Structural investigation and hydrogen storage properties of Ca3-xLaxMg2Ni13 alloys

The phase structures and hydrogen storage properties of the Ca_3-xLa_xMg₂Ni₁₃ alloys were investigated. It was found that the La substitution is unfavorable for the formation of the Ca₃Mg₂Ni₁₃-type phase. The La-substituted alloys consist of multiple phases. Increasing La content to x = 2.25 leads to a disappearance of Ca₃Mg₂Ni₁₃-type phase. Among these alloys, the Ca_1.5La_1.5Mg₂Ni₁₃ alloy has highest equilibrium pressures of hydrogen absorption–desorption and a highest hydrogen desorption capacity of 1.34 wt.% at 318 K. The discharge capacity decreases for La-substituted alloys. However, the cycling capacity retention rate (S₃₀) increases from 13.7 to 67.6% when x increases from 0 to 3.     

Influence of annealing treatment on the hydrogen storage properties of La2−xTixMgNi9 (x = 0.2, 0.3) alloys

La_2−xTi_xMgNi₉ (x = 0.2, 0.3) alloys have been prepared by magnetic levitation melting under an Argon atmosphere, and the as-cast alloys were annealed at 800 °C, 900 °C for 10 h under vacuum. The effects of annealing on the hydrogen storage properties of the alloys were investigated systematically by XRD, PCT and electrochemical measurements. For the La_2−xTi_xMgNi₉ (x = 0.2, 0.3) alloys, LaNi₅, LaMg₂Ni₉ and LaNi₃ are the main phases and a Ti₂Ni phase appears at 900 °C. The effective hydrogen storage capacity increases from 1.10, 1.10 wt.% (as-cast) to 1.22, 1.16 wt.% (annealed 800 °C) and 1.31, 1.27 wt.% (annealed 900 °C), respectively. The annealing not only improves the hydrogen absorption/desorption kinetics but also increases the maximum discharge capacity and enhances the cycling stability. The La_1.8Ti_0.2MgNi₉ alloy annealed at 900 °C exhibits good electrochemical properties, and the discharge capacities decrease from 366.1 mA h/g to 219.6 mA h/g after 177 charge-discharge cycles.     

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.     

Hydrogen storage and cyclic properties of V60Ti(21.4+x)Cr(6.6−x)Fe12 (0 ≤ x ≤ 3) alloys

Hydrogen storage and cyclic properties of V₆₀Ti_(21.4+x)Cr_(6.6−x)Fe₁₂ (0 ≤ x ≤ 3) alloys were investigated systematically. All alloys were composed of single BCC phase and exhibited good activation performance. V₆₀Ti_22.4Cr_5.6Fe₁₂ showed the highest desorption capacity of 2.12 wt% with the plateau pressure of 0.061 MPa. In the absorption–desorption cycle tests, both the hydrogen desorption capacity and the micro-strain of V₆₀Ti_22.4Cr_5.6Fe₁₂ alloy showed exponential relationship with the increase of cycle numbers, which indicated that the micro-strain induced and thereafter accumulated during the absorption–desorption cycles might lead to the decrease of the desorption capacity.     

Effect of substituting Mn for Ni on the hydrogen storage and electrochemical properties of ReNi2.6−xMnxCo0.9 alloys

ReNi_2.6−xMn_xCo_0.9 (x = 0.0, 0.225, 0.45, 0.675, 0.90) alloys were prepared by induction melting. The effects of partially substituting Mn for Ni on the phase structure and electrochemical properties of the alloys were investigated systematically. In the alloys, (La, Ce)₂Ni₇ phase with a Ce₂Ni₇-type structure, (Pr, Ce)Co₃ phase with a PuNi₃-type structure, and (La, Pr)Ni₅ phase with a CaCu₅-type structure were the main phases. The (La,Pr)Ni phase appeared when x increased to 0.45, and the (La, Pr)Ni₅ phase disappeared with further increasing x (x > 0.45). The hydrogen-storage capacity of the ReNi_2.6−xMn_xCo_0.9 (x = 0.0, 0.225, 0.45, 0.675, 0.90) alloys initially increased and reached a maximum when Mn content was x = 0.45, and then decreased with further increasing Mn content. The ReNi_2.6−xMn_xCo_0.9 (x = 0.0, 0.225, 0.45, 0.675, 0.90) alloy exhibited a hydrogen-storage capacity of 0.81, 0.98, 1.04, 0.83 and 0.53 wt.%, respectively. Electrochemical studies showed that the maximum discharge capacity of the alloy electrodes initially increased from 205 mAh/g (x = 0.0) to 352 mAh/g (x = 0.45) and then decreased to 307 mAh/g (x = 90). The hydrogen absorption rate first increased and then decreased with addition of Mn element. The ReNi_2.15Mn_0.45Co_0.9 alloy showed faster hydrogen absorption kinetics than that of the other alloys. The presence of Mn element slowed hydrogen desorption kinetics.     

