A sort of rare earth Mg-based system hydrogen storage alloys with AB3-type was prepared by double-roller rapid quenching method. The alloys were nanocrystalline multi-phase structures composed of LaNi3 phase and LaNi5...A sort of rare earth Mg-based system hydrogen storage alloys with AB3-type was prepared by double-roller rapid quenching method. The alloys were nanocrystalline multi-phase structures composed of LaNi3 phase and LaNi5 phase by X-ray diffraction and scanning electron microscopy analyses, and the suitable absorption/desorption plateau was revealed by the measurement of P-C-I curve. Electrochemical studies indicate that the alloys exhibit good electrochemical properties such as high capacity and stable cycle life, and the discharge capacity is 369 mAh·g-1 at 0.2 C (72 mA·g-1), after 460 cycles, the capacity decay was only 19.4% at 2 C (720 mA·g-1).展开更多
The effect of heat-treatment process on the properties of Mm0.8Mg0.2(NiCoAlMn)3.5 hydrogen storage alloy was discussed. The electrochemical properties such as cycling stability, activation property, and the plateau vo...The effect of heat-treatment process on the properties of Mm0.8Mg0.2(NiCoAlMn)3.5 hydrogen storage alloy was discussed. The electrochemical properties such as cycling stability, activation property, and the plateau voltage of the alloy which was heat-treated in various temperatures and times had different changes during the cycle process, the optimum heat-treatment conditions of this alloy were determined by this work.展开更多
The hydriding/dehydriding thermodynamic properties of the slurry system formed by suspending La rich mischmetal nickel hydrogen storage alloy (MlNi 5) in Benzene (C 6H 6) were investigated. The pressure compositi...The hydriding/dehydriding thermodynamic properties of the slurry system formed by suspending La rich mischmetal nickel hydrogen storage alloy (MlNi 5) in Benzene (C 6H 6) were investigated. The pressure composition isotherms for both the alloy powder and the slurry suspended with MlNi 5 were measured at several temperatures(10, 20, 30, 40 ℃). The standard enthalpy of formation Δ H ° and standard entropy of formation Δ S ° for the alloy powder with and without benzene were determined respectively. The experimental results show that the values of Δ H ° and Δ S ° for the hydriding reaction of hydrogen storage alloy (MlNi 5) of the slurry system and the gas solid system are all very close.展开更多
The rare earth based hydrogen storage alloys Ml_ 0.7Mm_ 0.3(Ni_ 3.55Co_ 0.75Mn_ 0.4Al_ 0.3) were chosen as objects of investigation in this paper. The effects of particle size on electrochemical properties of the allo...The rare earth based hydrogen storage alloys Ml_ 0.7Mm_ 0.3(Ni_ 3.55Co_ 0.75Mn_ 0.4Al_ 0.3) were chosen as objects of investigation in this paper. The effects of particle size on electrochemical properties of the alloy were investigated. The results indicate that the alloy with particle size of 100 and 150 mesh shows good activation behavior and high discharge capacity (the first discharge capacity and the maximum discharge capacity), but poor cycling stability, low capacity retention and high discharge capacity rate. The Ml_ 0.7Mm_ 0.3(Ni_ 3.55Co_ 0.75Mn_ 0.4Al_ 0.3) alloy with particle size of 150 mesh shows excellent electrochemical properties.展开更多
The rare earth based hydrogen storage alloys MmxM1 1 - x ( Ni3.55 Co0.75 Mn0.4 A10.3 ) ( x = 0 ~ 0.5 ) were investigated in this work.Adjusted Ml: Mm ratio to change the content of La,Ce,Pr and Nd in the alloys and t...The rare earth based hydrogen storage alloys MmxM1 1 - x ( Ni3.55 Co0.75 Mn0.4 A10.3 ) ( x = 0 ~ 0.5 ) were investigated in this work.Adjusted Ml: Mm ratio to change the content of La,Ce,Pr and Nd in the alloys and then to change the phase structure, the influences of phase structure on the electrochemical properties were analyzed.The results indicate that the main phase of all alloys is LaNi5 with CaCu5 type structure and the crystal lattices constants of LaNi5 are changed with increasing x value, i.e, decreased a-axis, increased c-axis and axis ratio and nonlinear decreased crystal volume.The crystal volume of the alloy with x = 0.3 is larger than others.There is second phase A1LaNi4 in alloys when x≥0.3, which decrease the discharge capacity, but increase the cycling stability and high rate discharge ability.Compared comprehensively, the alloy with x = 0.3 shows the higher discharge capacity and the better cycling stability.展开更多
