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1.
In the present work, we have studied the hydrogen absorption–desorption properties of the Ti2CrV alloy, and effect of cycling on the hydrogen storage capacity. The material has been characterized for the structure, morphology, pressure composition isotherms, hydrogen storage capacity, hydrogen absorption kinetics and the desorption profile at different temperatures in detail. The Ti2CrV crystallizes in body centered cubic (bcc) structure like TiCrV. The pressure composition isotherm of the alloy has been measured at room temperature and at 373K. The Ti2CrV alloy shows maximum hydrogen storage capacity of 4.37 wt.% at room temperature. The cyclic hydrogen absorption capacity of Ti2CrV alloy has been investigated at room temperature upto 10th cycle. The hydrogen storage capacity decreased progressively with cycling initially, but the alloy can maintain steady cyclic hydrogen absorption capacity 3.5 wt.% after 5th cycle. To get insight about the desorption behavior of the hydride in-situ desorption has been done at different temperatures and the amount of hydrogen desorbed has been calculated. The TG (Thermo gravimetric) and DTA analysis has been done on uncycled hydride shows that the surface poisoned sample gives a desorption onset temperature of 675K. The DSC measurement of uncycle and multi-cycled saturated hydrides shows that the hydrogen desorption temperature decreasing with cycling.  相似文献   

2.
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 TiCr1.9−xMn0.1Fex (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 TiCr1.4−yMnyFe0.6 (y = 0.1–0.3) alloys, except for the plateau slope factor. Compared with the stoichiometric TiCr1.1Mn0.3Fe0.6 alloy, the titanium super-stoichiometric Ti1+zCr1.1Mn0.3Fe0.6 (z = 0.02, 0.04) alloys have larger hydrogen storage capacities and lower hydrogen desorption plateau pressures. Among the studied alloys, Ti1.02Cr1.1Mn0.3Fe0.6 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 (ΔHd) is 16.24 kJ/mol H2.  相似文献   

3.
ZrCo1−xNix (x = 0, 0.1, 0.2 and 0.3) alloys were prepared and their hydrogen storage behavior were studied. ZrCo1−xNix alloys of compositions with x = 0, 0.1, 0.2 and 0.3 prepared by arc-melting method and characterized by X-ray diffraction analysis. XRD analysis showed that the alloys of composition with x = 0, 0.1, 0.2 and 0.3 forms cubic phase similar to ZrCo with traces of ZrCo2 phase. A trace amount of an additional phase similar to ZrNi was found for the alloy with composition x = 0.3. Hydrogen desorption pressure–composition–temperature (PCT) measurements were carried out using Sievert's type volumetric apparatus and the hydrogen desorption pressure–composition isotherms (PCIs) were generated for all the alloys in the temperature range of 523–603 K. A single sloping plateau was observed for each isotherm and the plateau pressure was found to increase with increasing Ni content in ZrCo1−xNix alloys at the same experimental temperature. A van't Hoff plot was constructed using plateau pressure data of each pressure–composition isotherm and the thermodynamic parameters were calculated for desorption of hydrogen in the ZrCo1−xNix–H2 systems. The enthalpy and entropy change for desorption of hydrogen were calculated. In addition, the hydrogen absorption–desorption cyclic life studies were performed on ZrCo1−xNix alloys at 583 K up to 50 cycles. It was observed that with increasing Ni content the durability against disproportionation of alloys increases.  相似文献   

4.
La2−xTixMgNi9 (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 La2−xTixMgNi9 (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 La1.8Ti0.2MgNi9 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.  相似文献   

5.
The effect of the addition of 4th element on the hydrogen storage capacity of Ti0.32Cr0.43V0.25 alloy was evaluated by simulation and confirmed experimentally. The crystal lattice volume, phase formation energy, and hydrogen absorption energy of the alloys were calculated by ab initio calculation for the alloys containing the third-period transition metals as Sc, Cr, Mn, Fe, Co, Ni, Cu, and Zn. It was postulated that the hydrogen absorption would be favored by large crystal volume and low hydrogen absorption energy. The calculation suggested Sc as the most suitable element and the hydrogen capacities of a series of Ti0.32Cr0.43−xV0.25Scx alloys (x = 0.02–0.1) were determined accordingly. Among the alloys, the capacities of Ti0.32Cr0.41V0.25Sc0.02 and Ti0.32Cr0.39V0.25Sc0.04 alloys were higher than that of the Ti0.32Cr0.43V0.25 alloy. The capacity of both alloys could be enhanced further by the heat treatment at 1250 °C due to the elimination of the second-phase TiCr2.  相似文献   