Hydrogen release properties of lithium alanate for application to fuel cell propulsion systems

In this paper the results of an experimental study on LiAlH₄ (lithium alanate) as hydrogen source for fuel cell propulsion systems are reported. The compound examined in this work was selected as reference material for light metal hydrides, because of its high hydrogen content (10.5 wt.%) and interesting desorption kinetic properties at moderate temperatures. Thermal dynamic and kinetic of hydrogen release from this hydride were investigated using a fixed bed reactor to evaluate the effect of heating procedure, carrier gas flow rate and sample form. The aim of this study was to characterize the lithium alanate decomposition through the reaction steps leading to the formation of Li₃AlH₆ and LiH. A hydrogen tank was designed and realized to contain pellets of lithium alanate as feeding for a fuel cell propulsion system based on a 2-kW Polymeric Electrolyte Fuel Cell (PEFC) stack. The fuel cell system was integrated into the power train comprising DC-DC converter, energy storage systems and electric drive for moped applications (3 kW). The experiments on the power train were conducted on a test bench able to simulate the vehicle behaviour and road characteristics on specific driving cycles. In particular the efficiencies of individual components and overall power train were analyzed evidencing the energy requirements of the hydrogen storage material.     

Hydrogen storage properties of Ti0.72Zr0.28Mn1.6V0.4 alloy prepared by mechanical alloying and copper boat induction melting

In the present study, two process techniques, mechanical alloying and innovative vacuum copper boat induction melting, were used to produce Ti_0.72Zr_0.28Mn_1.6V_0.4 alloy for hydrogen storage applications. The hydrogen absorption and desorption properties of the alloy were studied. The material structure and phases were characterized by XRD and SEM. The hydrogen absorption and desorption properties of the alloy were measured by an automatically controlled Sieverts apparatus. The results showed that the samples consisted of two main phases, C14 Lave phase and V-base solid solution phase. The maximum capacity of abs/desorption was achieved at mediate temperature (150 °C). The hydrogen capacity of the induction melted samples in various temperatures was higher than that for the samples produced by mechanical alloying method. The maximum absorption capacity of the induction melted and mechanically alloyed samples were 2 and 1.2 wt%, respectively. The maximum desorption capacity of the induction melted and mechanically alloyed samples were 0.45 and 0.1 wt%, respectively.     

Effect of particle size on the electrochemical properties of MmNi3.8Co0.75Mn0.4Al0.2 hydrogen storage alloy

Charge and discharge testing, linear polarization, electrochemical impedance spectroscopy (EIS) and potential step chronoamperometry (PSCA) were used to investigate the electrochemical properties of the Ce-rich mischmetal MmNi_3.8Co_0.75Mn_0.4Al_0.2 hydrogen storage alloy with different particle sizes. At a discharge current density of 900 mA/g, the alloy with small original particle size maintained a high rate dischargeability (HRD) above 86% while the alloy with large particle size could not discharge in the same potential region. The alloy with small original particle size also showed lower contact resistances and polarization resistance after full activation. Both the exchange current density and the hydrogen diffusion coefficient increased when the hydrogen concentration decreased. The charge-transfer reaction on the surface of alloy particles with different sizes should be mainly responsible for the differences in electrochemical properties, especially the HRD.     