On the basis of typical high Co MI(Lanthanum rich mischmetal) based hydrogen storage alloy, a series oflow Co or Co free alloys have been prepared by means of partial or full replacement of Co by a combination of othe...On the basis of typical high Co MI(Lanthanum rich mischmetal) based hydrogen storage alloy, a series oflow Co or Co free alloys have been prepared by means of partial or full replacement of Co by a combination of other elements. The microstructures, p c T (pressure concentration temperature) characteristics and electrochemical propertiesunder different charge discharge conditions of the alloys have been investigated. Compared with the high Co alloy, thelow Co or Co free alloys have the lower hydrogen equilibrium pressure and discharge capacity, but have the nearly samehigh rate and high temperature discharge capability, and better charge discharge cycling stability. The reason is revealedby SEM, XPS and XRD results. \[展开更多
Rare earth-based hydrogen storage alloy used as negative electrode materials for nickel-metal hydride (Ni-MH) batteries are used commercially.The effect of annealing treatment with different annealing temperature and ...Rare earth-based hydrogen storage alloy used as negative electrode materials for nickel-metal hydride (Ni-MH) batteries are used commercially.The effect of annealing treatment with different annealing temperature and time on the MLNi3.68 Co0.78 Mn0.35 Al0.27 and MMNi3.55 Co0.75 Mn0.40 Al0.30 alloys were investigated.The crystal microstructure,pressure-composition-isotherms (p-C-T) and electrochemical properties of alloys were examined by X-ray diffraction (XRD), automatic PCI monitoring system and electrical performance testing instruments.The optimum annealing treatment conditions of two kinds of alloys were determined.展开更多
The SC technique is now being applied widely in material preparation, especially in rare earth functional materials in virtue of its advanced process and high performance product. The applications of SC technique in r...The SC technique is now being applied widely in material preparation, especially in rare earth functional materials in virtue of its advanced process and high performance product. The applications of SC technique in rare earth permanent magnet alloys and hydrogen storage alloys were analyzed integrative, on the basis of summary of SC technique development in this paper. The paper mainly includes development history of SC technology, effect of SC technology on alloy microstructure, application of SC technology in RE storage hydrogen alloy and sintered Nd-Fe-B alloy, development of SC equipment and SC product industry. At the same time, the paper points out the existing problem of SC products.展开更多
The structure of β-LaNi2Hx is mentioned. Special emphasis is laid on the influence of substitutions with metallic elements on the thermodynamic properties of the rare-earth-nickel hydrogen storage alloys. The models ...The structure of β-LaNi2Hx is mentioned. Special emphasis is laid on the influence of substitutions with metallic elements on the thermodynamic properties of the rare-earth-nickel hydrogen storage alloys. The models of the heat of hydride formation are studied attentively. The relation between the stability and the heat of formation of intermetallic compounds including with other physical properties is discussed. The relations between hydriding properties and the geometric and electronic structure of the intermetallic compounds are presented.展开更多
The rare earth based hydrogen storage alloys Mm_xMl_ 1-xNi_ 3.55Co_ 0.75Mn_ 0.4Al_ 0.3(x=0~0.50) were investigated in this work. The influences of phase structure on the PCT characteristics were analyzed by means of ...The rare earth based hydrogen storage alloys Mm_xMl_ 1-xNi_ 3.55Co_ 0.75Mn_ 0.4Al_ 0.3(x=0~0.50) were investigated in this work. The influences of phase structure on the PCT characteristics were analyzed by means of electrochemical measurements. The results indicate that there is a strict relationship between crystal volume and PCT characteristics.展开更多
