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1.
Crystal structure and hydrogen storage properties of a novel equiatomic TiZrNbCrFe high-entropy alloy (HEA) were studied. The selected alloy, which had a A3B2-type configuration (A: elements forming hydride, B: elements with low chemical affinity with hydrogen) was designed to produce a hydride with a hydrogen-to-metal atomic ratio (H/M) higher than those for the AB2- and AB-type alloys. The phase stability of alloy was investigated through thermodynamic calculations by the CALPHAD method. The alloy after arc melting showed the dominant presence of a solid solution C14 Laves phase (98.4%) with a minor proportion of a disordered BCC phase (1.6%). Hydrogen storage properties investigated at different temperatures revealed that the alloy was able to reversibly absorb and fully desorb 1.9 wt% of hydrogen at 473 K. During the hydrogenation, the initial C14 and BCC crystal structures were fully converted into the C14 and FCC hydrides, respectively. The H/M value was 1.32 which is higher than the value of 1 reported for the AB2- and AB-type HEAs. The present results show that good hydrogen storage capacity and reversibility at moderate temperatures can be attained in HEAs with new configurations such as A3B2/A3B2H7.  相似文献   

2.
The hydrogen storage properties of the novel equiatomic TiZrNbFeNi and non-equiatomic Ti20Zr20Nb5Fe40Ni15 high entropy alloys (HEAs) were studied. These alloys were designed with the aid of thermodynamic calculations using the CALPHAD method due to their tendency to form single C14 Laves phase, a phase desirable for room-temperature hydrogen storage. The alloys, which were synthesized by arc melting, showed a dominant presence of C14 Laves phases with the (Zr, Ti)1(Fe, Ni, Nb, Ti)2 constitution and small amounts of cubic phases (<1.4 wt%), in good agreement with the thermodynamic predictions. Hydrogen storage properties, examined at room temperature without any activation procedure, revealed that a maximum hydrogen storage capacity was reached for the equiatomic alloy in comparison to the non-equiatomic alloy (1.64 wt% vs 1.38 wt%) in the first cycle; however, the non-equiatomic alloy presented superior reversibility of 1.14 wt% of hydrogen. Such differences on reversibility and capacity among the two alloys were discussed based on the chemical fluctuations of hydride-forming and non-hydride-forming elements, the volume per unit cell of the C14 Laves phases and the distribution of valence electrons.  相似文献   

3.
In the present study, the hydrogen storage performance of multi-principal-component ZrTiVNiCrFe alloy produced through rapid solidification has been examined by electrochemical methods and gas-solid reactions. XRD and EBSD analyses reveal the hexagonal Laves phase structure (type C14) with average grain size of 300 nm and root-mean-square microstrain of 0.19%. Cyclic voltammetry and electrochemical impedance spectroscopy analyses in the hydrogen sorption/desorption region give insight to the sorption/desorption kinetics and the change in the desorption charge in terms of the applied potential. The pressure-composition isotherms measured in course of gas-solid reaction confirm the hydrogen storage capacity reaching 1.6 wt% at the first hydrogenation at room temperature, then reducing to 1.3–1.4% during subsequent cycling. According to the calorimetric titration study, there is a significant hysteresis primarily caused by the non-equilibrium character of the hydrogenation process.  相似文献   

4.
ZrTiVFe high-entropy alloy has shown desirable hydrogen absorption and desorption properties due to its lattice distortion effect and high content of C14 phase that can store hydrogen. In this study, element Cu was used to improve the reversible hydrogen storage properties of equimolar ZrTiVFe alloy by increasing valence-electron concentration (VEC), and (ZrTiVFe)1-xCux (x = 0.05, 0.1, 0.2) alloys were prepared. After studying their microstructural features and hydrogen storage properties, the results indicate that (ZrTiVFe)0.95Cu0.05 and (ZrTiVFe)0.90Cu0.10 alloys are mainly consisted of C14 Laves phase and a small amount of α-Ti and α-Zr phases. When the Cu content increases to 20 at. %, the microstructure transforms to reticular ZrTiCu2 phase around C14 Laves phase, and the Cu8Zr3 phase is formed in final solidification stage. The fastest hydrogen absorption rate of (ZrTiVFe)0.80Cu0.20 alloy at room temperature suggests the ZrTiCu2 and Cu8Zr3 phases can provide preferential paths for hydrogen atoms diffusion. The amount of hydrogen in (ZrTiVFe)0.90Cu0.10 hydride that cannot be desorbed at 400 °C in vacuum is greatly reduced from 0.370 wt% to 0.084 wt% comparing with ZrTiVFe hydride. The addition of element Cu reduces the stability of ZrTiVFe hydride significantly, which favors the hydrogen desorption of the (ZrTiVFe)1-xCux alloys.  相似文献   