Structure, morphology and hydrogen storage properties of a Ti0.97Zr0.019V0.439Fe0.097Cr0.045Al0.026Mn1.5 alloy

The Ti_0.97Zr_0.019V_0.439Fe_0.097Cr_0.045Al_0.026Mn_1.5 alloy is a hexagonal C14 Laves phase material that reversibly stores hydrogen under ambient temperatures. Structural changes are studied by XRD and SEM with regard to hydrogenation and dehydrogenation cycling at 25, 40 and 60 °C. The average particle size is reduced after hydrogenation and dehydrogenation cycling through decrepitation. The maximum hydrogen capacity at 25 °C is 1.71 ± 0.01 wt. % under 78 bar H₂, however the hydrogen sorption capacity decreases and the plateau pressure increases at higher temperatures. The enthalpy (ΔH) and entropy (ΔS) of hydrogen absorption and desorption have been calculated from a van’t Hoff plot as −21.7 ± 0.1 kJ/mol H₂ and −99.8 ± 0.2 J/mol H₂/K for absorption and 25.4 ± 0.1 kJ/mol H₂ and 108.5 ± 0.2 J/mol H₂/K for desorption, indicating the presence of a significant hysteresis effect.     

Hydrogen storage in a Li–Al–N ternary system

Hydrogen-storage properties and mechanisms of a novel Li–Al–N ternary system were systematically investigated by a series of performance evaluation and structural examinations. It is found that ca. 5.2 wt% of hydrogen is reversibly stored in a Li₃N–AlN (1:1) system, and the hydrogenated product is composed of LiNH₂, LiH, and AlN. A stepwise reaction is ascertained for the dehydrogenation of the hydrogenated Li₃N–AlN sample, and AlN is found reacting only in the second step to form the final product Li₃AlN₂. The calculation of the reaction enthalpy change indicates that the two-step dehydrogenation reaction is more thermodynamically favorable than any one-step reaction. Further investigations exhibit that the presence of AlN in the LiNH₂–2LiH system enhances the kinetics of its first-step dehydrogenation with a 10% reduction in the activation energy due likely to the higher diffusivity of lithium and hydrogen within AlN.     

Structural characteristics and hydrogen storage properties of Ca3.0−xMgxNi9 (x = 0.5, 1.0, 1.5 and 2.0) alloys

The effect of Mg content on the structural characteristics and hydrogen storage properties of the Ca_3.0−xMg_xNi₉ (x = 0.5, 1.0, 1.5 and 2.0) alloys was investigated. The lattice parameters and unit cell volume of the PuNi₃-type (Ca, Mg)Ni₃ main phase decreased with increasing Mg content. The 6c site of PuNi₃-type structure was occupied by both Ca and Mg atoms. Moreover, the occupation factor of Ca on the 6c site decreased with the increase of Mg content. The hydrogen absorption capacity of the alloys decreased due to higher Mg content. However, the thermodynamic properties of hydrogen absorption and desorption were improved and the plateau pressures were increased. When x = 1.5–2.0, the Ca_3.0−xMg_xNi₉ alloys had favorable enthalpy (ΔH) and entropy (ΔS) of hydride formation.     

Hydrogen storage properties of Zr2Co crystalline and amorphous alloys

To further explore the application feasibility of Zr₂Co alloy in tritium-related fields, hydrogenation/dehydrogenation properties of this material of crystalline or amorphous structure, prepared by arc melting or melt spinning, were studied by pressure-composition temperature measurement, X-ray diffraction, differential scanning calorimeter, thermal desorption spectroscopy. It was found that the two kinds of Zr₂Co alloys can absorb hydrogen in a close full concentration of ~9 mmol/g, and may have similar equilibrium hydrogen pressure in the order of 10^?6 Pa at room temperature. In their hydrogenated samples various hydrides were observed to form, including ZrH₂, Zr₂CoH₅, ZrCoH₃ and an amorphous one with gradually decreasing general thermostability. The amorphous alloy exhibited easier hydrogen induced disproportionation caused by highly stable ZrH₂ and much slower hydrogen absorption kinetics. This disproportionation behavior of the crystalline alloy was found to be entirely suppressed by changing heating process. The results firmly indicate that crystalline Zr₂Co alloy could be more favorable for tritium treatment due to very low equilibrium pressure and the feasibility of eliminating the disproportionation.     

