Effect of V content on hydrogen storage properties and cyclic durability of V–Ti–Cr–Fe alloys

Vanadium-based body-centered-cubic (BCC) alloys are ideal hydrogen storage media because of their high reversible hydrogen capacities at moderate conditions. However, the rapid capacity decay in hydrogen ab-/desorption cycles prevents their practical application. In this work, V-based BCC alloys with three different V contents (V₂₀Ti₃₈Cr_41.4Fe_0.6, V₄₀Ti_28.5Cr_30.1Fe_1.4, V₆₀Ti₁₉Cr₁₉Fe₂, named as V20, V40, V60) were prepared by arc melting, and their microstructures and hydrogen ab-/desorption properties were investigated systematically. XRD results show that there is a number of C15-Laves phase presence in V20, which does not appear in V40 and V60. Meanwhile, the lattice constant of the BCC phase clearly decreases as the V content rises. These differences result in a hydrogen storage capacity of only 1.82 wt% for V20 alloy, but 2.13 wt% for V40 and 2.14 wt% for V60, and an increment in hydrogen ab-/desorption plateau pressure. The V40 and V60 alloys are chosen in de-/hydrogenation cycle test owing to higher effective storage capacities, and the results show that the V60 alloy has better cycle durability. According to the microstructural analysis of the two alloys during the cycles, the micro-strain accumulates, the cell volume expands, the particles pulverizes and the defects increase during the cycles, which eventually lead to the attenuation of the hydrogen storage capacity. The increment of the V content obviously improves the elastic properties of the alloy, which further diminishes the micro-strain accumulation, cell volume expansion, particle pulverization and defect increase, eventually resulting in a higher capacity retention and better cyclic durability.     

Influence of Cr on the hydrogen storage properties of Ti-rich Ti–V–Cr alloys

In the present work, we studied the effects of Cr on the crystal structures and hydrogen storage properties of ternary alloys, Ti_0.7V_0.3−xCr_x and Ti_0.8V_0.2−xCr_x. Metal–hydrogen interactions were characterised by Thermal Desorption Spectroscopy (TDS) and in situ Synchrotron X-ray diffraction (SR-XRD). All initial alloys crystallise with body-centred cubic (BCC) crystal structures formed as solid solutions of V and Cr in Ti. Upon hydrogenation, the dihydrides (Ti,V,Cr)H₂ with face-centred cubic (FCC) structures are formed. An increase in the Cr content leads to systematic changes in the structure and hydrogenation behaviours. The changes include (a) contraction of the unit cells for the initial alloys and for the corresponding dihydrides; (b) slower hydrogen absorption kinetics and an increase in the incubation period for hydrogenation; (c) a decrease in the thermal stability of the saturated hydrides; and (d) a reduction in the apparent activation energy of hydrogen desorption. In situ SR-XRD and TDS studies of the FCC Ti–V–Cr hydrides indicated that their decomposition consists of five individual desorption events.     

Microstructure and hydrogen storage properties of Ti–V–Cr based BCC-type high entropy alloys

In this work, the crystal structure and hydrogen storage properties of V₃₅Ti₃₀Cr₂₅Fe₁₀, V₃₅Ti₃₀Cr₂₅Mn₁₀, V₃₀Ti₃₀Cr₂₅Fe₁₀Nb₅ and V₃₅Ti₃₀Cr₂₅Fe₅Mn₅ BCC-type high entropy alloys have been investigated. It was found that high entropy promotes the formation of BCC phase while large atomic difference (δ) has the opposite effect. Among the four alloys, the V₃₅Ti₃₀Cr₂₅Mn₁₀ alloy shows the highest hydrogen absorption capacity while the V₃₅Ti₃₀Cr₂₆Fe₅Mn₅ alloy exhibits the highest reversible capacity. The cause of the loss of desorption capacity is mainly due to the high stability of the hydrides. The higher room-temperature desorption capacity of the V₃₅Ti₃₀Cr₂₅Fe₅Mn₅ alloy is due to higher hydrogen desorption pressure. After pumping at 400 °C, the hydrides can return to the original BCC structure with only a small expansion in the cell volume.     