5.
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   

6.
The effect of long-term hydrogen absorption/desorption cycling up to 3500 cycles on the hydrogen storage properties of LaNi3.8Al1.0Mn0.2 alloy was investigated. The pressure-composition (PC) isotherms for absorption/desorption and the absorption kinetics were measured at 433 K, 453 K and 473 K. X-ray diffraction analysis revealed that the alloy had a homogeneous hexagonal CaCu5 type structure and kept this structure even after 3500 cycles, but the diffraction peaks were broadened. The degree of peak broadening was increased with increase of the cycle number, but exhibiting a maximum after initial activation. The shapes of PCT curves after 300, 2000 and 3500 cycles were similar to that after initial activation. It was found that the alloy subjected to 300 cycles did not exhibit significant changes in hydrogen storage capacity, but the long-term cycling up to 2000 and 3500 cycles resulted in obvious decrease in hydrogen storage capacity. The degradation of the hydrogen capacity might be resulted from the formation of the irreversible sites and more stable hydride phase, though no new phase was found after absorption/desorption cycling from XRD pattern as shown in Fig. 6 because of the limitation of XRD analysis sensibility. The hydrogen absorption kinetics after 300 cycles was deteriorated but improved again after 2000 and 3500 cycles compared with that of after initial activation. The changes in hydrogenation properties of the alloy induced by cycling were discussed by considering the crystal structure, lattice strain and pulverization of the sample.  相似文献   

7.
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.  相似文献   

8.
The microstructure and hydrogen storage properties of Ti10+xV80-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.  相似文献   

9.
In the present study, two process techniques, mechanical alloying and innovative vacuum copper boat induction melting, were used to produce Ti0.72Zr0.28Mn1.6V0.4 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.  相似文献   

10.
Nanostructured materials for hydrogen storage with a composition of Mg85Ni15−xMx (M = Y or La, x = 0 or 5) are formed by devitrification of amorphous and amorphous-nanocrystalline precursors produced by melt-spinning. All three compositions exhibit a maximum storage capacity of about 5 mass % H at 573 K. When ball-milled for 30 min in hexanes, the binary alloy can be activated (first-cycle hydrogen absorption) at 473 K. DSC experiments indicate that desorption in this sample begins at 525 K, compared to 560 K when the material is activated at 573 K; which indicates an improvement in the hydride reaction thermodynamics due to capillarity effects. Additions of Y and La improve the degradation in storage capacity observed during cycling of the binary alloy by slowing microstructural coarsening. Alloying with La also shows a decrease of about 8 kJ/mol and 5 kJ/mol in the enthalpy of reaction for MgH2 and Mg2NiH4 formation, respectively, compared to the binary alloy; resulting in some desorption of H2 at 473 K. The improved thermodynamics are discussed in terms of destabilization of the hydrides relative to new equilibrium phases introduced by alloying additions. The proposed hydriding reaction for the La-containing material is in agreement with previously reported experimental results.  相似文献   

11.
Mechanical milling is widely recognized as the best method to prepare nano-structured magnesium based hydrogen storage materials. The composites La7Sm3Mg80Ni10 + 5 wt% TiO2 (named La7Sm3Mg80Ni10–5TiO2) whose structures are nano-crystal and amorphous accompanied by great hydrogen absorption and desorption properties were fabricated by mechanical milling. The research focuses on the effect of milling duration on the thermodynamics and dynamics. The instruments of researching the gaseous hydrogen storing performances include Sievert apparatus, DSC and TGA. The calculation of dehydrogenation activation energy was realized by applying Arrhenius and Kissinger formulas. The calculation results show the specimen milled for 10 h exhibits the optimal activation performance and hydrogenation and dehydrogenation kinetics. Extending or shrinking the milling duration will lead to the degradation of hydrogen storage performances. The as-milled (10 h) alloy at the full activated state can absorb 4 wt% hydrogen in 87 s at 473 K and 3 MPa and release 3 wt% H2 in 288 s at 573 K and 1 × 10−4 MPa. The changed milling durations have little impact on the thermodynamic properties of experimental samples and the enthalpy change (ΔH) of the alloy milled for 10 h is 74.23 kJ/mol. Moreover, it is found that the as-milled (10 h) alloy displays the minimum apparent activation energy of dehydrogenation (59.1 kJ/mol), suggesting the optimal hydrogen storing property of the as-milled (10 h) alloy.  相似文献   