The effect of annealing on the electrochemical properties of Zr0.5Ti0.5Mn0.5V0.3Co0.2Ni1.1 alloy electrodes

The annealing treatment was found to result in the improvement in the cyclic stability but the degradation of discharge capacity, activation and high-rate dischargeability for Zr_0.5Ti_0.5Mn_0.5V_0.3Co_0.2Ni_1.1 alloy electrode. A lower discharge potential in the annealed alloy electrode was found owing to a more homogeneous alloy, which is consistent with the pressure–composition isotherms (P–C–T) measurement. We found that the annealed alloy also had lower and flatter pressure plateaus, and larger pressure hysteresis. At high discharge rates, the hydrogen diffusion in the bulk of the alloy was the rate-determining step. The diffusion coefficients for hydrogen in the annealed and as-cast alloys were calculated to be 1.4×10⁻¹² cm² s⁻¹ and 4.3×10⁻¹² cm² s⁻¹, respectively. The lowering of high-rate discharge capacity can be ascribed to the reason that the hydrogen diffusion coefficient is lower due to homogeneous microstructure in the annealed alloy.     

Effects of substituting Al for Cr in the Ti0.32Cr0.43V0.25 alloy on its microstructure and hydrogen storage properties

Substituting Al for part of Cr in Ti_0.32Cr_0.43V_0.25 alloy caused BCC lattice parameter and crystallite size to increase and lattice strain to decrease. These microstructual changes caused the decrease in the hydrogen storage capacity and the increase in both the plateau pressure and the hysteresis. The results were contradictory to the general observation that the plateau pressure decreases with the increase in the lattice parameter. The fact that the bond structure between H and Al and that between H and the transition metals differ can account for this discrepancy. This difference also resulted in the decrease in the hydrogen storage capacity. The increased hysteresis resulting from the increase in the Al content can be ascribed to the increased crystallite size and the decreased lattice strain.     

H2 refueling assessment of composite storage tank for fuel cell vehicle

Hydrogen as compressed gas is a promising option for zero-emission fuel cell vehicle. The fast and efficient refueling of high pressure hydrogen can provide a convenient platform for fuel cell vehicles to compete with conventional gasoline vehicles. This paper reports the finding of adiabatic simulation of the refueling process for Type IV tank at nominal working pressure of 70 MPa with considering the station refueling conditions. The overall heat transfer involved in refueling process was investigated by heat capacity model based on MC method defined by SAE J2601. The simulation results are validated against experimental data of European Commission's Gas Tank Testing Facility at Joint Research Centre (GasTef JRC), Netherlands. The results confirmed that end temperature and state of charge significantly depends on refueling parameters mainly supply hydrogen temperature and filling rate.     

Hydrogen storage properties of Ti2−xCrVMx (M = Fe,Co, Ni) alloys

In this work, quaternary alloys having compositions Ti_1.9CrVM_0.1 and Ti_1.8CrVM_0.2 (M = Fe, Co and Ni) have been studied in detail for their structural aspects and hydrogen absorption–desorption properties. All the alloys form bcc phase solid solutions and after hydrogen absorption the structures change to fcc. The pressure composition isotherms, hydrogen storage capacities and hydrogen absorption kinetics were studied using Sievert's type of volumetric setup. The Ti_1.9CrVFe_0.1, Ti_1.9CrVCo_0.1 and Ti_1.9CrVNi_0.1 alloys are found to absorb maximum 3.80, 3.68 and 3.91 wt.% of hydrogen respectively; whereas, Ti_1.8CrVCo_0.2 and Ti_1.8CrVNi_0.2 alloys show 3.52 and 3.67 wt.% of hydrogen at room temperature. All the alloys show fast hydrogen absorption kinetics at the room temperature. From differential scanning calorimetric measurements, it has been found that Fe, Ni and Co substitution in place of Ti decreased the hydrogen desorption temperature drastically compared to the parent alloy.     

