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1.
Baozhong Liu Yude Zhang Guofa Mi Zhi Zhang Limin Wang 《International Journal of Hydrogen Energy》2009
Ti45Zr35Ni20−xPdx (x = 0, 1, 3, 5 and 7, at%) alloys were prepared by melt-spinning. The phase structure and electrochemical hydrogen storage performances of melt-spun alloys were investigated. The melt-spun alloys were icosahedral quasicrystalline phase, and the quasi-lattice constant increased with increasing x value. The maximum discharge capacity of alloy electrodes increased from 79 mAh/g (x = 0) to 148 mAh/g (x = 7). High-rate dischargeability and cycling stability were also enhanced with the increase of Pd content. The improvement in the electrochemical hydrogen storage characteristics may be ascribed to better electrochemical activity and oxidation resistance of Pd than that of Ni. 相似文献
2.
Xiangyu Zhao Junfeng ZhouXiaodong Shen Meng Yang Liqun Ma 《International Journal of Hydrogen Energy》2012
Elemental substitution of part Ti by Zr has been carried out for Ti2Ni alloy to form Ti2−xZrxNi (x = 0, 0.2, 0.4) alloys. Mechanical milling and subsequent heat treatment have been used to prepare non-equilibrium Ti–Zr–Ni alloys. The effects of Zr addition on the structure and discharge properties of Ti2Ni alloy were investigated. The addition of Zr could enhance the discharge capacity of the non-equilibrium Ti2Ni alloy at electrolyte temperatures of 313 and 333 K. For instance, the non-equlibrium Ti1.6Zr0.4Ni alloy had a stable discharge capacity of about 210 mAh/g at 313 K. However, the protective surface layer formed during heat treatment was destroyed at a high electrolyte temperature of 333 K, and thus a severe capacity loss during cycling. 相似文献
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Abeer Dagher Hanadi G. Salem Tarek M. Moustafa Eman Bellah Mettawee Ehab Abdel-Rahman 《International Journal of Hydrogen Energy》2014
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
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《International Journal of Hydrogen Energy》2004,29(8):881-888
A series of multi-component Zr1−xTixV0.4Ni1.2Mn0.4LMy (x=0.3, 0.4; y=0.0,0.02,0.05,0.1,0.2,0.3, LM; lantanum-rich-mischmetal) alloys are prepared and their crystal structure and P–C–T curves are analyzed. The alloys have been modified by adding LM and their gaseous and electrochemical hydrogenation properties are studied to find out the effect of LM elements. Also, the second phase and initial activation performance are investigated. The Zr1−xTixV0.4Ni1.2Mn0.4LMy (x=0.3,0.4; y=0.0,0.02,0.05,0.1,0.2,0.3) alloys have C14 Laves phase hexagonal structure, so the volume expansion ratio of lattice parameters with LM has increased. As the amount of LM in alloy has increased, correspondingly the second phase is also increased. The second phase is LM, Ti and V-rich. The second phase improve the activation of La-rich misch-metal, and also the concentration of elements Ti, V〉LM〉 matrix in alloys.The addition of LM in Zr1−xTixV0.4Ni1.2Mn0.4LMy (x=0.3, 0.4) alloys have increased the activation rate and hydrogen storage capacity significantly, but the plateau pressure and the discharge capacity have been decreased due to the formation of second phase. For more Zr in electrode alloys, the activation of rate becomes slow. 相似文献
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La–Mg–Ni alloys are potential candidates for hydrogen storage materials. In this study, mechanical alloying with subsequent annealing under an argon atmosphere at 973 K for 0.5 h, were used to produce La2-xMgxNi7 alloys (x = 0, 0.25, 0.5, 0.75, 1). Shaker type ball mill was used. An objective of the present study was to investigate an influence of amount of Mg in alloy on electrochemical, hydrogenation and dehydrogenation properties of La–Mg–Ni materials. X-ray diffraction analyses revealed formation of material with multi-phase structure. Obtained materials were studied by a conventional Sievert's type device at 303 K. It was observed that electrochemical discharge capacity and gaseous hydrogen storage capacity of La–Mg–Ni alloys increases with Mg content to reach maximum for La1.5Mg0.5Ni7 alloy. Moreover, all of La–Mg–Ni alloys were characterized by improved hydrogen sorption kinetics in comparison to La–Ni alloy. 相似文献
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Mg1.5Ti0.5−xZrxNi (x = 0, 0.1, 0.2, 0.3, 0.4), Mg1.5Ti0.3Zr0.1Pd0.1Ni and Mg1.5Ti0.3Zr0.1Co0.1Ni 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 (Mg1.5Ti0.4Zr0.1Ni 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. 相似文献
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The non-stoichiometric C15 Laves phase alloys namely Zr0.9Ti0.1Vx (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 Zr0.9Ti0.1Vx 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 Zr0.9Ti0.1Vx Laves alloys are discussed. 相似文献
10.