Development of Ti–Cr–Mn–Fe based alloys with high hydrogen desorption pressures for hybrid hydrogen storage vessel application

Three series of Ti–Cr–Mn–Fe based alloys with high hydrogen desorption plateau pressures for hybrid hydrogen storage vessel application were prepared by induction levitation melting, as well as their crystallographic characteristics and hydrogen storage properties were investigated. The results show that all of the alloys were determined as a single phase of C14-type Laves structure. As the Fe content in the TiCr_1.9−xMn_0.1Fe_x (x = 0.4–0.6) alloys increases, the hydrogen absorption and desorption plateau pressures increase, and the hydrogen storage capacity and plateau slope factor decrease respectively. The same trends are observed when increasing the Mn content in the TiCr_1.4−yMn_yFe_0.6 (y = 0.1–0.3) alloys, except for the plateau slope factor. Compared with the stoichiometric TiCr_1.1Mn_0.3Fe_0.6 alloy, the titanium super-stoichiometric Ti_1+zCr_1.1Mn_0.3Fe_0.6 (z = 0.02, 0.04) alloys have larger hydrogen storage capacities and lower hydrogen desorption plateau pressures. Among the studied alloys, Ti_1.02Cr_1.1Mn_0.3Fe_0.6 has the best overall properties for hybrid hydrogen storage application. Its hydrogen desorption pressure at 318 K is 41.28 MPa, its hydrogen storage capacity is 1.78 wt.% and its dissociation enthalpy (ΔH_d) is 16.24 kJ/mol H₂.     

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.     

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.     

Study on low-vanadium Ti–Zr–Mn–Cr–V based alloys for high-density hydrogen storage

To reduce the cost and modulate hydrogen storage performances of Ti-based Laves phase alloys for the application of inputting 3.2 MPa feed hydrogen and outputting 8 MPa hydrogen with water bath, three series of less-vanadium Ti–Zr–Mn–Cr–V based alloys were prepared by induction levitation melting, and their microstructure and hydrogen storage properties were systematically investigated. All alloys consist of a single C14-type Laves phase with well-distributed elements. With vanadium decreasing in Ti_0.95Zr_0.05Mn_0.9+xCr_0.9+xV_0.2-2x (x = 0–0.02) and Ti_0.93Zr_0.07Mn_1.1+yCr_0.7+zV_0.2-y-z (y = 0, 0.05, z = 0–0.05) stoichiometric alloys, the hydrogen equilibrium pressure increases and hydrogenation kinetics is slightly deteriorated. After introducing Ti hyper-stoichiometry, Ti_0.93+wZr_0.07Mn_1.15Cr_0.7V_0.15 (w = 0–0.04) alloys show decreased hydrogen equilibrium pressure, high hydrogen capacity and enhanced kinetics. Among alloys mentioned, Ti_0.95Zr_0.07Mn_1.15Cr_0.7V_0.15 has optimum performances including useable capacity of 1.07 wt% at working conditions, together with satisfactory cycling durability. This study guides for compositional design of high-density hydrogen storage multi-component alloys.     

Effect of partial niobium and iron substitution on short-term cycle durability of hydrogen storage Ti–Cr–V alloys

The effect of partial niobium and iron substitution on the short-term (up to 10 cycles) cycle durability of hydrogen absorption and desorption was evaluated for Ti–Cr–V alloys. Partial iron substitution improved the durability of Ti₁₆Cr₃₄V₅₀ alloy, but reduced its hydrogen storage capacity. In contrast, partial niobium substitution improves its durability while not affecting its hydrogen storage capacity. Similar experimental results were obtained for Ti₂₅Cr₅₀V₂₅ alloy. The effective hydrogen storage capacity decreased to 84.9 and 94.2% of its initial value after 10 cycles of hydrogen absorption and desorption for Ti₂₅Cr₅₀V₂₅ and Ti₂₅Cr₄₅V₂₅Nb₅ alloys, respectively. This reduction in the effective hydrogen storage capacity of Ti₂₅Cr₅₀V₂₅ alloy during hydrogen absorption and desorption is attributed to reduced hydrogen storage capacity during absorption and a greater residual hydrogen during desorption.     