12.
We propose a simple strategy to effectively improve the hydrogenation and dehydrogenation kinetics of Mg based hydrogen storage alloys. We designed and prepared an Mg91.9Ni4.3Y3.8 alloy consisting of a large quantity of long-period stacking ordered (LPSO) phases. A type of highly dispersed multiphase nanostructure, which can markedly promote the de/hydrogenation kinetics, has been obtained utilizing the decomposition of LPSO phases at first a few of hydrogenation reactions. The fine structures of LPSO phases and the microstructural evolutions of the alloy during hydrogenation and dehydrogenation reactions were in detail characterized by means of transmission electron microscopy (TEM). The LPSO phases transformed to MgH2, Mg2NiH4, and YH3 after the first hydrogenation. The highly dispersed nanostructure at macro and micro (nano) scale range remains even after several de/hydrogenation cycles. The alloy shows excellent hydrogen storage properties and its reversible hydrogen absorption/desorption capacities are about 5.8 wt% at 300 °C. Particularly, the alloy exhibits very fast dehydrogenation kinetics. The dehydrogenated sample can release approximately 5 wt% hydrogen at 300 °C within 200 s and 5.5 wt% within 600 s. We elucidate the structural mechanism of the alloy with outstanding hydrogen storage performance.  相似文献   

13.
The compositions of TiMn (100-x, Ti/Mn=5/8)Vx (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.  相似文献   

14.
The crystal structure, microstructure, hydrogen storage properties and thermal stability of the as-cast and annealed V35Ti20Cr45 alloys prepared by arc-melting were studied in this work. It was confirmed that the as-cast alloy is a body-centered cubic (bcc) single phase, while it consists of bcc main phase and C14-typed Laves secondary phase after annealed at 973 K for 72 h. As a result of the microstructure change, the activation performance and kinetic properties of the annealed alloy are improved greatly due to the catalysis of C14-typed Laves secondary phase in the annealed alloy. The kinetic mechanism of hydrogen absorption/desorption processes in the as-cast and annealed alloys was discussed using the Johnson-Mehl-Avrami (JMA) equation. Based on the plateau pressure data from pressure-composition-temperature (PCT) measurements with the Van't Hoff equation, the calculated formation enthalpies of the hydride formed in the as-cast and annealed alloys indicate that heat treatment results in lower thermal stability of the hydride in the as-cast alloy. Furthermore, using the Kissinger method with the peak temperatures from differential scanning calorimeter (DSC) measurements at different heating rates, the calculated activation energies of the dehydrogenation in the as-cast and annealed alloys suggest that heat treatment is very beneficial to improve hydrogen absorption/desorption capacities in the alloy.  相似文献   

15.
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.  相似文献   

16.
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   

17.
The Ti0.97Zr0.019V0.439Fe0.097Cr0.045Al0.026Mn1.5 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.  相似文献   

18.
A systematic investigation was performed on the hydrogen storage behaviors of ball-milled MgH2-activated carbon (AC) composites. Differential Scanning Calorimetry (DSC) measurement on the desorption temperature was carried out and indicated that the onset and peak temperatures both decreased with increasing AC adding amount, for example, the desorption peak temperature shifted from 349 °C for 1 wt% AC to 316 °C for 20 wt% AC. Furthermore, it is noted that the hydrogen absorption capacity and hydriding kinetics of the composites were also dependent on the adding amount of AC, and the optimum condition could be achieved by mechanical milling of MgH2 with 5 wt% AC. The Mg-5wt%AC composite can absorb about 6.5 wt% hydrogen within 7 min at 300 °C and 6.7 wt% within 2 h at 200 °C, respectively. It is also demonstrated that MgH2-5wt% AC exhibited good hydrogen desorption property that could release 6.5 wt% at 330 °C within 30 min. X-ray diffraction patterns (XRD) and transmission electron microscopy (TEM) observations revealed that the grain size of the synthesized composites decreased with increasing AC amount. This may contribute to the improvement of hydrogen storage in MgH2-AC composites.  相似文献   

19.
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   

20.
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   

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