Study on the structure and hydrogen storage characteristics of as-cast La0.7Mg0.3Ni3.2Co0.35−XCuX alloys

In this paper, the structure, hydrogen storage performance, electrochemical discharge and cyclic characteristics of La_0.7Mg_0.3Ni_3.2Co_0.35−XCu_X alloys were investigated using X-ray diffraction (XRD), pressure composition isotherm (PCT) and electrochemical tests. XRD tests showed that all of the alloys were composed of La₂Ni₇ and LaNi phases. The ratio of LaNi phase in these alloys increased with increasing substitution of Cu for Co. PCT tests showed that increasing substitution of Cu for Co resulted in the decrease of hydrogen storage capacity and the increase of plateau pressure. Electrochemical discharge tests showed that the discharge capacity increased first and then decreased with increasing substitution of Cu for Co.     

Enhanced hydrogen storage properties of Ti–Cr–Nb alloys by melt-spin and Mo-doping

Ti–Cr–Nb hydrogen storage alloys with a body centered cubic (BCC) structure have been successfully prepared by melt-spin and Mo-doping. The crystalline structure, solidification microstructural evolution, and hydrogen storage properties of the corresponding alloys were characterized in details. The results showed that the hydrogen storage capacity of Ti–Cr–Nb ingot alloys increased from 2.2 wt% up to around 3.5 wt% under the treatment of melt-spin and Mo-doping. It is ascribed that the single BCC phase of Ti–Cr–Nb alloys was stabilized after melt-spin and Mo-doping, which has a higher theoretical hydrogen storage site than the Laves phase. Furthermore, the melt-spin alloy after Mo doping can further effectively increase the de-/absorption plateau pressure. The hydrogen desorption enthalpy change ΔH of the melt-spin alloy decreased from 48.94 kJ/mol to 43.93 kJ/mol after Mo-doping. The short terms cycling test also manifests that Mo-doping was effective in improving the cycle durability of the Ti–Cr–Nb alloys. And the BCC phase of the Ti–Cr–Nb alloys could form body centered tetragonal (BCT) or face center cubic (FCC) hydride phase after hydrogen absorption and transform to the original BCC phase after desorption process. This study might provide reference for developing reversible metal hydrides with favorable cost and acceptable hydrogen storage characteristics.     

Structural characterization and hydrogen storage properties of the Ti31V26Nb26Zr12M5 (M = Fe,Co, or Ni) multi-phase multicomponent alloys

Structure and hydrogen storage properties of three Ti₃₁V₂₆Nb₂₆Zr₁₂M₅ multicomponent alloys with M = Fe, Co and Ni are investigated. The alloys synthesized by arc melting are characterized via X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). The as-cast ingots present multi-phase dendritic structures composed mainly of BCC phases and small amounts of C14 Laves phases. Upon hydrogenation, each alloy absorbs around 1.9 H/M (number of hydrogen atoms per metal atoms) at room temperature. XRD of fully hydrogenated samples shows the formation of multi-phase structures composed of FCC and C14 hydrides. Thermo Desorption Spectroscopy (TDS) shows that the hydrogenated alloys present multi-step desorption processes with wide temperature ranges and low onset temperatures. XRD of partially hydrogenated samples indicate the presence of intermediate BCC hydrides. XRD of desorbed samples suggest reversible reactions of absorption/desorption: BCC + C14 alloy ? intermediate BCC hydride + C14 hydride ? FCC + C14 hydrides.     

Influence of Fe addition on hydrogen storage characteristics of Ti–V-based alloy

In order to improve the hydrogen storage properties and reduce the cost of Ti–V-based BCC alloys, the effect of Fe substitution for part V on hydrogen absorption–desorption characteristics of Ti–10Cr–18Mn–32V alloy was investigated. It was found that proper amount of Fe addition was effective in improving the activation performance, enhancing the hydrogen absorption–desorption plateau pressure, reducing the hysteresis of hydrogen absorption–desorption plateau, increasing the hydrogen desorption capacity and decreasing the alloy's cost, while it depressed the hydrogen absorption capacity. X-ray diffraction (XRD) patterns and back scattering electron (BSE) images display that the single BCC phase of Fe-free alloy transformed into two phases of, BCC and C14 Laves, of Fe-containing alloy. Three phase transformations happened in the two alloys during the hydrogen release process, which resulted from the formation of three different hydride phases in the two hydrided alloys.     