In order to investigate the effect of substituting La with Pr on structural and hydrogen storage properties of La-Mg-Ni system (AB3.5-type) hydrogen storage alloys, a series of La0.65-xPrxNd0.12Mg0.23Ni3.4Al0.1(x=0...In order to investigate the effect of substituting La with Pr on structural and hydrogen storage properties of La-Mg-Ni system (AB3.5-type) hydrogen storage alloys, a series of La0.65-xPrxNd0.12Mg0.23Ni3.4Al0.1(x=0, 0.10, 0.15, 0.2) hydrogen storage alloys were prepared. X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS) analyses revealed that two alloys (x=0.0 and 0.10) were composed of (La,Mg)2(Ni,Al)7 phase, La(Ni,A1)5 phase and (La,Mg)Ni2 phase, while other alloys (x=0.15 and 0.20) consisted of (La,Mg)2(Ni,A1)7 phase, La(Ni,A1)5 phase, (La,Mg)Ni2 phase and (La,Mg)(Ni,A1)3 phase. All alloys showed, however, only one pressure plateau in P-C isotherms. The Pr/La ratio in alloy composition influenced hydrogen storage capacity and kinetics properties. Electrochemical studies showed that the discharge capacity decreased from 360 mAh/g (x=-0.00) to 335 mAh/g (x=-0.20) as x increased. But the high-rate dischargeability (HRD) of alloy electrodes increased from 26% (x=0.00) to 56% (x=-0.20) at a discharge current density of Id=1800 mA/g. Anode polarization measurements were done to further understand the electrochemical kinetics properties after Pr substitution.展开更多
The effects of surface treatment, particle size distribution,rare earth composition and B additive on the high rate discharge performance of hydrogen storage alloys were investigated. It is found that the activity, di...The effects of surface treatment, particle size distribution,rare earth composition and B additive on the high rate discharge performance of hydrogen storage alloys were investigated. It is found that the activity, discharge capacity and high rate dischargeability of the alloys are improved after physical and chemical modification as a result of the increase of the surface area and formation of the electrocatalysis layers, which increase both the electrochemical reaction rate on the alloy surface and H diffusion rate in the alloy bulk. It is also found that both the over-coarse and over-fine particle size increase the contact resistance of the electrode, resulting in a decrease of discharge capacity, deterioration of high rate dischargeability and lower discharge plateau. In another word, a suitable particle size distribution can enhance the alloy activity, discharge capacity and high rate dischargeability. In addition, the high rate dischargeability is enhanced by increasing La content and decreasing Ce content of the alloy composition because of enlargement of the unit cell volume and the improvement of the surface activity. Moreover, B additive resultes in the formation of the second phase, and makes the alloys easier pulverization, which greatly improves the activity, discharge capacity and high rate dischargeability.展开更多
The effect of thickness (1 similar to 10 mm) of the ingots on the electrochemical properties of as-cast and annealed strip cast LPCNi3.55Co0.75Mn0.4Al0.3 hydrogen storage alloys was investigated. It is found that the ...The effect of thickness (1 similar to 10 mm) of the ingots on the electrochemical properties of as-cast and annealed strip cast LPCNi3.55Co0.75Mn0.4Al0.3 hydrogen storage alloys was investigated. It is found that the 0.2 C discharge capacity of as-cast LPCNi3.55Co0.75Mn0.4Al0.3 alloy increases with the increase of the thickness of the ingots. As-east alloy with the thickness of 10 mm shows better activation property, higher 1C discharge capacity and better cyclic stability than others. It is mainly contributed to its larger unit cell volume and less internal stress. Annealed LPCNi3.55Co0.75Mn0.4Al0.3 alloy with the thickness of 3 mm shows much better comprehensive electrochemical properties than as-east one; The cyclic. stability of the alloy with the thickness of 6 mm and the activation properties of the alloys with the thickness of 3 similar to 6 mm are improved after annealing. It is mainly owing to the great release of internal stress and the decrease of the segregation of Mn in the alloys.展开更多