《Journal of power sources》1999,77(2):159-163
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, Ti0.5Zr0.5V0.2Mn0.7Cr0.5Ni0.6, 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. 相似文献
11.
《International Journal of Hydrogen Energy》2002,27(3):287-293
The effect of Zr substitution for Ti on the microstructures and electrochemical properties of the electrode alloys Ti1−xZrxV1.6Mn0.32Cr0.48Ni0.6 (x=0.2,0.3,0.4,0.5) has been studied. It is found by X-ray powder diffraction and energy dispersive X-ray spectroscope analyses that all the alloys consist of a C14 Laves main phase with hexagonal structure and a V-based solid solution secondary phase with b.c.c. structure. A small amount of TiNi-based third phase with b.c.c. structure has been found precipitated in the C14 Laves main phase in addition. With the increase in the amount of Zr substitution, the lattice parameters of the main phase and secondary phase are found increased and decreased, respectively. The electrochemical PCT curves indicate that the maximum hydrogen absorption capacity [H/M]max decreases with increasing Zr substitution, which may be attributed to the decrease in the content of V-based solid solution. The maximum discharge capacity and high rate dischargeability of the alloy electrodes both decrease, while the cyclic durability increases with the increasing amount of Zr substitution. 相似文献
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In hydrogen solid–gas reaction at 300 K and 1 bar, the hydrogen content for Ti3.87Ni1.73Fe0.7Ox (0.2≤ × ≤0.8) alloys was in range 1.93–0.05 (Cwt.H,%), and discharge capacity of 360–235 A h/kg was achieved accordingly. The ΔHH2 and ΔSH2 values of −32.29 kJ mol−1 and −111.04 J mol−1 K−1, respectively, for Ti3.87Ni1.73Fe0.7O0.5 alloy were obtained using experimental PCT relations, where hysteresis effect was only slightly visible. The half-cell potentials (vs. Hg/HgO) of metal hydride (MH) electrodes based on Ti3.87Ni1.73Fe0.7Ox (0.2≤ ×≤ 0.8) alloys were calculated. 相似文献
15.
In order to improve kinetic properties of La–Mg–Ni-based hydrogen storage alloys, Mo–Ni treatment was applied to La0.88Mg0.12Ni2.95Mn0.10Co0.55Al0.10 alloy powders. FESEM results showed that after Mo–Ni treatment some network-shaped substance with nano-size formed on the surface of the alloy particles. The EDS results revealed increase in Ni content and emerge of Mo element. EIS and Linear polarization showed that charge-transfer resistance decreased and exchange current density increased for the treated alloy electrode, and the high rate dischargeability (HRD) was consequently improved. HRD at 1500 mA/g increased from 22.5% to 39.5%. Mo- and Ni-single treatments were performed compared with the Mo–Ni treatment, and the results showed that the single treatment improved HRD slightly, far less than the Mo–Ni treatment. 相似文献
16.
Yang-Huan Zhang Xiao-Ping Dong Guo-Qing Wang Shi-Hai Guo Jiang-Yuan Ren Xin-Lin Wang 《International Journal of Hydrogen Energy》2007
In order to improve the electrochemical performances of La–Mg–Ni system (PuNi3-type) hydrogen storage alloy, a trace of B was added in La2Mg(Ni0.85Co0.15)9 alloy. La2Mg(Ni0.85Co0.15)9Bx (x=0,0.05,0.1,0.15,0.2) hydrogen storage alloys were prepared by casting and rapid quenching. The electrochemical charging-discharging cycling lives and microstructures of the as-cast and quenched alloys were measured and analyzed. The effects of B additive on the microstructures and cycling lives of as-cast and quenched alloys were investigated in detail. The results show that the as-cast and quenched alloys are composed of the (La, Mg)Ni3 phase (PuNi3 structure), the LaNi5 phase and the LaNi2 phase. A trace of the Ni2B phase exists in the as-cast alloys containing B. The Ni2B phase in the alloys containing B nearly disappears after rapid quenching and the relative ratio of each phase in the alloys changes with the variety of the quenching rate. The addition of B obviously enhances the charging-discharging cycling stabilities of the as-cast and quenched alloys. When B content x increases from 0 to 0.2, the cycling lives of the as-cast and quenched at 20 m/s alloys were increased from 72 to 94 cycles and from 86 to 104 cycles, respectively. 相似文献
17.