Understanding crystal structure roles towards developing high-performance V-free BCC hydrogen storage alloys

Current bottlenecks in the supply and high cost of V have negatively impacted their application. There is great interest in developing V-based hydrogen storage alloys that use less or free V. Here, we investigate the role of V in deliberately designed V-based alloys. Our results affirm that V plays an undeniable role in enhancing hydrogen storage properties. It is found that V maintains the stable single BCC structure but leads to more residual hydrogen (1.4 wt%) because of the high stability of the dihydride and smaller hydriding rate because of the small lattice parameter, which offers unexpected but encouraging perspectives towards reducing the need of V in such alloys. Mo substitution for V effectively alleviates the higher residual hydrogen to achieve a high dehydriding capacity of 2.5 wt%. Moreover, the suction-cast (Ti_0.46Cr_0.54)_97.5Mo_2.5 alloy, which keeps BCC structure after suction-cast process and contains a low-Mo content, also exhibits dehydriding capacity of 2.3 wt%. The enthalpy change as well as dehydriding capacity of V-Free alloys obtained were similar to those reported V-based alloys. These findings are attractive for developing new V-free BCC hydrogen storage alloys and higher hydrogen capacity.     

Microstructure and hydrogen storage properties of Ti10+xV80-xFe6Zr4 (x=0~15) alloys

The microstructure and hydrogen storage properties of Ti_10+xV_80-xFe₆Zr₄ (x = 0, 5, 10, 15) alloys have been studied. XRD and SEM analyses show that all alloys consist of a BCC main phase and a small fraction of C14 Laves secondary phase, in which the latter precipitates along the grain boundary of the former becoming network structure. With increasing Ti content in the alloy, the lattice parameter and cell volume of the BCC main phase of the alloy increase. The chemical composition of each phase is analysed by EDS, from which the lattice parameters of BCC phase have a good linear relationship with their average atomic radii. All bulk alloys have good activation behaviors and hydriding kinetics. With the increase of Ti content, the incubation time for activation decreases first and then increases under an initial hydrogen pressure of 4 MPa at 298 K. The incubation time of Ti₁₅V₇₅Fe₆Zr₄ alloy is only 12 s. It is one of the shortest incubation time in V-based solid solution alloys as far as we know, which may be related to the existence of C14 Laves phase. All the alloys have relatively high hydrogen absorption capacities of above 3 wt%, which increase first and then decrease as the Ti content increases, achieving the maximum capacity of 3.61 wt% at x = 10 at 298 K. With increasing x, the equilibrium plateau pressure of dehydrogenation of the samples at 353 K decreases owing to the expansion of unit cell of main phase, which is far below 0.1 MPa for x = 10 and 15. The maximum desorption capacity of 1.94 wt% (desorbed to 0.001 MPa) is obtained at x = 5, compared to that of 1.6 wt% (desorbed to 0.1 MPa) achieved at x = 0.     

Structural,hydrogen storage,and electrochemical properties of Laves phase-related body-centered-cubic solid solution metal hydride alloys

Structure, gaseous phase hydrogen storage, and electrochemical properties of a series of Laves phase-related BCC solid solution metal hydride alloys with BCC/C14 ratios ranging from 0.09 to 8.52 were studied. Some properties are correlated to the phase abundance and V-content in the alloy with monotonic evolutions, for example, lattice constant, phase abundance, and hydrogen storage pressure. Other properties such as gaseous phase capacities, PCT hysteresis, high-rate dischargeability, and bulk hydrogen diffusion correlate better with the C14 phase crystallite size, which are considered to be more related to the synergetic effect between main and secondary phases. In contrast with conventional metal hydride alloys used in NiMH batteries, the electrochemical discharge capacities of these alloys are not between the maximum and the reversible hydrogen storage measured in the gaseous phase. The current study's alloys have electrochemical capacities that are insensitive to composition but have much room for improvement, with high-rate dischargeabilities that are superior compared to other commercially available alloys. With further research, these alloys show potential for high-rate battery applications.     