6.
Hydrogenation properties of LaNi5  xInx alloys (x = 0.1, 0.2 and 0.5) were examined by their direct reaction with gaseous hydrogen and by cathodic charging in 6 M KOH solution. The gas phase measurements were carried out using Sievert's type apparatus in 300–400 K temperature range and at hydrogen pressures up to 40 bars. Indium substitution for Ni in LaNi5 significantly modifies the hydrogenation behavior, decreasing the equilibrium pressure of hydrogen and limiting the hydrogen capacity as compared to LaNi5. The LaNi4.9In0.1 revealed a distinct presence of two pressure plateaus on the high temperature isotherms. Apart from the α-phase (hydrogen solid solution) and β-phase (LaNi5H6 hydride), formation of a new σ*-hydride phase was postulated at the hydrogen content extended over the region of H/f.u. = 1.3–1.8. Thermodynamic functions: enthalpy and entropy of the hydrogen absorption process were calculated from the H2-pressure/composition (p–c) isotherms at several temperatures, applying the Van't Hoff's (lnp − 1/T) dependence. Electrochemical galvanostatic hydrogenation experiments at 185 mA/g charge/discharge rate revealed the greatest discharge current capacity of 319 mAh/g for LaNi4.9In0.1 alloy after 4–5 cycles. The hydrogen discharge capacities decrease with further increase of indium content in the alloy.  相似文献   

7.
The influence of Fe content on the microstructure and hydrogen storage properties of Ti16Zr5Cr22V57−xFex (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.  相似文献   

8.
TixCr1 ? yFeyMn1.0 (x = 1.02, 1.05, 1.1, 0.05 ≤ y ≤ 0.25) alloys were prepared by plasma arc melting and annealing at 1273 K for 2 hours. The XRD results show that the main phase of all alloys is the C14 type Laves phase, and a little secondary phase exists in a mixture of the binary alloy phase. The lattice parameters increase with Ti super‐stoichiometry ratio increasing, whereas smaller lattice parameters emerge with increasing Fe stoichiometry content. Additionally, as the Ti super‐stoichiometry ratio decreases, the pressure‐composition‐temperature measurements indicated that hydrogen absorption and desorption plateau pressures of TixCr0.9Fe0.1Mn1.0 (x = 1.1, 1.05, 1.02) alloys increase from 3.15, 0.67, to 5.94, 1.13 MPa at 233 K, respectively. On the other hand, with the Fe content increasing in Ti1.05Cr1 ? yFeyMn1.0 (0.1 ≤ y ≤ 0.25) alloys from 0.1 to 0.25, the hydrogen desorption plateau pressures increased from 1.41 to 2.46 MPa at 243 K. The hydrogen desorption plateau slopes reduce to 0.2 with Ti super‐stoichiometry ratio decreasing to 1.02, but the alloys are very difficult to activate for hydrogen absorption and cannot activate when the Fe substituting for Cr exceeds 0.2. The maximum hydrogen storage capacities were more than 1.85 wt% at 201 K. The reversible hydrogen storage capacities can remain more than 1.55 wt% at 271 K. The enthalpy and entropy for all hydride dehydrogenation are in the range of 21.0 to 25.5 kJ/mol H2 and 116 to 122 J mol?1 K?1, respectively. Our results suggest that Ti1.05Cr0.75Fe0.25Mn1.0 alloy with low enthalpy holds great promise for a high hydrogen pressure hybrid tank in a hydrogen refueling station (45 MPa at 333 K), and the other alloys of low cost may be used for a potable hybrid tank due to high dissociation pressure at 243 K and high volumetric density exceeding 40 kg/m3.  相似文献   