The kinetics of liquid-phase hydrogenation of toluene catalyzed by MlNi_5 was studied by investigating the influences of the reaction temperature and pressure on the mass transfer-reaction processes inside the slurry....The kinetics of liquid-phase hydrogenation of toluene catalyzed by MlNi_5 was studied by investigating the influences of the reaction temperature and pressure on the mass transfer-reaction processes inside the slurry. The results show that the reaction rate accelerates when the reaction temperature increases, and reaches its maximum at about 490 K, but if temperature is higher than 510 K, the reaction rate decreases rapidly. The whole reaction process is controlled by the reaction at the surface of the catalyst particles. The mass transfer resistance at gas-liquid interface and that from the bulk liquid phase to the surface of the catalyst particle can be neglected. The apparent reaction rate is zero order for toluene concentration and first order for hydrogen concentration in the liquid phase. The kinetic model is obtained. The kinetic model fits the experimental data very well. The apparent activation energy of the hydrogen absorption reaction of MlNi_5-toluene slurry system is 41.01 kJ·mol^(-1).展开更多
The phase structure and hydrogen storage properties of LaMg 3.70 Ni 1.18 alloy were investigated. The LaMg 3.70 Ni 1.18 alloy consists of main LaMg 2 Ni phase, minor La 2 Mg 17 and LaMg 3 phases. The alloy can be acti...The phase structure and hydrogen storage properties of LaMg 3.70 Ni 1.18 alloy were investigated. The LaMg 3.70 Ni 1.18 alloy consists of main LaMg 2 Ni phase, minor La 2 Mg 17 and LaMg 3 phases. The alloy can be activated in the first hydriding/dehydriding process, and initial LaMg 2 Ni, La 2 Mg 17 , and LaMg 3 phases transfer to LaH 2.34 , Mg, and Mg 2 Ni phases after activation. The reversible hydrogen storage capacity of the LaMg 3.70 Ni 1.18 alloy is 2.47 wt.% at 558 K, which is higher than that of the LaMg 2 Ni alloy. The pressure-composition-temperature (PCT) curves display two hydriding plateaus, corresponding to the formation of MgH 2 and Mg 2 NiH 4 . However, only one dehydriding plateau is observed, owing to the synergetic effect of hydrogen desorption between MgH 2 and Mg 2 NiH 4 . The uptake time for hydrogen content to reach 99% of saturated state is less than 250 s, and 90% hydrogen can be released in 1200 s in the experimental conditions, showing fast kinetics in hydriding and dehydriding. The activation energies of the LaMg 3.70 Ni 1.18 alloy are –51.5 ± 1.1 kJ/mol and –57.0 ± 0.6 kJ/mol for hydriding and dehydriding, respectively. The hydriding/dehydriding kinetics of the LaMg 3.70 Ni 1.18 alloy is better than that of the Mg 2 Ni alloy, owing to the lower activation energy values.展开更多
The absorption of hydrogen was studied in metal hydride slurry, which is formed by benzene and hydrogen storage alloy powder. The influence of temperature on the rate of absorption was discussed using three phase mas...The absorption of hydrogen was studied in metal hydride slurry, which is formed by benzene and hydrogen storage alloy powder. The influence of temperature on the rate of absorption was discussed using three phase mass transfer model. It is also concluded that the suitable absorption temperature is 313 K.展开更多
In order to reduce the cost of LaNi5 based hydrogen storage alloys, effect of substitution of Mn for Ni on structural and electrochemical properties of LaNi4-xFeMnx (x=0-0.8) hydrogen storage alloys was studied system...In order to reduce the cost of LaNi5 based hydrogen storage alloys, effect of substitution of Mn for Ni on structural and electrochemical properties of LaNi4-xFeMnx (x=0-0.8) hydrogen storage alloys was studied systematically. X-ray diffraction (XRD) and scanning electron microscope (SEM) showed that LaNi5 and La2Ni7 phases were invariably present in all alloy samples, and when x >= 0.4, (Fe, Ni) phase was observed. Electrochemical studies revealed that the discharge capacity reached a maximum value of 306.4 mAh/g when x=0.2 and the cycling stability decreased with the increase of x. With the increase of Mn content, hydrogen diffusion coefficient decreased, whereas high rate discharge-ability (HRD) and exchange current density first increased slowly when x <= 0.2 and then decreased markedly when x=0.8, indicating that electrochemical reaction on the surface of alloy electrodes had strong influence on kinetic property.展开更多