Hydrogen storage properties of ultrahigh pressure Mg12NiY alloys with a superfine LPSO structure

Ultrahigh pressure (UP) plays a crucial role in modifying structures and properties of functional materials. The effects of UP treatment (4 GPa) on phase transition and hydrogen storage properties of Mg₁₂NiY alloys has been investigated at the temperature range of 800–1300 °C. The results show that the dimension of 18R-type long period stacking ordered (LPSO) structure in the Mg₁₂NiY sample after UP treatment at 1300 °C is two orders of magnitude smaller than that in the as-cast sample. The hydrogen storage capacity, kinetics and cycle properties of Mg₁₂NiY alloys are concurrently improved after UP treatment. The two-step reaction process is confirmed during hydrogenation process by combining cycle testing and in-situ transmission electron microscopy (TEM) observations. The reasons for high hydrogen storage properties are mainly related to three aspects: the increased volume fraction of high angle interfaces between LPSO phase and matrix, the reduction of hydrogen diffusion distance, and the low energy barrier of hydrogen diffusion in the interior of superfine LPSO structures.     

Hydrogen storage capability of Se@C120 system

A single-walled, capped and selenium doped, carbon nanotube, Se@C₁₂₀, was doped endohedrally with hydrogen molecules to obtain a series of (n_H2+Se)@_C120$(n{\mathrm{H}}_2+\mathrm{Se})@{\mathrm{C}}_{120}$, (n  : 0–11) systems. Then, they were subjected to quantum chemical treatment using PM3 method at the level of RHF approach. Calculations indicated that these systems were stable but endothermic in nature. In (10_H2+Se@_C120)$(10{\mathrm{H}}_2+\mathrm{Se}@{\mathrm{C}}_{120})$ and (11_H2+Se@_C120)$(11{\mathrm{H}}_2+\mathrm{Se}@{\mathrm{C}}_{120})$ systems, the hydrogen molecule nearest to the Se atom tends to dissociate to form a quasi-_H2Se${\mathrm{H}}_2\mathrm{Se}$ structure.     

Hydrogen absorption/desorption behavior of Mg50La20Ni30 bulk metallic glass

In this work, Mg₅₀La₂₀Ni₃₀ bulk metallic glass (BMG) was prepared and its hydrogen absorption/desorption behavior was studied. The amorphous structure was found to be retained after gaseous hydrogenation. The T_g and T_x of the hydrogenated Mg₅₀La₂₀Ni₃₀ BMG was 561 K and 619 K respectively, much higher than the corresponding value of 463 K and 504 K of the unhydrogenated sample. Mg₅₀La₂₀Ni₃₀ BMG absorbed 0.73 and 1.85 wt% hydrogen within 1 h at 313 K and 423 K respectively, which was higher than that of ball-milled Mg₂Ni alloy. Mg₅₀La₂₀Ni₃₀ BMG exhibited an equilibrium hydrogen absorption plateau with a pressure of 0.07 MPa in pressure–composition isotherm curve at 423 K. It suggested that Mg-based BMGs are promising materials for hydrogen storage applications.     

Effect of LaH3 additive on microstructures and hydrogen storage properties of V40Ti26Cr26Fe8 alloys prepared by hydride powder sintering method

Hydride-Powder-Sintering(HPS) as a new preparation approach was applied in the low cost V₄₀Ti₂₆Cr₂₆Fe₈ hydrogen storage alloys successfully, which provides an alternative preparation route for other types of hydrogen storage alloys. V₄₀Ti₂₆Cr₂₆Fe₈ alloy exhibits ideal hydrogen absorption-desorption performance after adding moderate content of LaH₃. Optimizing sintering process by increasing the sintering temperature and time has improved hydrogen desorption plateau evidently. X-ray diffraction analysis results show that the Ti-Oxide phase basically no longer exists when the LaH₃ content is greater than or equal to 3 wt% as compared to that of LaH₃ content below 3 wt%. Pressure-Compose-Temperature(PCT) curves show that the hydrogen absorption and desorption capacities increase gradually with the increase of LaH₃ content. The lattice parameters calculated by Rietveld refinement has the same variety rule as the hydrogen absorption-desorption capacities with the increase of LaH₃ content. It can be inferred that the addition of LaH₃ has reduced the content of Ti-Oxide and then the lattice parameters increase, which leads to the improvement of hydrogen performance of the alloy. The most appropriate preparation process is 3 wt% of LaH₃ additive with a sintering process 1673 K-6h, correspondingly, the hydrogen absorption and desorption capacities are 3.13 wt% and 1.97 wt%, respectively.