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1.
The La2−xTixMgNi9 (x = 0.1, 0.2, 0.3, 0.4) alloys were prepared by magnetic levitation melting under Ar atmosphere. The effects of partial substitution Ti for La on the phase structures, hydrogen-storage properties and electrochemical characteristics of the alloys were investigated systematically. For La2−xTixMgNi9 (x = 0.1, 0.2, 0.3, 0.4) alloys, LaNi5, LaNi3 and LaMg2Ni9 are the main phases, the maximum hydrogen-storage capacity is 1.51, 1.36, 1.35 and 1.22 wt%, respectively. The absorption–desorption plateau pressure of the alloys first decreases and then increases with increase of Ti content, and the La1.8MgTi0.2Ni9 alloy has the lowest absorption–desorption plateau pressure. The discharge voltage of the alloy electrodes rises with increasing the amount of Ti content. The La1.8Ti0.2MgNi9 alloy electrode presents good electrochemical performance.  相似文献   

2.
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   

3.
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   

4.
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 (V20Ti38Cr41.4Fe0.6, V40Ti28.5Cr30.1Fe1.4, 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.  相似文献   

5.
Hydrogen absorption/desorption has been investigated in the three series of solid solution bcc alloys Ti35VxCr65−x (x = 18,22), Ti40VxMn50−xCr10 (x = 32,36) and TixCr97.5−xMo2.5 (x = 43,46). It has been found that the H absorption at pressures smaller than 1 bar can only occur after elimination of the oxide films by heating the alloys to temperatures higher than 600 K. Hydrogen desorption from pre-loaded materials (nH = H/Me ≤ 0.27) takes place on heating at much lower temperatures in the Ti40VxMn50−xCr10 and Ti35VxCr65−x than in the TixCr97.5−xMo2.5 alloys. The H diffusion parameters W and Do deduced from high temperature (>450 K) absorption experiments are as follows: W = 0.318 ± 0.005 eV, Do = (4 ± 1)×10−7 m2/s for Ti40VxMn50−xCr10; W = 0.32 ± 0.02 eV, Do = (3 ± 2)×10−7 m2/s for Ti35VxCr65−x; W = 0.79 ± 0.06 eV, Do = (4 ± 2)×10−8 m2/s for TixCr97.5−xMo2.5. The higher value of the activation energy for H diffusion in Mo containing alloys is most likely due to remarkable attractive interactions between H and Mo atoms.  相似文献   

6.
The Zr(V1−xFex)2 (x = 0.02, 0.05, 0.10, 0.15, 0.25) alloys were prepared by the arc-melt method and annealed at 1273 K for 168 h in an argon atmosphere. Phase structure investigations of the as-cast and annealed Zr(V1−xFex)2 alloys indicate the annealing treatment can eliminate the minority phases originating from the non-equilibrium solidification of as-cast alloys. The ZrV2-type phase becomes the dominant one in each annealed alloy. The substitution of Fe in V sites leads to the contraction of their lattice. For annealed Zr(V1−xFex)2 alloys, the P–t and PCT curves obtained between 673 K and 823 K give the evidence that the absorption process is controlled by a rate-controlling hydrogen diffusion. With the increase of iron, the equilibrium pressure and the plateau slope increase while the hydrogenation capacity and the absolute value of enthalpy and entropy decrease accordingly. The stability of metal hydride reduces gradually as the Fe content varies from x = 0.02 to 0.25 which promotes the hydrogen release and favors the practical applications of the Zr(V1−xFex)2 alloys.  相似文献   

7.
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   

8.
In this work, quaternary alloys having compositions Ti1.9CrVM0.1 and Ti1.8CrVM0.2 (M = Fe, Co and Ni) have been studied in detail for their structural aspects and hydrogen absorption–desorption properties. All the alloys form bcc phase solid solutions and after hydrogen absorption the structures change to fcc. The pressure composition isotherms, hydrogen storage capacities and hydrogen absorption kinetics were studied using Sievert's type of volumetric setup. The Ti1.9CrVFe0.1, Ti1.9CrVCo0.1 and Ti1.9CrVNi0.1 alloys are found to absorb maximum 3.80, 3.68 and 3.91 wt.% of hydrogen respectively; whereas, Ti1.8CrVCo0.2 and Ti1.8CrVNi0.2 alloys show 3.52 and 3.67 wt.% of hydrogen at room temperature. All the alloys show fast hydrogen absorption kinetics at the room temperature. From differential scanning calorimetric measurements, it has been found that Fe, Ni and Co substitution in place of Ti decreased the hydrogen desorption temperature drastically compared to the parent alloy.  相似文献   