Effect of Ce addition on microstructure and hydrogen storage performance of Ti24Cr17.5V50Fe8.5Cex(x=0, 0.5at.%, 0.8at.% and 1.0at.%) alloys was studied by X-ray diffraction, scanning electron microscopy and P-C-isot...Effect of Ce addition on microstructure and hydrogen storage performance of Ti24Cr17.5V50Fe8.5Cex(x=0, 0.5at.%, 0.8at.% and 1.0at.%) alloys was studied by X-ray diffraction, scanning electron microscopy and P-C-isotherm measurements.The results indicated that Ce addition was a useful way to improve the flatness of the plateau and increase hydrogen storage capacity of Ti24Cr17.5V50Fe8.5 alloy.It was indicated that both homogenization of composition and increase of hydrogen diffusion coefficient were the main reasons for improving the hydrogen storage performance of Ti24Cr17.5V50Fe8.5Cex alloys.展开更多
Surface-treated MmNi3.55Co0.75Mn0.4Al0.3 alloy as negative electrode material of nickel-metal hydride battery was employed to improve the high-rate dischargeability. Surface treatment was realized by dipping and stirr...Surface-treated MmNi3.55Co0.75Mn0.4Al0.3 alloy as negative electrode material of nickel-metal hydride battery was employed to improve the high-rate dischargeability. Surface treatment was realized by dipping and stirring the alloy into a HCl aqueous solution with various concentrations at room temperature. The microstructure of the alloy before and after surface treatment was analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The electrochemical properties before and after surface treatment were compared, and the alloy treated in 0.025 mol/L HCl solution showed the optimal high-rate dischargeability.展开更多
The effects of rapid solidification on the microstructure and electrochemical properties of Nd0.8Mg0.2(Ni0.8Co0.2)3.8 alloy were systematically investigated.The microstructure of alloys was characterized by scanning e...The effects of rapid solidification on the microstructure and electrochemical properties of Nd0.8Mg0.2(Ni0.8Co0.2)3.8 alloy were systematically investigated.The microstructure of alloys was characterized by scanning electron microscopy(SEM),X-ray diffractometer(XRD) and transmission electron microscopy(TEM).It was found that the melt-spun Nd0.8Mg0.2(Ni0.8Co0.2)3.8 ribbons became thinner and the average grain size of the ribbons became smaller with increasing wheel speed.A fraction of amorphous phase was obs...展开更多
文摘A sort of rare earth Mg-based system hydrogen storage alloys with AB3-type was prepared by double-roller rapid quenching method. The alloys were nanocrystalline multi-phase structures composed of LaNi3 phase and LaNi5 phase by X-ray diffraction and scanning electron microscopy analyses, and the suitable absorption/desorption plateau was revealed by the measurement of P-C-I curve. Electrochemical studies indicate that the alloys exhibit good electrochemical properties such as high capacity and stable cycle life, and the discharge capacity is 369 mAh·g-1 at 0.2 C (72 mA·g-1), after 460 cycles, the capacity decay was only 19.4% at 2 C (720 mA·g-1).
文摘The effect of heat-treatment process on the properties of Mm0.8Mg0.2(NiCoAlMn)3.5 hydrogen storage alloy was discussed. The electrochemical properties such as cycling stability, activation property, and the plateau voltage of the alloy which was heat-treated in various temperatures and times had different changes during the cycle process, the optimum heat-treatment conditions of this alloy were determined by this work.
文摘The hydriding/dehydriding thermodynamic properties of the slurry system formed by suspending La rich mischmetal nickel hydrogen storage alloy (MlNi 5) in Benzene (C 6H 6) were investigated. The pressure composition isotherms for both the alloy powder and the slurry suspended with MlNi 5 were measured at several temperatures(10, 20, 30, 40 ℃). The standard enthalpy of formation Δ H ° and standard entropy of formation Δ S ° for the alloy powder with and without benzene were determined respectively. The experimental results show that the values of Δ H ° and Δ S ° for the hydriding reaction of hydrogen storage alloy (MlNi 5) of the slurry system and the gas solid system are all very close.
