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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.
Starting from two precursors LaNi5 and LaMgNi4, four alloys with different phase structures were prepared by powder sintering technique. The results suggest that LaNi5 phase can consecutively react with LaMgNi4 phase generating (La,Mg)Ni3 and (La,Mg)2Ni7 phases, and the mole ratio of precursors LaNi5/LaMgNi4 (x) affects the phase structures of alloys significantly. XRD and Rietveld refinement results demonstrate that the alloys mainly consist of (La,Mg)Ni3 and (La,Mg)2Ni7 phases (x = 0.28 and 0.59) or (La,Mg)2Ni7 and LaNi5 phases (x = 0.87 and 1.47). When x increases from 0.28 to 0.59, the main phase becomes (La,Mg)2Ni7 phase with Ce2Ni7- and Gd2Co7-type from PuNi3-type (La,Mg)Ni3 phase. As x rises from 0.59 to 0.87, the secondary phase (La,Mg)Ni3 disappears with CaCu5-type LaNi5 phase emerging. When x grows from 0.87 to 1.47, the content of LaNi5 phase increases from 17.88 to 60.72 wt.% with (La,Mg)2Ni7 phase content declining. The alloy with (La,Mg)2Ni7 as the main phase and (La,Mg)Ni3 as the secondary phase is conducive to cyclic stability and the alloy with (La,Mg)2Ni7 as the main phase and LaNi5 as the secondary phase is beneficial to the high-rate dischargeability.  相似文献   

3.
The partial replacement of La by M (M = Pr, Zr) has been performed in order to ameliorate the electrochemical hydrogen storage performances of La–Mg–Ni-based A2B7-type electrode alloys. For this purpose, we adopt melt spinning technology to prepare the La0.75−xMxMg0.25Ni3.2Co0.2Al0.1 (M = Pr, Zr; x = 0, 0.2) electrode alloys. Then systemically investigate the effects that the preparation methods and M (M = Pr, Zr) substitution have on the structures and electrochemical hydrogen storage characteristics of the alloys. The analysis of XRD and TEM reveals that the as-cast and spun alloys hold a multiphase structure, containing two main phases (La, Mg)2Ni7 and LaNi5 as well as a trace of residual phase LaNi2. Besides, the as-spun (M = Pr) alloy displays an entire crystalline structure, while an amorphous-like structure is detected in the as-spun (M = Zr) alloy, implying the replacement of La by Zr facilitates forming amorphous phase. Based upon electrochemical measurements, an impact engendered by melt spinning on the electrochemical performances of the alloys appears to be evident. The cycle stabilities monotonously augment with the growing of the spinning rate. The discharge capacity and high rate discharge ability (HRD), however, exhibit difference. For the (M = Pr) alloy, they first mount up and then fall with the rising of the spinning rate, whereas for the (M = Zr) alloy, they always decline as the spinning rate elevates. Furthermore, the replacement of La by M (M = Pr, Zr) considerably enhances the cycle stability of the alloys and the replacement of La by Pr clearly increases the discharge capacity, but the Zr replacement results in an adverse impact.  相似文献   

4.
The effect of Mg content on the structural characteristics and hydrogen storage properties of the Ca3.0−xMgxNi9 (x = 0.5, 1.0, 1.5 and 2.0) alloys was investigated. The lattice parameters and unit cell volume of the PuNi3-type (Ca, Mg)Ni3 main phase decreased with increasing Mg content. The 6c site of PuNi3-type structure was occupied by both Ca and Mg atoms. Moreover, the occupation factor of Ca on the 6c site decreased with the increase of Mg content. The hydrogen absorption capacity of the alloys decreased due to higher Mg content. However, the thermodynamic properties of hydrogen absorption and desorption were improved and the plateau pressures were increased. When x = 1.5–2.0, the Ca3.0−xMgxNi9 alloys had favorable enthalpy (ΔH) and entropy (ΔS) of hydride formation.  相似文献   

5.
The microstructure and electrochemical hydrogen storage characteristics of (La0.7Mg0.3)1−xCexNi2.8Co0.5 (x = 0, 0.05, 0.10, 0.15 and 0.20) alloys have been investigated. The results show that all alloys consist of (La, Mg)Ni3 and LaNi5 phases. The cyclic stability (S100) of the alloy electrodes increases from 58.7% (x = 0) to 69.8% (x = 0.20) after 100 charge/discharge cycles. The high rate dischargeability (HRD) increases from 66.8% (x = 0) to 69.6% (x = 0.10), then decreases to 65.1% (x = 0.20) at the discharge current density of 1200 mA/g. Moreover, the electrochemical kinetic characteristics of the alloy electrodes are also improved by increasing Ce content.  相似文献   