9.
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   

10.
Ti0.85Zr0.17Cr1.2-xFe0.8Vx (x = 0–0.2), Ti0.85Zr0.17Cr1.2-yFe0.7+yV0.1 (y = 0–0.25) and Ti0.87-zZr0.15+zCr0.95Fe0.95V0.1 (z = 0–0.04) alloys for metal hydride hydrogen compressor at moderate working temperatures were prepared by induction levitation melting. Their microstructures and hydrogen storage properties were systematically investigated. The results show that all Ti–Zr–Cr–Fe–V based alloys have a single C14 Laves phase structure. As the V content in the Ti0.85Zr0.17Cr1.2-xFe0.8Vx (x = 0–0.2) alloys increases, better activation kinetics and larger hydrogen storage capacity are achieved, while the plateau pressure decreases and the plateau slope factor increases. Similarly, the hydrogen storage capacity, the plateau pressure and the plateau slope factor of the Ti0.87-zZr0.15+zCr0.95Fe0.95V0.1 (z = 0–0.04) alloys vary identically with Zr content increasing. Conversely, these three properties vary oppositely with increasing Fe content in the Ti0.85Zr0.17Cr1.2-yFe0.7+yV0.1 (y = 0–0.25) alloys. Among the studied alloys, Ti0.85Zr0.17Cr0.95Fe0.95V0.1 possesses the best overall properties for the designed moderate hydrogen compression application.  相似文献   

11.
Hydrogen storage properties, activation performance and thermodynamics of Ti0.7Zr0.3(Mn1−xVx)2 (x = 0.1, 0.2, 0.3, 0.4, 0.5) alloys and associated microstructures and surface chemical states were investigated by hydrogenation measurements and relevant structure and surface characterization methods. The results showed that the phase composition of the alloy changed from single C14 Laves phase (x ≤ 0.2) to coexistent Laves phase and V-based BCC solid solution phase with increasing V content (x ≥ 0.3). The V in the alloys catalyzed hydrogen dissociation and improved resistivity to oxygen poisoning, so that the alloys could be easily and quickly activated at 293 K even after being exposed in air for a long time. The hydrogen storage capacity of the alloy increased and the plateau pressure decreased with increasing V content. The x   = 0.2 and 0.3 alloys exhibited the best reversible hydrogen storage capacities of above 1.8 wt% at 1 kPa–4 MPa and 293 K. The relative partial molar enthalpy |ΔH||ΔH| increased but the relative partial molar entropy |ΔS||ΔS| decreased with increasing V content, and deviated from the linear relationship for x = 0.4 and 0.5 alloys due to coexisted BCC phase in the alloys.  相似文献   

12.
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   

13.
A series of carbon-coated layered structured Li[CrxLi(1/3−x/3)Ti(2/3−2x/3)]O2 samples (0.3 ≤ x ≤ 0.45) were prepared. Among them, the sample of x = 0.4 shows the highest initial reversible capacity of 207 mAh g−1 at 30 mA g−1 in 2.5–4.4 V. The reversible Li-storage capacities for the samples with high x values (x = 0.4, 0.45) faded slightly while the samples with low Cr content (x = 0.3 and 0.35) showed a capacity increase upon cycling. It was found that the relative intensity ratio of (0 0 3) peak to (1 0 4) peak (R(0 0 3) = I(0 0 3)/I(1 0 4)) is influenced strongly by x value in as-prepared samples. The samples of x = 0.35 and 0.4 turn to a similar structure with low R(0 0 3) value during cycling. These phenomena indicate that the cation mixing of Cr3+ in the lithium layer occurs in as-prepared samples and became more significant upon delithiation and lithiation. This is supposed being a necessary process for Cr-based layered structure materials possessing electrochemical reactivates. The occurrence of the cation mixing is beneficial from the local lattice distortion caused by the short-range ordering between Ti and Li. This is supposed to be helpful for the migration of Cr6+ and Cr3+ at tetrahedral and octahedral sites. Different from the case of LiNiO2, the cation mixing is essential for the transport and storage of lithium in the carbon-coated Li–Cr–Ti–O layered compounds.  相似文献   