文摘The rare earth based hydrogen storage alloys Ml_ 0.7Mm_ 0.3(Ni_ 3.55Co_ 0.75Mn_ 0.4Al_ 0.3) were chosen as objects of investigation in this paper. The effects of particle size on electrochemical properties of the alloy were investigated. The results indicate that the alloy with particle size of 100 and 150 mesh shows good activation behavior and high discharge capacity (the first discharge capacity and the maximum discharge capacity), but poor cycling stability, low capacity retention and high discharge capacity rate. The Ml_ 0.7Mm_ 0.3(Ni_ 3.55Co_ 0.75Mn_ 0.4Al_ 0.3) alloy with particle size of 150 mesh shows excellent electrochemical properties.
文摘The rare earth based hydrogen storage alloys MmxM1 1 - x ( Ni3.55 Co0.75 Mn0.4 A10.3 ) ( x = 0 ~ 0.5 ) were investigated in this work.Adjusted Ml: Mm ratio to change the content of La,Ce,Pr and Nd in the alloys and then to change the phase structure, the influences of phase structure on the electrochemical properties were analyzed.The results indicate that the main phase of all alloys is LaNi5 with CaCu5 type structure and the crystal lattices constants of LaNi5 are changed with increasing x value, i.e, decreased a-axis, increased c-axis and axis ratio and nonlinear decreased crystal volume.The crystal volume of the alloy with x = 0.3 is larger than others.There is second phase A1LaNi4 in alloys when x≥0.3, which decrease the discharge capacity, but increase the cycling stability and high rate discharge ability.Compared comprehensively, the alloy with x = 0.3 shows the higher discharge capacity and the better cycling stability.
文摘On the basis of typical high Co MI(Lanthanum rich mischmetal) based hydrogen storage alloy, a series oflow Co or Co free alloys have been prepared by means of partial or full replacement of Co by a combination of other elements. The microstructures, p c T (pressure concentration temperature) characteristics and electrochemical propertiesunder different charge discharge conditions of the alloys have been investigated. Compared with the high Co alloy, thelow Co or Co free alloys have the lower hydrogen equilibrium pressure and discharge capacity, but have the nearly samehigh rate and high temperature discharge capability, and better charge discharge cycling stability. The reason is revealedby SEM, XPS and XRD results. \[
文摘Rare earth-based hydrogen storage alloy used as negative electrode materials for nickel-metal hydride (Ni-MH) batteries are used commercially.The effect of annealing treatment with different annealing temperature and time on the MLNi3.68 Co0.78 Mn0.35 Al0.27 and MMNi3.55 Co0.75 Mn0.40 Al0.30 alloys were investigated.The crystal microstructure,pressure-composition-isotherms (p-C-T) and electrochemical properties of alloys were examined by X-ray diffraction (XRD), automatic PCI monitoring system and electrical performance testing instruments.The optimum annealing treatment conditions of two kinds of alloys were determined.
文摘The SC technique is now being applied widely in material preparation, especially in rare earth functional materials in virtue of its advanced process and high performance product. The applications of SC technique in rare earth permanent magnet alloys and hydrogen storage alloys were analyzed integrative, on the basis of summary of SC technique development in this paper. The paper mainly includes development history of SC technology, effect of SC technology on alloy microstructure, application of SC technology in RE storage hydrogen alloy and sintered Nd-Fe-B alloy, development of SC equipment and SC product industry. At the same time, the paper points out the existing problem of SC products.
文摘The structure of β-LaNi2Hx is mentioned. Special emphasis is laid on the influence of substitutions with metallic elements on the thermodynamic properties of the rare-earth-nickel hydrogen storage alloys. The models of the heat of hydride formation are studied attentively. The relation between the stability and the heat of formation of intermetallic compounds including with other physical properties is discussed. The relations between hydriding properties and the geometric and electronic structure of the intermetallic compounds are presented.