6.
The microstructures and electrochemical properties of La0.8−xCexMg0.2Ni3.5 (x = 0.00–0.20) hydrogen storage alloys are investigated systematically. XRD and Rietveld analyses indicate that all these alloys mainly consist of two phases: (La, Mg)2Ni7 phase with the hexagonal Ce2Ni7-type structure and LaNi5 phase with the hexagonal CaCu5-type structure. The lattice parameters of the component phases gradually decreased with increasing Ce content. It is concluded that, compared to that of room temperature (298 K), the deterioration in capacity is due to the enhanced corrosion of electrode active material and self-discharge at 333 K. The electrode corrosion was alleviated effectively with the increasing x, whereas the high-temperature dischargeability decreases from 92.7% (x = 0.00) to 80.5% (x = 0.20) accordingly. As the discharge current density is 1000 mA g−1, the high-rate dischargeability (HRD) increases from 77.2% (x = 0.00) to 89.7% (x = 0.10) and then decreases to 73.5% (x = 0.20).  相似文献   

7.
In view of the importance of Mg in R-Mg-Ni-type alloys (R generally represents rare earth elements), the effect of Mg on the morphology and electrochemical performance of the as-cast La1-xMgxNi3.4Al0.1 (x = 0.1, 0.2, 0.3 and 0.4) hydrogen storage alloys were studied in this work. The samples possess multiphase structures, including Gd2Co7-, Ce2Ni7-, Pr5Co19-and CaCu5-type, PuNi3-and MgCu4Sn-type phases. It is found that reasonably increasing Mg contents can promote the formation of Gd2Co7-and Ce2Ni7-type phase as well as Mg contents have important effects on phase morphology. Furthermore, fine-dispersed LaNi5 structure in (La, Mg)2Ni7 matrix is beneficial to facilitate the hydrogen diffusion and exert the electrochemical properties for the alloys.The EIS results indicate that the charge transfer resistance decreases nonlinearly with increase of (La, Mg)2Ni7 phase content and presents approximately linear relationship with LaNi5 phase content. When x equals to 0.2, the alloy displays more optimal comprehensive electrochemical properties, i.e. the discharge capacity reaches 357.4 mA/g, the high rate dischargeability at 1200 mA/g 60.1% and the cycling performance 74.5%.  相似文献   

8.
ReNi2.6−xMnxCo0.9 (x = 0.0, 0.225, 0.45, 0.675, 0.90) alloys were prepared by induction melting. The effects of partially substituting Mn for Ni on the phase structure and electrochemical properties of the alloys were investigated systematically. In the alloys, (La, Ce)2Ni7 phase with a Ce2Ni7-type structure, (Pr, Ce)Co3 phase with a PuNi3-type structure, and (La, Pr)Ni5 phase with a CaCu5-type structure were the main phases. The (La,Pr)Ni phase appeared when x increased to 0.45, and the (La, Pr)Ni5 phase disappeared with further increasing x (x > 0.45). The hydrogen-storage capacity of the ReNi2.6−xMnxCo0.9 (x = 0.0, 0.225, 0.45, 0.675, 0.90) alloys initially increased and reached a maximum when Mn content was x = 0.45, and then decreased with further increasing Mn content. The ReNi2.6−xMnxCo0.9 (x = 0.0, 0.225, 0.45, 0.675, 0.90) alloy exhibited a hydrogen-storage capacity of 0.81, 0.98, 1.04, 0.83 and 0.53 wt.%, respectively. Electrochemical studies showed that the maximum discharge capacity of the alloy electrodes initially increased from 205 mAh/g (x = 0.0) to 352 mAh/g (x = 0.45) and then decreased to 307 mAh/g (x = 90). The hydrogen absorption rate first increased and then decreased with addition of Mn element. The ReNi2.15Mn0.45Co0.9 alloy showed faster hydrogen absorption kinetics than that of the other alloys. The presence of Mn element slowed hydrogen desorption kinetics.  相似文献   