Synthesis and hydrogen storage behavior of Mg–V–Al–Cr–Ni high entropy alloys

The ternary MgVAl, MgVCr, MgVNi, quaternary MgVAlCr, MgVAlNi, MgVCrNi and quinary MgVAlCrNi alloys were produced by high energy ball milling (HEBM) under hydrogen pressure (3.0 MPa) as a strategy to find lightweight alloys for hydrogen storage applications. Most of the ternary and quaternary alloys presented multiphase structure, composed mainly of body-centered cubic (BCC) solid solutions and Mg-based hydrides. Only the quinary MgVAlCrNi high entropy alloy (HEA) formed a single-phase structure (BCC solid solution), which is a novel lightweight (ρ = 5.48 g/cm³) single-phase HEA. The hydrogen storage capacity of this alloy was found to be very low (approximately 0.3 wt% of H). Two non-equiatomic alloys with higher fraction of Mg and V (strong hydride former elements), namely Mg₂₈V₂₈Al₁₉Cr₁₉Ni₆ and Mg₂₆V₃₁Al₃₁Cr₆Ni₆, were then designed, aiming at higher storage capacity. Both alloys were produced by HEBM. The results show that the non-stoichiometric alloys also presented low hydrogen storage capacity. The low affinity of these alloys with hydrogen was discussed in terms of enthalpy of hydrogen solution and enthalpy of hydride formation of the single components. This study brought to light the importance of considering both enthalpy of hydrogen solution and enthalpy of hydride formation of the alloying elements for designing Mg-containing HEA for hydrogen storage. Once Mg has a positive enthalpy of hydrogen solution, the alloys composition must be balanced with alloying elements with higher hydrogen affinity, i.e., negative values of enthalpy of solution and hydride formation.     

Effect of oxygen on the microstructure and hydrogen storage properties of V–Ti–Cr–Fe quaternary solid solutions

The effect of low (<300 ppm O) and high (10,000 ppm O) residual oxygen concentration in vanadium raw metals on the microstructure and hydrogenation properties of V₄₀Fe₈Ti₂₆Cr₂₆, was investigated by means of XRD, SEM, TEM and pressure-composition isotherms. A high oxygen concentration in the vanadium raw metal led to the formation of an oxygen-rich secondary phase isostructural with α-Ti. The lattice parameter of the BCC main phase of the high-oxygen sample was reduced to 3.0141 (3) Å compared to 3.0308 (2) Å for the low-oxygen sample. As a result of the high oxygen content the equilibrium hydrogen pressure of the material was increased from 1 MPa to 4 MPa. Deoxidization through the addition of 1 at% rare earth metal could be achieved. The lattice constant of the deoxidized sample was 3.0297 (3) Å, and the thermodynamic properties were also the same as in case of the low-oxygen sample.     

An improvement on cycling stability of Ti–V–Fe-based hydrogen storage alloys with Co substitution for Ni

In this work, the effects of Co substitution for Ni on the microstructures and electrochemical properties of Ti_0.8Zr_0.2V_2.7Mn_0.5Cr_0.6Ni_1.25−xCo_xFe_0.2 (x = 0.00–0.25) alloys were investigated systematically by XRD, SEM and electrochemical measurements. The structural investigations revealed that the main phases of all of the alloys were the C14 Laves phase in a three-dimensional network and the V-based solid solution phase with a dendritic structure. The lattice parameters and unit cell volumes of the two phases gradually increased with the increase of Co concentration. The relative abundance of the C14 Laves phase slightly increased from 47.3% to 49.6%, accordingly that of the V-based solid solution phase decreased, with the increase of x from 0.00 to 0.25. The crystal grain of the V-based solid solution phase was obviously refined after Co substitution. The electrochemical investigations showed that the proper substitution of Co for Ni improved the cycling durability of the alloy electrodes mainly due to the suppression of both the pulverization of the alloy particles and the dissolution of the main hydrogen absorbing elements (V and Ti) into the KOH solution. The cycling stability of the alloy electrode with x = 0.1 was 79.8% after 200 cycles. However, the maximum discharge capacity (C_max) was decreased from 340.5 to 305.6 mAh g⁻¹, and the high rate dischargeability (HRD) gradually decreased from 66.8% to 55.0% with increasing x from 0.00 to 0.25.     