9.
Nominal Ti2Ni was synthesized under argon atmosphere at room temperature using a planetary high-energy ball mill. The effect of milling time and Zr substitution for Ti on the microstructure was characterized by XRD, SEM and TEM, and the discharge capacities of Ti2−xZrxNi (x = 0, 0.1, 0.2) were examined by electrochemical measurements at galvanostatic conditions. XRD analysis shows that amorphous phase of Ti2Ni can be elaborated by 60 h of milling, whereas Zr substitution hinders amorphization process of the system. The products of ball milling nominal Ti2−xZrxNi (x = 0.1, 0.2) were austenitic (Ti, Zr)Ni and partly TiO, despite the fact that the operation was carried out under argon atmosphere. By comparing the SEM micrographs, it is found that the amorphous phase of Ti2Ni was formed in the stage of cold-welding during milling, while with Zr substitution particles were flaky and finer, inhomogeneous in size distribution with massive agglomeration. TEM analysis was carried out and confirmed the observations via XRD. In the electrochemical tests, amorphous Ti2Ni shows the best discharge capacity at 102 mAh/g at a current density of 40 mA/g. Without need of activation, it exhibits extraordinary cycling stability under room temperature. On the other hand, the effect of Zr substitution on the electrochemical property of Ti2Ni is tricky, as superficially the discharge capacity drops drastically with Zr substitution, but with increase of Zr content (from x = 0.1 to x = 0.2), the discharge capacity increases generally, which credits to larger unit-cell-volume provided by ZrNi compared to TiNi. It is also found that the Ti–Ni system becomes significantly susceptible to oxidation when Zr is introduced to the initial powders as mechanical alloying is deployed as a synthesis method.  相似文献   

10.
The effects of Zr substitution for Ti on the hydrogen absorption–desorption characteristics of Ti1−xZrxCrV 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 Ti1−xZrxCrV 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.  相似文献   

11.
The effect of the vanadium content on the cyclic stability of V–Ti binary alloys was investigated. V1−xTix, x = 0.2 and 0.5 samples were hydrogenated and dehydrogenated at 410 K and 553 K respectively, for more than 100 times. During hydrogen cycling, reduction in the reversible hydrogen storage capacity was clearly observed from both samples. No prominent V-effect was found. In fact, the reduction rates of two samples were similar; both samples showed a ∼25% reduction in the reversible hydrogen storage capacity after 100 cycles. In addition, the shape of the pressure–composition-isotherm (PCT) curves was significantly altered over the testing cycle period; the absorption and desorption plateaus got markedly inclined and the hysteresis became evidently smaller. We found that even after the hydrogen storage capacity of V1−xTix was significantly reduced, at low enough temperature V1−xTix was able to absorb hydrogen as much as it did at the first cycle. Furthermore, the reversible hydrogen storage capacity of V0.8Ti0.2 at 410 K was recovered to a certain degree after hydrogenating the sample at low temperatures.  相似文献   

12.
In this paper, Fe is partly substituted by Ni for improving the hydrogen storage properties of the TiFe alloy, such as the activation performance, hydrogen storage capacity, reactivation ability, optimum temperature range, thermodynamics and kinetics. The as-cast TiFe alloy contains the majority phase of TiFe and the minority phases of Ti2Fe and TiFe2. Increasing Ni content causes the majority phase of TiFe to increase firstly and then decrease again. The activation temperature reduces from 573 K for the TiFe alloy to 523 and 443 K for the TiFe0·8Ni0.2 and TiFe0·6Ni0.4 alloys respectively. Substituting Fe with Ni partly can lower the platform pressure for the P-C-T curves and increase the dehydrogenation enthalpy (ΔHdes). The TiFe0·8Ni0.2 alloy possesses the highest hydrogenation capacity. Adding Ni also is beneficial to expand the optimum temperature range, corresponding to the hydrogenation capacity higher than 0.800 wt%, which is 313–383, 313–503 and 313–573 K for the TiFe1-xNix (x = 0.1, 0.2 and 0.4) alloys, respectively. All the alloys can be activated again at 573 K after being exposed to air for 5 min.  相似文献   

