measurements showed that the CoO additive was first reduced chemically to metallic Co during the initial stage of thermal dehydrogenation, and the newly produced metallic Co acted as the catalytic active species in favor of the creation of B–N bonding. More importantly, approximately 1.1 wt% of hydrogen could be recharged into the fully dehydrogenated 0.05CoO-added sample at 350 °C and a hydrogen pressure of 110 atm, which represents much better performance than that exhibited by the pristine sample.     

Hydrogen desorption performance of high-energy ball milled Mg2NiH4 catalyzed by multi-walled carbon nanotubes coupling with TiF3

The Mg₂NiH₄ complex hydrides were synthesized by high-energy ball milling (HEBM) MgH₂ + Ni mixtures. Multi-walled carbon nanotubes (MWCNTs) or TiF₃ as catalysts were added and the catalytic-dehydrogenation behaviors were investigated. All prepared samples are characterized by X-ray diffraction (XRD) spectroscopy, scanning electron microscope (SEM) and differential scanning calorimetry (DSC) to acquire information of microstructure, phase compositions, surface and dehydrogenation properties. The results indicate that the method of adding catalysts by HEBM is reasonable and the hydrogen desorption property of Mg₂NiH₄ is improved by catalysts. It is worth noting that the dehydrogenation temperature (T_D) and the activation energy (E_a) of Mg₂NiH₄ catalyzed by MWCNTs coupling with TiF₃ are reduced to 230 °C (243.6 °C of Mg₂NiH₄) and 53.24 kJ/mol (90.13 kJ/mol of Mg₂NiH₄), respectively. The addition of proper catalysts is proved to be an effective strategy to decrease T_D and E_a of Mg₂NiH₄ hydrides.     

Hydrogenation of Mg and two chosen Mg–Ni alloys

Structure changes during hydrogenation are observed in pure Mg, Mg₂Ni intermetallic (I) and Mg eutectic alloy – 23.5 wt.% Ni (E). Samples were prepared by (i) ball-milling and compacting (alloys I and E) and (ii) by mould casting (Mg and alloy E). Phase composition was checked by SEM and XRD. It was found that the hydrogenated cast alloy I and ball-milled alloy I hydrogenated below the transition temperature T_tr = 508 K contained a much higher amount of low-temperature un-twinned phase LT1 than the ball-milled alloy I hydrogenated above T_tr. It was shown that micro-twinned phase LT2 slows down the rate of hydrogen desorption. Persistent changes of morphology were observed in all materials after the first hydrogen charging cycle which may explain the so-called activation of Mg-based hydrogen-storage materials described in the literature.     

Electrochemical properties of ball-milled LaMg12–Ni composites containing carbon nanotubes

Nanocrystalline LaMg₁₂–Ni composites containing carbon nanotubes (CNTs) were prepared by two ball-milling ways, and the resulting microstructure and electrochemical characteristics were investigated. It is found that the discharge capacities and high-rate dischargeabilities (HRDs) of the CNT-containing composites prepared by ball-milling as-prepared nanocrystalline LaMg₁₂–Ni composite and CNTs for 1 h (denoted as Composite-CNT1-1) were obviously higher than that by ball-milling LaMg₁₂ alloy, Ni powder and CNT1 together for 12 h (denoted as Composite-CNT1-2). The highest discharge capacity reaches 999.8 mA h/g. Raman spectra and X-ray diffraction (XRD) patterns show that the structure of the CNTs still exists and the defect increases in Composite-CNT1-1. However, in Composite-CNT1-2, due to the overlong ball-milling time, the crystalline structure of the CNTs has been destroyed and amorphous carbons have formed. Cyclic voltammetry and electrochemical impedance spectra measurements indicate that the CNT modification in Composite-CNT1-1 increases the electrocatalytic activity and surface area, which leads to its higher discharge capacity and HRD. The larger electrochemical reaction resistance caused by amorphous carbon in Composite-CNT1-2 results in its lower discharge capacity and HRD. The CNT modification has negligible effect on the diffusion process of hydrogen from the surface to the bulk of the composites.     

Thermal decomposition of non-catalysed MgH2 films

Nanocrystalline Mg films with thicknesses between 45 and 900 nm were prepared by e-beam on fused-SiO₂ substrates and hydrogenated at 280 °C to investigate the H-absorption/desorption process. Films were characterized by XRD, RBS, Raman, FEG, “in situ” optical measurements and TPD-MS. Whereas practically full conversion into MgH₂ is observed in thinner films (d < 150–200 nm), higher amount of hydrogen is not absorbed by thicker films (d > 200–250 nm) that is attributed to the formation of Mg₂Si–MgO phases (observed by RBS and Raman) as well as the slow kinetics of MgH₂ formation. H-desorption process is controlled by a nucleation and growth process and hydrogen is released at lower desorption temperatures (T_d = 425 °C) than bulk MgH₂. T_d are slightly lower (ΔT ∼ 25 °C) in thickest hydrogenated films (d > 200–250 nm) suggesting an influence of Mg₂Si and MgO phases, formed during hydrogenation.     