文摘The rare earth based hydrogen storage alloys Mm_xMl_ 1-xNi_ 3.55Co_ 0.75Mn_ 0.4Al_ 0.3(x=0~0.50) were investigated in this work. The influences of phase structure on the PCT characteristics were analyzed by means of electrochemical measurements. The results indicate that there is a strict relationship between crystal volume and PCT characteristics.
基金supported by the Key Projects in International Science and Technology Cooperation from Ministry of Science and Technology of the PRC (2006DFB52550, 2007DFA51020)the National Natural Science Foundation of China (20363001)
文摘In order to investigate the effect of substituting La with Pr on structural and hydrogen storage properties of La-Mg-Ni system (AB3.5-type) hydrogen storage alloys, a series of La0.65-xPrxNd0.12Mg0.23Ni3.4Al0.1(x=0, 0.10, 0.15, 0.2) hydrogen storage alloys were prepared. X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS) analyses revealed that two alloys (x=0.0 and 0.10) were composed of (La,Mg)2(Ni,Al)7 phase, La(Ni,A1)5 phase and (La,Mg)Ni2 phase, while other alloys (x=0.15 and 0.20) consisted of (La,Mg)2(Ni,A1)7 phase, La(Ni,A1)5 phase, (La,Mg)Ni2 phase and (La,Mg)(Ni,A1)3 phase. All alloys showed, however, only one pressure plateau in P-C isotherms. The Pr/La ratio in alloy composition influenced hydrogen storage capacity and kinetics properties. Electrochemical studies showed that the discharge capacity decreased from 360 mAh/g (x=-0.00) to 335 mAh/g (x=-0.20) as x increased. But the high-rate dischargeability (HRD) of alloy electrodes increased from 26% (x=0.00) to 56% (x=-0.20) at a discharge current density of Id=1800 mA/g. Anode polarization measurements were done to further understand the electrochemical kinetics properties after Pr substitution.
文摘The effects of surface treatment, particle size distribution,rare earth composition and B additive on the high rate discharge performance of hydrogen storage alloys were investigated. It is found that the activity, discharge capacity and high rate dischargeability of the alloys are improved after physical and chemical modification as a result of the increase of the surface area and formation of the electrocatalysis layers, which increase both the electrochemical reaction rate on the alloy surface and H diffusion rate in the alloy bulk. It is also found that both the over-coarse and over-fine particle size increase the contact resistance of the electrode, resulting in a decrease of discharge capacity, deterioration of high rate dischargeability and lower discharge plateau. In another word, a suitable particle size distribution can enhance the alloy activity, discharge capacity and high rate dischargeability. In addition, the high rate dischargeability is enhanced by increasing La content and decreasing Ce content of the alloy composition because of enlargement of the unit cell volume and the improvement of the surface activity. Moreover, B additive resultes in the formation of the second phase, and makes the alloys easier pulverization, which greatly improves the activity, discharge capacity and high rate dischargeability.
文摘The effect of thickness (1 similar to 10 mm) of the ingots on the electrochemical properties of as-cast and annealed strip cast LPCNi3.55Co0.75Mn0.4Al0.3 hydrogen storage alloys was investigated. It is found that the 0.2 C discharge capacity of as-cast LPCNi3.55Co0.75Mn0.4Al0.3 alloy increases with the increase of the thickness of the ingots. As-east alloy with the thickness of 10 mm shows better activation property, higher 1C discharge capacity and better cyclic stability than others. It is mainly contributed to its larger unit cell volume and less internal stress. Annealed LPCNi3.55Co0.75Mn0.4Al0.3 alloy with the thickness of 3 mm shows much better comprehensive electrochemical properties than as-east one; The cyclic. stability of the alloy with the thickness of 6 mm and the activation properties of the alloys with the thickness of 3 similar to 6 mm are improved after annealing. It is mainly owing to the great release of internal stress and the decrease of the segregation of Mn in the alloys.