9.
The microstructure and electrochemical hydrogen storage characteristics of La0.67Mg0.33−xCaxNi2.75Co0.25 (x = 0, 0.05, 0.10 and 0.15) alloys are investigated. The results show that all alloys mainly consist of (La, Mg)Ni3 and LaNi5 phases, besides a small amount of (La, Mg)2Ni7 phase. The cycle stability (S80) after 80 charge/discharge cycles of all alloy electrodes first increases from 60.1% (x = 0) to 64.2% (x = 0.05), then decreases to 45.9% (x = 0.15). The high rate dischargeability of all alloy electrodes first increases from 52.6% (x = 0) to 61.4% (x = 0.10), then decreases to 57.2% (x = 0.15). Moreover, the charge-transfer resistance (Rct) first decreases from 168.2 mΩ (x = 0) to 125.7 mΩ (x = 0.10), then increases to 136.6 mΩ (x = 0.15). All the results indicate that the substitution of Mg with a certain amount of Ca can improve the overall electrochemical characteristics.  相似文献   

10.
The effect of partial substitution of Ce by La in CeNi3Cr2 hydrogen storage alloy has been systematically investigated. All intermetallic compounds Ce1-xLaxNi3Cr2 (x = 0.2, 0.4, 0.6, 0.8, 1) synthesized by arc melting method are well characterized by the means of XRD and SEM. XRD results show that all the alloys are crystallized as a single-phase compound in the hexagonal CaCu5 type structure. The substitution of Ce by La leads to increase the unit cell volume of the alloy. Hydrogen storage capacity has been investigated in the temperature and pressure range of 293 K ≤ T ≤ 323 K and 0.5 ≤ P ≤ 45 bar respectively using pressure-composition isotherm. The P-C isotherm curves show that the plateau pressure of the hydrogen absorption decreases and hydrogen storage capacity increases with increasing La content in the alloy. The enthalpy (?H) and entropy (?S) of dissolved hydrogen for all systems has been calculated using Van’t Hoff plot. The variation of ?H and ?S with hydrogen content has also been studied which confirm the phase boundaries.  相似文献   

11.
In order to improve the electrochemical performance of the La–Mg–Ni system A2B7-type electrode alloys, La in the alloy was partially substituted by Pr and melt spinning technology was used for preparing La0.75−xPrxMg0.25Ni3.2Co0.2Al0.1 (x = 0, 0.1, 0.2, 0.3, 0.4) electrode alloys. The microstructures and electrochemical performance of the as-cast and spun alloys were investigated in detail. The results obtained by XRD, SEM and TEM show that the as-cast and spun alloys have a multiphase structure which consists of two main phases (La, Mg)Ni3 and LaNi5 as well as a residual phase LaNi2. The substitution of Pr for La leads to an obvious increase of the (La, Mg)Ni3 phase and a decrease of the LaNi5 phase in the alloys. The results of the electrochemical measurement indicate that the discharge capacity of the alloys first increases and then decreases with variation of the Pr content. The cycle stability of the alloy monotonically rises with increasing Pr content. When the Pr content rises from 0 to 0.4, the discharge capacity increases from 389.4 (x = 0) to 392.4 (x = 0.1) and then drops to 383.7 mAh/g (x = 0.4) for the as-cast alloy. Discharge capacity increases from 393.5 (x = 0) to 397.9 (x = 0.1), and then declines to 382.5 mAh/g for the as-spun (5 m/s) alloys. The capacity remaining after 100 cycles increases from 65.32 to 79.36% for the as-cast alloy, and from 73.97 to 93.08% for the as-spun (20 m/s) alloy.  相似文献   

12.
The phase structures and hydrogen storage properties of the Ca3-xLaxMg2Ni13 alloys were investigated. It was found that the La substitution is unfavorable for the formation of the Ca3Mg2Ni13-type phase. The La-substituted alloys consist of multiple phases. Increasing La content to x = 2.25 leads to a disappearance of Ca3Mg2Ni13-type phase. Among these alloys, the Ca1.5La1.5Mg2Ni13 alloy has highest equilibrium pressures of hydrogen absorption–desorption and a highest hydrogen desorption capacity of 1.34 wt.% at 318 K. The discharge capacity decreases for La-substituted alloys. However, the cycling capacity retention rate (S30) increases from 13.7 to 67.6% when x increases from 0 to 3.  相似文献   