14.
Improvement of cyclic durability of Ti-Cr-V alloy by Fe substitution   总被引:1,自引:0,他引:1  
Cyclic durability of hydrogen storage Ti-Cr-V alloys has been investigated. After 100 absorption/desorption cycles, Ti12Cr23V64Fe1 desorbs 2.34 mass% of hydrogen while Ti12Cr23V65 desorbs 2.19 mass% of hydrogen. These desorption capacities of Ti12Cr23V64Fe1 and Ti12Cr23V65 correspond to 97% and 88% of their initial capacities, respectively. The X-ray diffraction profiles of the alloys suggest that Fe substitution inhibits the increase of the lattice strain and the decrease of the crystallite size accompanied by hydrogen absorption and desorption. This inhibition most likely relates to the improvement of cyclic durability by Fe substitution.  相似文献   

15.
The deuterium thermal desorption of various YFe2Dx (x = 1.3, 2.5, 3.5, 4.2) compounds has been studied using differential scanning calorimetry (DSC) and thermal desorption (TD) experiments. These studies show that the number of desorption peaks increases with the deuterium content. In order to understand the origin of this multipeak behaviour, in situ neutron diffraction experiments during thermal desorption have been performed from 290 K to 680 K on YFe2D4.2. Upon heating, a multipeak TD spectrum is observed. It relates to the existence of several YFe2Dx phases with different stabilities. The rate limiting step of this thermal desorption has been therefore attributed to several successive phase transformations rather than to different types of interstitial sites as proposed in previous TD models reported for C15-Laves phase compounds.  相似文献   

16.
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.  相似文献   

17.
Doping of interstitial elements B or C into a BCC-type Ti25V35Cr40 alloy to raise effective desorption hydrogenation capacity was investigated. Ti25V35Cr40Mx alloys (M = B or C and x = 0, 0.1, 1, or 5) were prepared by arc-melting followed by homogenization treatment. X-ray diffraction shows that the as-cast specimens have a BCC structure, but they contain some amount of precipitates that increases with the doping concentration of B and C. Doping-induced precipitates can be greatly eliminated by annealing treatment at 1200 °C, indicating that B or C might have been partially dissolved into the interstitial sites in the BCC lattice of matrix phase of specimens. With the doping of C, the second plateau pressure of annealed specimens in the PCI curves at T = 30 °C significantly increases with the amount of C, but the maximum hydrogenation capacity is reduced. On the other hand, the second plateau pressure and maximum hydrogenation capacity are only slightly affected by the B doping. Under optimum doping conditions, the effective hydrogen desorption capacities are increased from 0.80 H/M of the sample without doping to 0.86 H/M and 0.87 H/M for Ti25V35Cr40B1 and Ti25V35Cr40C0.1, respectively. The improvement might be ascribed to the increase in second plateau pressure caused by less stable hydrogen atoms at the lattice sites of Ti25V35Cr40 containing interstitial B or C.  相似文献   

18.
Structural evolution during topotactical electrochemical lithium insertion and deinsertion reactions in ramsdellite-like LixTi2O4 has been followed by means of in situ X-ray diffraction techniques. The starting LixTi2O4 (x = 1) exists as a single phase with variable composition which extends in the range 0.50 ≤ x ≤ 1.33. However, beyond the lower and upper compositional limits, two other single phases, with ramsdellite-like structure, are detected. The composition of these single phases are: TiO2 upon lithium deinsertion and Li2Ti2O4 upon lithium insertion. Both TiO2 and Li2Ti2O4 are characterized by narrow compositional ranges. The close structural relationship between pristine LiTi2O4 and the inserted and deinserted compounds together with the relative small volume change over the whole insertion–deinsertion range (not more than 1.1% upon reduction) is a guaranty for the high capacity retention after long cycling in lithium batteries. The small changes in cell parameters well reflect the remarkable flexibility of the ramsdellite framework against lithiation and delithiation reactions.  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.
Effects of the Mn substitution on microstructures and hydrogen absorption/desorption properties of LaNi3.8Al1.2−xMnx (x = 0.2, 0.4, 0.6) hydrogen storage alloys were investigated. The pressure-composition (PC) isotherms and absorption kinetics were measured in a temperature range of 433 K ≤ T ≤ 473 K by the volumetric method. XRD analyses showed that with the increase of the Mn content in the LaNi3.8Al1.2−xMnx alloys, the lattice parameter a was decreased, c increased and the unit cell volume V reduced. It was found that the absorption/desorption plateau pressure was increased and the hydrogen storage capacity was enhanced with the increase of Mn content. The absorption/desorption plateau pressure of the alloys was linearly changed with the Mn content x and the lattice parameter a, while the hydrogen storage capacity was linearly increased with the increase of c/a ratio. It was also found that the slope factor Sf was closely correlated with the lattice strain of the alloys.  相似文献   

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