Effect of heat treatment on microstructure and hydrogen storage properties of mass-produced Ti0.85Zr0.13(Fex–V)0.56Mn1.47Ni0.05 alloy

Hydrogen storage as a metal hydride is the most promising alternative because of its relatively large hydrogen storage capacities near room temperature. TiMn₂-based C14 Laves phases alloys are one of the promising hydrogen storage materials with easy activation, good hydriding-dehydriding kinetics, high hydrogen storage capacity and relatively low cost. In this work, multi-component, hyper-stoichiometric TiMn₂-based C14 Laves phase alloys were prepared by a vacuum induction melting method for a hydrogen storage tank and electrochemical applications. Since TiMn₂ alloy shows high equilibrium plateau pressure, Ti and Mn were partially replaced by other metallic elements such as Zr, V, and Ni. Since pure vanadium (V) is quite expensive, the substitution of the V element in these alloys has been tried and some interesting results were achieved by replacing V by commercial ferrovanadium, FeV, raw material. XRD pattern and SEM analysis of the as-cast VIM Ti_0.85Zr_0.13(Fe_x–V)_0.56Mn_1.47Ni_0.05 alloy revealed that the main phase of the C14 Laves phase and the secondary phase of FeO formed along the grain boundary. Also, the as-cast VIM Ti_0.85Zr_0.13(Fe_x–V)_0.56Mn_1.47Ni_0.05 alloy showed a high plateau pressure slope from measurement of P–C-isotherms, which led to a decrease in reversible hydrogen storage capacity. It was found that a suitable heat treatment was very effective in the formation of the C14 single phase and improving the sloping properties. The improvement of sloping properties was mainly attributed to the strain energy effect and the homogeneity of chemical composition. In this work, hydrogen storage capacity was evaluated by a volumetric method using P–C-isotherms and a gravimetric method using magnetic suspension balance.     

Crystal structure and hydrogen storage properties of Ti-V-Mn alloys

The compositions of TiMn _{(100-x, Ti/Mn=5/8)}V_x (x = 25, 30, 35, 40, 45 and 50) alloys have been investigated comprehensively for their microstructure and hydrogen absorption/desorption properties. The proportion of BCC and C14 Laves phases changes with the V content, and BCC phase increases with increasing V content. With increasing BCC phase, more number of cycles are needed to reach to the saturated hydrogen absorption, and the hydrogen storage capacity first increases and then decreases after 40 at.% of the V content. It is indicated that the brittle C14 Laves phase plays as the “path” for hydrogen atom diffusion into the BCC phase. For the samples of V₄₅Ti₂₁Mn₃₄ and V₅₀Ti₁₉Mn₃₁ with less content of C14 Laves phase, it is difficult for hydrogen to diffuse into the BCC phase leading to low absorption capacity. The results of XRD and DSC analyses show that hydrides are less stable in V-poor samples. V₄₀Ti₂₃Mn₃₇ has the best hydrogen storage properties in this study: Its maximum hydrogen absorption capacity is 3.5 wt% at 293 K, dissociation enthalpy is 34.88 kJ/mol H₂, and desorption plateau platform is 0.05 Mpa at 303 K.     