Notable hydrogen storage in Ti–Zr–V–Cr–Ni high entropy alloy

In the present investigation, we discussed the synthesis, structural and hydrogen storage behavior of high-entropy Ti–Zr–V–Cr–Ni equiatomic intermetallic alloy. This alloy was synthesized by arc melting in an argon atmosphere where base pressure was in the order of 10^?5 atm before purging with argon gas. The X-ray diffraction study revealed that the alloy is C14 type hexagonal Laves phase. The pressure composition isotherms (PCI) of this alloy were investigated with pressure ranges at 0–40 atmosphere. The total hydrogen storage capacities were found to be 1.52 wt%. The reversible hydrogen storage capacity was quite stable and only slight decreases in the storage capacity was observed after 10 cycles during hydrogen soaking. The demonstrations of hydrogen storage capacity of the Ti–Zr–V–Cr–Ni equiatomic alloy were thus established, indicating the future potential of developing this class of high entropy intermetallic based materials for hydrogen storage.     

Investigation of hydrogen isotope effect on storage properties of Zr–Co–Ni alloys

The deuterium desorption pressure-composition isotherms (PCIs) of ZrCo_1−xNi_x-D₂ (x = 0, 0.1, 0.2 and 0.3) systems were generated in this study in the temperature range of 524–603 K using Sievert's type volumetric apparatus. Thermodynamic parameters like enthalpy and entropy change for deuterium desorption reactions involved in the ZrCo_1−xNi_x-D₂ systems were derived using the equilibrium pressure data of PCIs. In order to interpret the hydrogen isotope effect on the storage behaviour of ZrCo_1−xNi_x alloys, the results obtained in the present study were compared with the earlier reported data on the ZrCo_1−xNi_x-H₂ (x = 0, 0.1, 0.2 and 0.3) systems. This comparison revealed that these alloys show normal hydrogen isotope effect where the equilibrium pressure of D₂ is higher than that of H₂ at all experimental temperatures. Based on these observation, it is expected that at the ITER SDS operating conditions the equilibrium pressure of tritium, deuterium and hydrogen will follow the order: p(T₂) > p(D₂) > p(H₂) for these alloys.     

Optimizing Ti–Zr–Cr–Mn–Ni–V alloys for hybrid hydrogen storage tank of fuel cell bicycle

AB₂-type Ti-based alloys with Laves phase have advantages over other kinds of hydrogen storage intermetallics in terms of hydrogen sorption kinetics, capacity, and reversibility. In this work, Ti–Zr–Cr-based alloys with progressive Mn, Ni, and V substitutions are developed for reversible hydrogen storage under ambient conditions (1–40 atm, 273–333 K). The optimized alloy (Ti_0.8Zr_0.2)_1.1Mn_1.2Cr_0.55Ni_0.2V_0.05 delivers a hydrogen storage capacity of 1.82 wt%, the hydrogenation pressure of 10.88 atm, and hydrogen dissociation pressure of 4.31 atm at 298 K. In addition, fast hydrogen sorption kinetics and low hydriding-dehydriding plateau slope render this alloy suitable for use in hybrid hydrogen tank of fuel cell bicycles.     

Study on fracture strain of Cr–Mo steel in high pressure hydrogen

Cr–Mo steel is often used as the material of the hydrogen storage vessel, but its ductility can be deteriorated by high pressure hydrogen, which makes it possible that the local area of strain concentration on the hydrogen storage vessel made of Cr–Mo steel may fail due to excessive plastic deformation. The limit criterion of local strain established according to the study of the fracture strain is the basis for local failure assessment of the vessel. However, the correlation between the fracture strain and the stress state of Cr–Mo steel in high pressure hydrogen is still unclear, so the limit criterion of local strain for hydrogen storage vessel made of Cr–Mo steel has not been established. In this paper, the slow strain rate tensile test (SSRT) of notched specimens with different notch sizes was carried out in air, 45 MPa hydrogen and 100 MPa hydrogen, respectively. Based on the test results, the whole process from tensile to fracture of the specimens was simulated by finite element method. The distribution of stress triaxiality and plastic strain during the tensile process was analyzed, and the correlations between the stress triaxiality and the fracture strain in different environments were obtained. Finally, the limit criterion of local strain for local failure assessment of 4130X hydrogen storage vessel was established.     