13.
The structure and electrochemical characteristics of (La1−xDyx)0.8Mg0.2Ni3.4Al0.1 (x = 0–0.20) hydrogen storage alloys have been investigated. Dysprosium was adopted as a partial substitution element for lanthanum in order to improve electrochemical properties. The XRD, SEM and EDX results showed that the alloys were composed of (La, Mg)2Ni7, LaNi5 and (La, Mg)Ni2 phases. The introduction of Dy promoted the formation of (La, Mg)2Ni7 phase which possesses high hydrogen storage capacity, and controlling dysprosium content at 0.05 can obtain the maximum (La, Mg)2Ni7 phase abundance in the alloys. The maximum discharge capacity was heightened from 382.5 to 390.2 mAh/g, which was ascribed to (La, Mg)2Ni7 phase abundance increasing from 54.8% to a maximum (60.5%). Also, the biggest discharge capacity retention remained 82.7% after 100 cycles at discharge current density of 300 mA/g.  相似文献   

14.
La0.75Mg0.25Ni3.5 alloys with hexagonal (2H-) and rhombohedral (3R-) (La,Mg)2Ni7 phase were created by powder metallurgy. Partial crystal transformation of 2H- into 3R-type allotropes was realized by heat treatment and introducing LaNi5 compound. It was found that the alloy annealed within 1073–1223 K kept (La,Mg)2Ni7 phase and obvious crystal transformation of 2H- into 3R-type occurred as annealing temperature reached 1223 K. Electrochemical study showed similar discharge capacity and degradation behavior for La0.75Mg0.25Ni3.5 alloys with different amounts of 2H- and 3R-type allotropes while HRD was promoted by increasing 3R-type phase abundance. Introducing LaNi5 into La0.75Mg0.25Ni3.5 alloy increased 3R- to 2H-type phase ratio and led to an additional plateau in PC isotherms. LaNi5 introduction improved HRD, however it accelerated cycling degradation. Rietveld analysis indicated that after hydrogenation, the cell expansion of 2H- and 3R-type (La,Mg)2Ni7 phase was similar while the cell expansion of LaNi5 phase was smaller than that of (La,Mg)2Ni7 phase. This caused discrete cell expansion between (La,Mg)2Ni7 and LaNi5 phases, leading to severe pulverization and oxidation.  相似文献   

15.
The phase relations and hydrogen storage properties of the (Ca2−xMgx)Ni7 alloys were investigated. It was found that the maximum solid solubility of Mg in the (Ca,Mg)2Ni7 phase is about x = 0.5 in the present study. The ‘inter-block-layer’ type stacking faults exist in the (Ca,Mg)2Ni7 phase when Mg content is very low. However, the density of stacking faults decreases and the lattice parameters reduce as Mg content increases to its maximum solid solubility. Thus the (Ca1.5Mg0.5)Ni7 alloy has a good reversibility of hydrogen absorption–desorption.  相似文献   

16.
La0.7Mg0.3Ni2.6AlxCo0.5−x (x = 0.0–0.3) alloys were prepared by induction melting, and the effects of partially substituting Al for Co on the structure and hydrogen-storage properties of the alloys were investigated systematically. It is found that La(Ni, Co, Al)5 phase with hexagonal CaCu5-type structure, LaNi3 phase with PuNi3 structure and MgNi2 phase exist as the main phases in La0.7Mg0.3Ni2.6AlxCo0.5−x (x = 0.0–0.3) alloys, and the cell volume of the La(Ni, Co, Al)5 phase increases with the amount of Al added. The results show that the substitution of Al for Co can reduce the plateau pressure and the hysteresis between hydrogen absorption and desorption, and improve the hydrogen-absorption capacity and thermal stability of the hydride. Moreover, the addition of Al can delay the oxidation of the surface layer of the alloy electrodes in electrolyte, slow down the capacity degradation and prolong the cycling lifetime, and enhance the electrocatalytic activity of the hydrogen-storage electrodes for hydrogen oxidation.  相似文献   