Effects of Si addition on the microstructure and the hydrogen storage properties of Ti26.5V45Fe8.5Cr20Ce0.5 BCC solid solution alloys

The microstructure and the hydrogen storage properties of Ti_26.5(V_0.45Fe_0.085)_100−xCr₂₀Ce_0.5Si_x (x = 0 and 1) have been investigated by EPMA, XRD, in situ temperature XRD, neutron diffraction and P-C isotherm. Si addition results in the precipitation of a TiFe₂-type Laves phase and produces chemical heterogeneity in the BCC phase. As a consequence, Si-added alloy exhibits a lower hydrogen capacity and both a higher plateau pressure and slope factor as compared to Si-free alloy. Si enters in both Laves and BCC phases with a higher preference for the former phase. For both alloys, all metal atoms (Ti, V, Fe and Cr) are supposed to be randomly distributed in the 2a sites of the BCC phase and deuterium atoms occupy the 8c sites on fully charged deuterides. Si has no significant influence on the hydrogen occupation. Two hydrides are observed during the desorption process for Ti_26.5(V_0.45Fe_0.085)₁₀₀Cr₂₀Ce_0.5 alloy, a hydrogen rich one with distorted FCC structure (space group: P4/mmm) and a hydrogen poor one with BCT structure (space group: I4/mmm).     

Improvement of hydrogen storage properties of TiCrV alloy by Zr substitution for Ti

The effects of Zr substitution for Ti on the hydrogen absorption–desorption characteristics of Ti_1−xZr_xCrV alloys (x = 0, 0.05, 0.1 and 1.0) have been investigated. The crystal structure, maximum hydrogen absorption capacity, kinetics and hydrogen desorption properties have been studied in detail. While TiCrV crystallizes in body centered cubic (BCC) structure, ZrCrV is a C15 cubic Laves phase compound and the intermediate compositions with 5 and 10 at% Zr substitutions for Ti (x = 0.05 and 0.1) show the presence of a small amount of ZrCr₂ Laves phase along with the main BCC phase. The pressure–composition isotherms have been studied at room temperature. TiCrV shows separation of TiH₂ phase on cycling. A small amount of Zr substitution for Ti is found to have advantageous effects on the hydrogen absorption properties of TiCrV as it suppresses TiH₂ phase separation and decreases hysteresis. It is found that the hydrogen absorption capacity of Ti_1−xZr_xCrV decreases as the Zr content increases due to the increased fraction of Laves phase. Temperature-programmed desorption studies have been carried out on the saturated hydrides in order to find the relative desorption temperatures.     

Machine learning analysis of alloying element effects on hydrogen storage properties of AB2 metal hydrides

Zirconium-titanium-based AB₂ is a potential candidate for hydrogen storage alloys and NiMH battery electrodes. Machine learning (ML) has been used to discover and optimize the properties of energy-related materials, including hydrogen storage alloys. This study used ML approaches to analyze the AB₂ metal hydrides dataset. The AB₂ alloy is considered promising owing to its slightly high hydrogen density and commerciality. This study investigates the effect of the alloying elements on the hydrogen storage properties of the AB₂ alloys, i.e., the heat of formation (ΔH), phase abundance, and hydrogen capacity. ML analysis was performed on the 314 pairs collected and data curated from the literature published during 1998–2019, comprising the chemical compositions of alloys and their hydrogen storage properties. The random forest model excellently predicts all hydrogen storage properties for the dataset. Ni provided the most contribution to the change in the enthalpy of the hydride formation but reduced the hydrogen content. Other elements, such as Cr, contribute strongly to the formation of the C14-type Laves phase. Mn significantly affects the hydrogen storage capacity. This study is expected to guide further experimental work to optimize the phase structure of AB₂ and its hydrogen sorption properties.     

Investigation of ZrFe2-type materials for metal hydride hydrogen compressor systems by substituting Fe with Cr or V

In this study, the effects of partial substitution of Fe, in the ZrFe₂-system alloys, by Cr or V are presented. The two studied alloys, ZrFe_1.8V_0.2 and ZrFe_1.8Cr_0.2, have been synthesized by high frequency induction-levitation melting under inert Ar atmosphere. The induction furnace was equipped with a water-cooled copper crucible that permits the rapid solidification of the alloy after the melting. The crystal structures of the investigated alloys have been studied by the Rietveld analysis of the obtained X-ray diffraction (XRD) patterns. The microstructure has been observed by a scanning electron microscope (SEM) on polished samples of the alloys. Their hydriding properties have been studied with a high pressure Sievert's type apparatus, up to 200 bar. All pressure–composition–temperature (PCT) measurements have been obtained at 20, 60 and 90 °C. Two high temperature activation cycles have been conducted prior to PCT measurements. The results showed almost the same uptake for the alloys after identical activation and lowering of the plateau pressure in both cases.     