Electrochemical hydrogen storage performance of Mg–Ti–Zr–Ni alloys

Mg_1.5Ti_0.5−xZr_xNi (x = 0, 0.1, 0.2, 0.3, 0.4), Mg_1.5Ti_0.3Zr_0.1Pd_0.1Ni and Mg_1.5Ti_0.3Zr_0.1Co_0.1Ni alloys were synthesized by mechanical alloying and their electrochemical hydrogen storage characteristics were investigated. X-ray diffraction studies showed that all the replacement elements (Ti, Zr, Pd and Co) perfectly dissolved in the amorphous phase and Zr facilitated the amorphization of the alloys. When the Zr/Ti ratio was kept at 1/4 (Mg_1.5Ti_0.4Zr_0.1Ni alloy), the initial discharge capacity of the alloy increased slightly at all the ball milling durations. The further increase in the Zr/Ti ratio resulted in reduction in the initial discharge capacity of the alloys. The presence of Zr in the Ti-including Mg-based alloys improved the cyclic stability of the alloys. This action of Zr was attributed to the less stable and more porous characteristics of the barrier hydroxide layer in the presence of Zr due to the selective dissolution of the disseminated Zr-oxides throughout the hydroxide layer on the alloy surface. Unlike Co, the addition of Pd into the Mg–Ti–Zr–Ni type alloy improved the alloy performance significantly. The positive contribution of Pd was assumed to arise from the facilitated hydrogen diffusion on the electrode surface in the presence of Pd. As the Zr/Ti atomic ratio increased, the charge transfer resistance of the alloy decreased at all the depths of discharges. Co and Pd were observed to increase the charge transfer resistance of the Mg–Ti–Zr–Ni alloys slightly.     

Study of the performance of Ti–Zr based hydrogen storage alloys

The P–C–I and charging–discharging properties of three Ti–Zr based alloys have been studied. Ni substitution for Mn and Cr in the alloy was found to increase the plateau pressure of the P–C–I curve. In addition, the partial substitution of Cr by V greatly improved the discharge capacity. However, the six-element alloy, Ti_0.5Zr_0.5V_0.2Mn_0.7Cr_0.5Ni_0.6, degraded rapidly in the gas–solid reaction. Hydrogen contents in the alloy under low pressure were increased during hydrogen absorption–desorption cycling. Annealing at 1050°C for 4 h before the P–C–I experiment helped in releasing the retained hydrogen under low pressure. Only a slightly flattened P–C–I slope was obtained for the annealed alloy. Microstructures of the as-cast and annealed alloys were examined and related to the above results. Alloy powder was poisoned after 2-month storage in air, which resulted in the deterioration of discharge capacity. Surface pretreatment on alloy powders by HCl–HF solution decreased the activation time of charge–discharge reaction.     

Effect of hydrogenation on metal distribution in Ti–V–Cr alloys

The paper reports on the distribution of metal elements during aging after electrolytic hydrogenation in both (TiCr_1.8)_100-xV_x and (TiCr_1.8)_100-xV_x + 4 mol% Zr₇Ni₁₀ alloys. It is shown that insertion of hydrogen leads to self-diffusion of metals atoms. Moreover, after long time enough, stochastic aperiodic changes in the distribution of metal elements are observed.     

Effect of carbon coating on the electrochemical properties of La–Y–Ni-based hydrogen storage alloys

The A₂B₇-type (LaSmY) (NiMnAl)_3.5 alloys were prepared by induction melting, and then the alloy samples coated with different contents of nano-carbon were prepared by the mixing and sintering method using pitch as carbon source. The effects of the contents and structure of the coated-carbon on the electrochemical properties of alloy samples were investigated. With the carbon content increase from 0.1 to 1.0 wt%, the cyclic stability is improved and the high-rate dischargeabilitiy (HRD) of the alloy electrodes first increase and then decrease. The kinetic results show that the carbon coating improves the electrocatalytic activity and electrical conductivity of the alloy electrodes. The alloy electrode with 0.5 wt% carbon coating exhibits the best electrochemical properties. The maximum discharge capacity (C_max) is 345.7 mAh·g⁻¹, the HRD₁₂₀₀ is 72.49%, and the capacity retention rate (S₃₀₀) is 79.44%.