13.
In this paper, we present the synthesis, first hydrogenation kinetics, thermodynamics and effect of cycling on the hydrogen storage properties of a V0.3Ti0.3Cr0.25Mn0.1Nb0.05 high entropy alloy. It was found that the V0.3Ti0.3Cr0.25Mn0.1Nb0.05 alloy crystallizes in body-centred cubic (BCC) phase with a small amount of secondary phase. The first hydrogenation is possible at room temperature without incubation time and reaches a maximum hydrogen storage capacity of 3.45 wt%. The pressure composition isotherm (P–C–I) at 298 K shows a reversible hydrogen desorption capacity of 1.78 wt% and a desorption plateau pressure of 80.2 kPa. The capacity loss is mainly due to the stable hydride with the desorption enthalpy of 31.1 kJ/mol and entropy of 101.8 J/K/mol. The hydrogen absorption capacity decreases with cycling due to incomplete desorption at room temperature. The hydrogen absorption kinetics increases with cycling and the rate-limiting step is diffusion-controlled for hydrogen absorption.  相似文献   

14.
This paper describes the efficient preparation of an Mg2Ni alloy for hydrogen storage via high-energy ball milling mechanical alloying for 2 h. The degree of alloy amorphisation increases with increasing ball-milling time. Ball milling for 4 h affords partially amorphous alloys exhibiting the best hydrogen storage performance. Partial substitution of Ni with Cr and Mn improves the hydrogen absorption/desorption thermodynamics, kinetics and cycling performance of the alloy. Specifically, partial Mn substitution improves the cycling performance and reduces the activation energy of the hydrogen desorption reaction, effectively improving the hydrogen desorption kinetic performance. Mg2Ni0.8Mn0.2 shows the best cycling and hydrogen absorption/desorption kinetic performances. Partial Cr substitution reduces the entropy and enthalpy changes of the hydrogen absorption/desorption reaction and effectively reduces the temperature of the initial hydrogen absorption/desorption reaction. In particular, Mg2Ni0.9Cr0.1 shows the best thermodynamic performance.  相似文献   

15.
Hydrogen absorption/desorption properties of La0.2Y0.8Ni5−xMnx (x = 0.2, 0.3, 0.4) alloys for high-pressure hydrogen compression application were investigated systematically. The Pressure–Composition isotherms and absorption kinetics were measured at 293, 303 and 313 K by the volumetric method. XRD analyses showed that all the investigated alloys presented CaCu5 type hexagonal structure and the unit cell volume increased in both a and c lattice axes with Mn substitution. Hydrogen absorption/desorption measurements revealed that Mn could lower the plateau pressure effectively, improve the hydrogen storage capacity and absorption kinetics but slightly increase the slope of the pressure plateau and hysteresis. The study results suggest that La0.2Y0.8Ni4.8Mn0.2 is suitable for the high-pressure stage compression of the hydrogen compressor and the other two alloys, La0.2Y0.8Ni4.7Mn0.3 and La0.2Y0.8Ni4.6Mn0.4, for the preliminary stage.  相似文献   

16.
Commercial metal nanoparticles of Fe, Co, Ni, Cu, Zn were added to MgH2 by ball-milling to improve the kinetics of hydrogen release and the reversibility during successive absorption/desorption cycles. metal nanoparticles were well dispersed into the MgH2 matrix without formation of any ternary metal hydrides, nor binary compounds. Activation energy values were determined for the various samples by temperature programmed desorption experiments while the hydride formation enthalpy was deduced from Van't Hoff equation starting from high pressure volumetric isotherms acquired at different temperatures. The presence of transient effect during the absorption process was excluded by comparing successive hydrogenation/dehydrogenation cycles recorded at 350 °C on Ni and Fe-containing samples. Information about hydrogen absorption kinetics was also obtained. Promisingly, the Ni, Fe, and Co containing samples have shown a good stability, enhanced catalytic performance, and high rate of hydrogen absorption while Zn and Cu nanoparticles worked more like inhibitors than activators.  相似文献   