Study on the structure and hydrogen absorption-desorption characteristics of as-cast and annealed La0.78Mg0.22Ni3.48Co0.22Cu0.12 alloys

La_0.78Mg_0.22Ni_3.48Co_0.22Cu_0.12 alloy is one kind of nonstoichiometric AB_3.5 type hydrogen storage alloy with low cost and high capacity. In this paper, the effect of annealing treatment on the structure and hydrogen absorption-desorption characteristics of the alloy is discussed. The annealing temperature is determined by using thermogravimetry-differential scanning calorimetry (TG-DSC) tests. The structure of as-cast and annealed alloys is examined by X-ray diffraction (XRD) and scanning electron microscopy (SEM). XRD results show that the crystal cell volume decreases after annealing treatment. SEM tests reveal that the structure of the annealed alloys is more regular than that of the as-cast alloy. Influences of annealing treatment on maximum and reversible hydrogen storage capacity, hysteresis factor (H_f) between hydrogen absorption and desorption, sloping factor (S_f), enthalpy changes (ΔH) and entropy changes (ΔS) of hydrogen absorption are discussed in detail.     

Hydrogenation process in multiphase alloys of Ti-Zr-Mn-V system on the example of Ti42.75Zr27Mn20.25V10 alloy

The influence of phase composition and microstructure of Ti_42.75Zr₂₇Mn_20.25V₁₀ alloy on its hydrogenation kinetic and phase composition of hydrogenated product was studied. It is established that the process of dissociation of hydrogen molecules begins on the surface of Laves phase crystallites. The dissolution of atomic hydrogen in the material volume leads to the formation of cracks in the intermetallic crystallites, which further appear as additional centers of dissociation of hydrogen molecules and noticeably accelerate the diffusion of hydrogen into the bulk material. It was shown that the Laves phase acts as a donor of atomic hydrogen for the BCC solid solution during hydrogenation of two-phase structure, initiating intensive hydrogenation of the BCC phase at room temperature.     

Microstructure and hydrogen storage properties of Ti10V84−xFe6Zrx (x = 1–8) alloys

Ti₁₀V_84−xFe₆Zr_x (x = 1, 2, 4, 6, 8) hydrogen storage alloys were prepared by induction melting with magnetic levitation, and the effects of Zr content on the microstructures and hydrogen storage properties have been investigated systematically. The results show that the alloy with x = 1 has a single V-based solid solution phase with BCC structure, while other alloys with x = 2–8 consist of a BCC main phase and a C14 type Laves secondary phase, and the abundance ratio of the secondary phase increases with increasing Zr content. As the Zr content in the alloy increases, the activation behavior is improved, but the hydrogen absorption and desorption capacities decrease gradually. For the alloy with the Zr content of x = 1, the best overall hydrogen storage properties are obtained.     

Influence of Fe content on the microstructure and hydrogen storage properties of Ti16Zr5Cr22V57−xFex (x = 2–8) alloys

The influence of Fe content on the microstructure and hydrogen storage properties of Ti₁₆Zr₅Cr₂₂V_57−xFe_x (x = 2–8) alloys was investigated systematically. The results show that all alloys consist of a BCC main phase and a small amount of C14 Laves secondary phase. The crystal lattice parameters of the BCC main phase in the alloys decrease with the increase of the Fe content. Under moderate conditions, all the alloys have good activation behaviors and hydriding/dehydriding kinetics. As the x increases, the hydrogen desorption plateau pressure of the alloys increases consequently. Among the studied alloys, Ti₁₆Zr₅Cr₂₂V₅₅Fe₂ alloy has suitable hydrogen desorption plateau pressures indicated by the middle value of pressure range. (0.1–1 MPa) at 298 K and the best overall hydrogen storage properties.     