17.
Mg2Ni1−xMnx(x = 0, 0.125, 0.25, 0.375) electrode alloys are prepared by mechanical alloying (MA) under argon atmosphere at room temperature using a planetary high-energy ball mill. The microstructures are characterized by XRD and SEM. XRD analysis results indicate that the substitution of Mn for Ni could inhibit the formation of MgNi2 phase with the increases of x from 0 to 0.375. Replacing Ni with Mn can also promote the formation of the amorphous phase when x increases from 0 to 0.25 for the MA alloys milled for 48 h. The new phase Mg3MnNi2 is formed only when x = 0.375 after 48 h of milling. This new phase belongs to the face-centered cubic lattice (Fd-3m) with the lattice constant a being 1.1484 nm. Estimated from the peaks broadening, the crystallite size and lattice strain of Mg3MnNi2 phase are 15.6 ± 3.6 nm and 1.09 ± 0.34%, respectively. Curve fit of XRD shows that amorphous and nanocrystalline Mg2Ni coexist in the Mg2Ni1−xMnx (x = 0, 0.125, 0.25) alloys milled for 48 h. The SEM observation reveals that all the MA alloys particles are mainly flaky and show cleavage fracture morphology and these particles are agglomerates of many smaller particles, namely subparticles. Electrochemical measurements indicate that all MA alloys have excellent activation properties. The discharge capacities of MA alloys increase with the prolongation of milling time. For 16 h of milling, with the increase of Mn content, the discharge capacities of Mg2Ni1−xMnx (x = 0, 0.125, 0.25, 0.375) MA alloys monotonously decrease. For 24 h of milling, the discharge capacities of the Mg2Ni1−xMnx (x = 0, 0.125, 0.25, 0.375) alloys also show a rough tendency to decrease with the increase of Mn content except Mg2Ni0.875Mn0.125 MA alloy. On the other hand, for 48 h of milling, as the rise of Mn content from x = 0.125 to 0.375, the discharge capacities increase. Mg(OH)2 is formed during charge/discharge cycles in the KOH solution for all MA alloys. After 48 h of milling, the substitution of Mn for Ni for x = 0.25 improves the cycle stability at the expense of decreasing the discharge capacity. In contrast, Mg3MnNi2 phase is relatively stable during charge/discharge cycles and therefore can significantly enhance the cycle stability under simultaneously maintaining a high discharge capacity.  相似文献   

18.
《Journal of power sources》2005,144(1):255-261
In order to improve the electrochemical cycle stability of La–Mg–Ni system (PuNi3-type) hydrogen storage alloy, a trace of Cr was added and rapid quenching techniques were employed. The electrochemical performances and microstructures of the as-cast and -quenched alloys were determined and measured. The effects of Cr content and quenching rate on the microstructures and electrochemical properties of the alloys were investigated in detail. The obtained results show that the as-cast and -quenched alloys are composed of the (La, Mg)Ni3 phase (PuNi3-type structure) and the LaNi5 phase as well as the LaNi2 phase. The amount of the LaNi2 phase increases with the increase of Cr content. The addition of Cr enhances the cycle stability of the as-cast and -quenched alloys, but decreases the discharge capacities of the alloys. The cycle lives of the alloys increase with the increase of the quenching rate. The as-cast and -quenched alloys have an excellent activation performance.  相似文献   

19.
The crystal structure and electrochemical properties of the La2MgMn0.3Ni8.7−x(Co0.5Al0.5)x (x = 0, 1.0, 2.0 and 3.0, at%) hydrogen storage alloys are investigated systematically. The results show that all the alloys consist of (La, Mg)Ni3 and LaNi5 phases, the cyclic stability S60 increases from 61.2% (x = 0) to 78.7% (x = 3.0) after 60 charge/discharge cycles, and the peak high rate dischargeability (HRD) at the discharge current density of 1200 mA/g appears at the alloy of x = 2.0 with the value of 68.3%. Moreover, the electrochemical kinetic properties of the alloys are also improved at different extent with increasing x. All the results indicate that the substitution of Co and Al for Ni in AB3-type hydrogen storage alloys is effective to improving the overall electrochemical properties, and the optimum content is x = 2.0.  相似文献   

20.
The La–Mg–Ni system PuNi3-type hydrogen storage alloys La0.7Mg0.3Co0.45Ni2.55-xFex (x=0, 0.1, 0.2, 0.3, 0.4) were prepared by casting and rapid quenching. Ni in the alloy was partially substituted by Fe in order to improve the cycle stability of the alloys. The effects of the substitution of Fe for Ni combining rapid quenching on the microstructures and electrochemical performances of the as-cast and -quenched alloys were investigated in detail. The results indicate that the substitution of Fe for Ni obviously decreases the discharge capacity and high rate discharge (HRD) capability as well as the discharge potential of the as-cast and -quenched alloys, but it significantly improves their cycle stabilities. The microstructure of the alloys analyzed by XRD, SEM and TEM shows that the as-cast and -quenched alloys have a multiphase structure which is composed of two major phases (La, Mg)Ni3 and LaNi5 as well as a residual phase LaNi2. The substitution of Fe for Ni leads to an obvious increase in the LaNi2 phase in the as-cast alloys, and it also helps the formation of a like amorphous structure in the as-quenched alloy. With the increase of Fe content, the grain sizes of the as-quenched alloys significantly reduce, and the lattice constants and cell volumes of the alloys obviously enlarge.  相似文献   

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