17.
This study investigated how Fe substitution with Ni, Co, Cu, Mn, and Cr affected the first hydrogenation behavior of air-exposed TiFe-based hydrogen storage alloys. The alloy ingots were crushed into powders and exposed to air for 1 h to analyze the first hydrogenation kinetics. Although Fe was substituted with up to 30% of Ni, Co, and Cu, the alloys had a single TiFe phase. In addition, the TiFe0·7Ni0·2Co0.1 and TiFe0·7Co0·2Ni0.1 alloys also had a single TiFe phase in spite of the simultaneous substitution. The composition of the oxide layer changed by the addition of Ni, Co, and Cu, but the alloys did not absorb hydrogen. In the TiFe0·8Mn0.2 and TiFe0·8Cr0.2 alloys, a dual-phase microstructure consisting of TiFe and Mn/Cr-rich C14 Laves phase was formed, with a larger amount in TiFe0·8Cr0.2. Both samples absorbed hydrogen after air exposure without any thermal activation process. Comparing the first hydrogenation kinetics, TiFe0·8Cr0.2 had a shorter incubation time and faster hydrogen absorption rate than TiFe0·8Mn0.2.  相似文献   

18.
A first investigation into the production of amorphous and nanostructured Ti-based alloys with nominal compositions Ti41.5Zr41.5Ni17, Ti61Zr22Ni17, Ti41.5V41.5Ni17 and Ti61V22Ni17 by mechanical alloying (MA) technique is presented. This technique was adopted to produce alloys' powders with high fresh surface area that were active for hydrogen storage. Hydrogen absorption characteristics and structure changes in the alloys after hydrogenation were investigated. Gas phase hydrogenation of the Ti–Zr–Ni alloys, at 573 K and an initial hydrogen pressure of 2 MPa, exhibited good hydriding properties and started at a maximal rate without induction period with a hydrogenation capacity up to 1.2 wt%. However, hydriding of Ti–V–Ni alloys at the same conditions exhibited slower rates. The Ti61V22Ni17 composition showed high hydrogen absorption capacity of 1.8 wt% and exceeded 4 wt% at 345 K. In addition, the Ti–V–Ni alloys showed structure stability after hydrogenation and retained the amorphous structure.  相似文献   

19.
The non-stoichiometric Zr0.9TixV2 (x = 0, 0.2, 0.3, 0.4) alloys are designed to explore the effect of non-stoichiometry on phase constituent, microstructure and hydrogenation properties of Zr-based AB2 Laves alloys. The alloys are prepared by non-consumable arc melting and annealed at 1273 K for 168 h in argon atmosphere to ensure the homogeneity. Phase structure investigation shows the α-Zr/β-Zr phase and V-BCC phase originating from the non-equilibrium solidification can be reduced after annealing, C15-type ZrV2 becomes the dominant phase. Meanwhile, a small amount of Zr3V3O phase generates when x ≤ 0.2 and the β-Zr transforms to α-Zr when x > 0.2. High density annealing twins are observed in ZrV2 matrix by TEM. Activation behavior, hydrogenation kinetics and PCT characteristics of annealed Zr0.9TixV2 are investigated in the temperature range 673–823 K. With the decrease in B/A ratio or increase in Ti content, the initial hydrogen absorption speed decreases obviously, the plateaus of PCT curves become wide and flat, meanwhile the hydrogen absorption capacity and the stability of metal hydrides increases. Twin defects observed in these alloys play an important role in accelerating the hydrogenation kinetics. In addition, phase constituent after hydrogenation is analyzed.  相似文献   

20.
The study focuses on the reaction between hydrogen gas and LaNi5−xSnx alloys, where 0 ≤ x ≤ 0.5, in broad temperature and pressure ranges. It was performed by means of dynamic volumetric techniques using specific equipment developed at our laboratory. The substitution of Ni by Sn lowers the system equilibrium pressure and increases the hydrogen absorption reaction rate. Reaction pressures at room temperature range from 8 kPa (x = 0.5) to 250 kPa (x = 0). At 415 K the reaction pressure is within the range from 200 kPa to 4000 kPa for x = 0.5 and 0, respectively. The measured characteristic absorption time at 750 kPa for LaNi5 is around 1 min, while it remains below 2.5 s for LaNi4.5Sn0.5. The maximum H concentration goes from 1.3 wt.% for LaNi5 down to 0.95 wt.% for LaNi4.5Sn0.5. These results are useful to identify a metal system where the hydrogen interaction equilibrium properties can be tuned in a wide pressure range by choosing the chemical composition and the process temperature.  相似文献   

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