Bulk modulus and thermal expansion coefficient of mechano-chemically synthesized Mg2FeH6 from high temperature and high pressure studies

Mg₂FeH₆ was synthesized by ball milling MgH₂ and Fe (2:1 molar ratio) mixture for 72 h followed by heating at 400 °C under H₂ pressure. The hydride formation, its structure and homogeneity were investigated by scanning electron microscopy, X-ray diffraction, transmission electron microscopy and Raman spectroscopy. High pressure in situ synchrotron X-ray diffraction and Vienna ab initio simulation were used to determine bulk modulus of the sample. The bulk modulus of Mg₂FeH₆ was found to be 75.4(4) GPa by optimized experiment and 76.3 GPa by theoretical simulation. From high temperature in situ X-ray diffraction study the volumetric thermal expansion coefficient of Mg₂FeH₆ was found to be α_v = 5.85(3) × 10⁻⁵ + 7.47(7) × 10⁻⁸ (T − T_o)/°C. Decomposition of Mg₂FeH₆ was observed at 425 °C and the decomposition products were Mg, Fe and H₂.     

Characterization of Mg–20 wt% Ni–Y hydrogen storage composite prepared by reactive mechanical alloying

Mg–20 wt% Ni–Y composite was successfully prepared by reactive mechanical alloying (RMA). X-ray diffraction (XRD) measurement showed that both MgH₂ and Mg₂NiH₄ co-exist in the milled composite. The composite exhibits excellent hydrogen sorption kinetics and does not need activation on the first hydrogen storage process. It can absorb 3.92 and 5.59 wt% hydrogen under 3.0 MPa hydrogen pressure at 293 and 473 K in 10 min, respectively, and desorb 4.67wt% hydrogen at 523 K in 30 min under 0.02 MPa hydrogen pressure. The equilibrium desorption pressure of the composite are 0.142, 0.051 and 0.025 MPa at 573, 543 and 523 K, respectively. The differential scanning calorimetry (DSC) measurement showed that dehydrogenation of Mg–20 wt% Ni–Y composite was depressed about 100 K comparing to that of milled pure MgH₂. It is deduced that both the catalysis effect of Mg₂Ni and YH₃ distributed in Mg substrate and the crystal defects formed by RMA are the main reason for improving hydrogen sorption kinetics of the Mg–20 wt% Ni–Y composite.     

Mechanisms of hydrides’ nucleation and the effect of hydrogen pressure induced driving force on de-/hydrogenation kinetics of Mg-based nanocrystalline alloys

Aiming to gain insight on the hydrogen storage properties of Mg-based alloys, partial hydrogenation and hydrogen pressure related de-/hydrogenation kinetics of Mg–Ni–La alloys have been investigated. The results indicate that the phase boundaries, such as Mg/Mg₂Ni and Mg/Mg₁₇La₂, distributed within the eutectics can act as preferential nucleation sites for β-MgH₂ and apparently promote the hydrogenation process. For bulk alloy, it is observed that the hydrogenation region gradually grows from the fine Mg–Ni–La eutectic to primary Mg region with the extension of reaction time. After high-energy ball milling, the nanocrystalline powders with crystallite size of 12～20 nm exhibit ameliorated hydrogen absorption/desorption performance, which can absorb 2.58 wt% H₂ at 368 K within 50 min and begin to desorb hydrogen from ～508 K. On the other side, variation of hydrogen pressure induced driving force significantly affects the reaction kinetics. As the hydrogenation/dehydrogenation driving forces increase, the hydrogen absorption/desorption kinetics is markedly accelerated. The dehydrogenation mechanisms have also been revealed by fitting different theoretical kinetics models, which demonstrate that the rate-limiting steps change obviously with the variation of driving forces.     

Pressure DSC study of the hydrogenation and dehydrogenation of some intermetallic compounds Mg2Ni

Pressure differential scanning calorimetry (DSC) has been applied to a study of the hydrogenation and dehydrogenation of some intermetallic compounds Mg₂Ni. The effects of hydrogen pressure, pulverized compound's sizes as well as chemical composition of the compound, partial substitution of Mg in Mg₂Ni by Al, and the second phase MgNi₂ dispersed in Mg₂Ni on the hydrogenation and dehydrogenation of the intermetallic compound Mg₂Ni are elucidated in some detail by this experimental technique. It is emphasized that a pressure DSC is available as a rapid and convenient experimental means for assessing hydrogen absorption and desorption properties of hydrogen storage materials.