Yanghuan Zhang Haitao Wang Tingting Zhai Tai Yang Yan Qi Dongliang Zhao 《International Journal of Hydrogen Energy》2014
Nanocrystalline and amorphous Mg–Nd–Ni–Cu-based (Mg24Ni10Cu2)100−xNdx (x = 0–20) alloys were prepared by melt spinning and their structures as well as hydrogen storage characteristics were investigated. The analysis of XRD, TEM and SEM linked with EDS reveal that all the as-cast alloys hold a multiphase structure, containing Mg2Ni-type major phase as well as some secondary phases Mg6Ni, Nd5Mg41 and NdNi, whose amounts clearly grow with Nd content rising. Furthermore, the as-spun Nd-free alloy displays an entire nanocrystalline structure whereas the as-spun Nd-added alloys have a mixed structure of nanocrystalline and amorphous, moreover, the amorphization degree of the alloys visibly increases with Nd content rising, implying that the addition of Nd facilitates the glass forming in the Mg2Ni-type alloy. The addition of Nd results in a slight decrease in the hydrogen absorption capacity of the as-cast and spun alloys, but it significantly enhances their hydrogen storage kinetics and hydriding/dehydriding cycle stability of the alloy. In order to reveal the capacity degradation mechanism of the as-spun alloy, the structure evolution of the nanocrystalline and amorphous alloys during the hydriding–dehydriding cycles was investigated. It is found that the root causes of leading to the capacity degradation of the nanocrystalline and amorphous alloys are nanocrystalline coarsening, crystal defect decreasing and amorphous phase crystallizing. 相似文献
18.
The influence of substrate morphology and ageing on the charge–discharge performance of a Sn–Ni alloy anode electrodeposited on a Cu substrate are examined. The Sn–Ni alloy (Sn 82 at.%–Ni 18 at.% anode) shows a high capacity of around 480 mAh g−1 up to 12 cycles, but its capacity rapidly fades with cycling. The initial capacity and the cyclic properties of the alloy electrode are significantly improved when the surface morphology of the Cu substrate is changed from smooth-type to nodule-type. Optimized ageing treatment leads to further enhancement in the charge–discharge performance of the anode. The increase in the capacity and better cyclic properties are attributed to stronger adhesion between the Si–Ni anode and the Cu substrate. This is induced by inter-locking of the nodule-type Cu substrate and a buffering effect of Cu–Sn intermetallic compounds formed during ageing. 相似文献
19.
Rapidly quenched Zr2Ni amorphous and nanocrystalline ribbons were studied as electrocatalysts for hydrogen evolution in 6 M KOH. Linear polarization, potentiostatic hydrogen charge/discharge and EIS measurements at various potentials were carried out for the Zr alloys with different microstructure with the aim to extract information about the mechanism of hydrogen evolution and absorption and estimate the kinetic parameters of the hydrogen evolution reaction (HER). Though the melt-spun Zr67Ni33 alloys with varying microstructure do not show substantially different catalytic activity for HER, it could be clearly demonstrated that the nanocrystalline material reveals better catalytic performance than the entirely amorphous and nano-/amorphous alloys with the same chemical composition. It was found that all studied Zr–Ni alloys absorb hydrogen under the conditions of the hydrogen evolution experiments, as the amount of the absorbed hydrogen depends to a large degree on the alloys microstructure as well as on the applied potential during the HER experiment. The diffusion coefficient of hydrogen into the amorphous Zr67Ni33 alloy, as well as the thickness of the hydrided layer were found to be noticeably larger than those of the nanocrystalline alloy at the same conditions of hydrogen charging. Therefore the improved electrocatalytic properties of the nanocrystalline alloy could only be explained by its favorable microstructure (e.g. higher density of defects) and weaker hydrogen absorption into the nanostructured material under the conditions of the HER. 相似文献
20.
Structure changes during hydrogenation are observed in pure Mg, Mg2Ni intermetallic (I) and Mg eutectic alloy – 23.5 wt.% Ni (E). Samples were prepared by (i) ball-milling and compacting (alloys I and E) and (ii) by mould casting (Mg and alloy E). Phase composition was checked by SEM and XRD. It was found that the hydrogenated cast alloy I and ball-milled alloy I hydrogenated below the transition temperature Ttr = 508 K contained a much higher amount of low-temperature un-twinned phase LT1 than the ball-milled alloy I hydrogenated above Ttr. It was shown that micro-twinned phase LT2 slows down the rate of hydrogen desorption. Persistent changes of morphology were observed in all materials after the first hydrogen charging cycle which may explain the so-called activation of Mg-based hydrogen-storage materials described in the literature. 相似文献