Microstructure and hydrogen storage properties of non-stoichiometric Zr–Ti–V Laves phase alloys

The non-stoichiometric C15 Laves phase alloys namely Zr_0.9Ti_0.1V_x (x = 1.7, 1.8, 1.9, 2.1, 2.2, 2.3) are designed and expected to investigate the role of defect and microstructure on hydrogenation kinetics of AB₂ type Zr-based alloys. The alloys are prepared by non-consumable arc melting in argon atmosphere and annealed at 1273 K for 168 h to ensure the homogeneity. The microstructure and phase constitute of these alloys are examined by SEM, TEM and XRD. The results indicate the homogenizing can reduce the minor phases α-Zr and abundant V solid solution originating from the non-equilibrium solidification of as-cast alloys. Twin defects with {111}<011 > orientation relationship are observed, and the role of defects on hydrogenation kinetics is discussed. Hydrogen absorption PCT characteristics and hydrogenation kinetics of Zr_0.9Ti_0.1V_x at 673–823 K are investigated by the pressure reduction method using a Sievert apparatus. The results show the hypo-stoichiometric alloys preserve faster hydrogenation kinetics than the hyper-stoichiometric ones due to the decrease of dendritic V. The excess content of Zr₃V₃O phase decreases the hydrogenation kinetics and the stability of hydrides. In addition, the different rate controlled mechanisms during hydrogen absorption are analyzed. The effects of non-stoichiometry on the crystal structure and hydrogen storage properties of Zr_0.9Ti_0.1V_x Laves alloys are discussed.     

Thermodynamics,kinetics and microstructural evolution of Ti0.43Zr0.07Cr0.25V0.25 alloy upon hydrogenation

Zr substituted Ti₂CrV alloy with Ti_0.43Zr_0.07Cr_0.25V_0.25 composition was synthesized by arc melting method and its crystal structure, microstructure and hydrogen storage performance were investigated. XRD and microstructural analyses confirmed that the alloy forms Laves phase related BCC solid solution. The enthalpy of hydride formation as derived from pressure composition absorption isotherms is ?56.33 kJ/mol H₂. The desorption temperature of the hydride is significantly lower (by ～50 K) than that of Ti₂CrV hydride indicating lower thermal stability of the hydride compared to its unsubstituted analogue. The alloy shows better cyclic stability over the unsubstituted one. This work also offers mechanistic insight into hydrogen absorption reaction of Ti_0.43Zr_0.07Cr_0.25V_0.25 alloy by analyzing the hydriding kinetics data with standard kinetic models. The rate-determining steps of hydrogen absorption reaction were identified as random nucleation and growth of hydride followed by 1D and 3D diffusion of hydrogen atoms through the hydride layer. The present study is expected to provide valuable information for the better development of Ti–Cr–V based hydrogen storage alloys.     

Improved hydrogen storage properties of Ti2CrV alloy by Mo substitutional doping

Controllable hydrogen release is of great importance to the practical application of hydrogen storage materials. Ti₂CrV alloy possesses the maximum hydrogen absorption capacity in the Ti–Cr–V series alloys, however, can hardly meet the reversible storage capacity of practical applications due to its stable dihydride. Here we report an advancement in hydrogen storage property of the Ti₂CrV alloy by Mo partial substitution for Ti. Although the hydrogen absorption kinetics slightly decreased with the increase of Mo content, the Mo substitution alloy achieves an effective hydrogen capacity of 2.23 wt% cutting-off at 0.1 MPa, much higher than Ti₂CrV alloy (0.8 wt%). It is ascribed that Mo partial substitution for Ti significantly decreased the dihydride stability as well as the enthalpy change value. The cyclic property of Ti₂CrV alloy drastically decreased, while Mo substitution alloy with smaller FWHM value can maintain 90% storage capacity after 20 cycles. Because lattice strain and distortion of the Ti₂CrV alloy were decreased by Mo doping.