文摘The kinetics of liquid-phase hydrogenation of toluene catalyzed by MlNi_5 was studied by investigating the influences of the reaction temperature and pressure on the mass transfer-reaction processes inside the slurry. The results show that the reaction rate accelerates when the reaction temperature increases, and reaches its maximum at about 490 K, but if temperature is higher than 510 K, the reaction rate decreases rapidly. The whole reaction process is controlled by the reaction at the surface of the catalyst particles. The mass transfer resistance at gas-liquid interface and that from the bulk liquid phase to the surface of the catalyst particle can be neglected. The apparent reaction rate is zero order for toluene concentration and first order for hydrogen concentration in the liquid phase. The kinetic model is obtained. The kinetic model fits the experimental data very well. The apparent activation energy of the hydrogen absorption reaction of MlNi_5-toluene slurry system is 41.01 kJ·mol^(-1).
基金supported by the High-Tech Research and Development Program of China (No. 2007AA05Z117)the National Natural Science Foundation of China (Nos. 50971112 and 51001043)+1 种基金the China Post-doctoral Science Foundation Funded Project (20100470990)the Natural Science Foundation of Hebei Province, China (No. E2010001170)
文摘The phase structure and hydrogen storage properties of LaMg 3.70 Ni 1.18 alloy were investigated. The LaMg 3.70 Ni 1.18 alloy consists of main LaMg 2 Ni phase, minor La 2 Mg 17 and LaMg 3 phases. The alloy can be activated in the first hydriding/dehydriding process, and initial LaMg 2 Ni, La 2 Mg 17 , and LaMg 3 phases transfer to LaH 2.34 , Mg, and Mg 2 Ni phases after activation. The reversible hydrogen storage capacity of the LaMg 3.70 Ni 1.18 alloy is 2.47 wt.% at 558 K, which is higher than that of the LaMg 2 Ni alloy. The pressure-composition-temperature (PCT) curves display two hydriding plateaus, corresponding to the formation of MgH 2 and Mg 2 NiH 4 . However, only one dehydriding plateau is observed, owing to the synergetic effect of hydrogen desorption between MgH 2 and Mg 2 NiH 4 . The uptake time for hydrogen content to reach 99% of saturated state is less than 250 s, and 90% hydrogen can be released in 1200 s in the experimental conditions, showing fast kinetics in hydriding and dehydriding. The activation energies of the LaMg 3.70 Ni 1.18 alloy are –51.5 ± 1.1 kJ/mol and –57.0 ± 0.6 kJ/mol for hydriding and dehydriding, respectively. The hydriding/dehydriding kinetics of the LaMg 3.70 Ni 1.18 alloy is better than that of the Mg 2 Ni alloy, owing to the lower activation energy values.
文摘The absorption of hydrogen was studied in metal hydride slurry, which is formed by benzene and hydrogen storage alloy powder. The influence of temperature on the rate of absorption was discussed using three phase mass transfer model. It is also concluded that the suitable absorption temperature is 313 K.
基金Project supported by the National Nature Science Foundation of China (NSFC50571072)GD-MOE Coordination Project of Industry Academic and Research (2008B090500274)
文摘In order to reduce the cost of LaNi5 based hydrogen storage alloys, effect of substitution of Mn for Ni on structural and electrochemical properties of LaNi4-xFeMnx (x=0-0.8) hydrogen storage alloys was studied systematically. X-ray diffraction (XRD) and scanning electron microscope (SEM) showed that LaNi5 and La2Ni7 phases were invariably present in all alloy samples, and when x >= 0.4, (Fe, Ni) phase was observed. Electrochemical studies revealed that the discharge capacity reached a maximum value of 306.4 mAh/g when x=0.2 and the cycling stability decreased with the increase of x. With the increase of Mn content, hydrogen diffusion coefficient decreased, whereas high rate discharge-ability (HRD) and exchange current density first increased slowly when x <= 0.2 and then decreased markedly when x=0.8, indicating that electrochemical reaction on the surface of alloy electrodes had strong influence on kinetic property.
基金supported by Hi-Tech Research and Development Program of China (2006AA05Z144)
文摘Effect of Ce addition on microstructure and hydrogen storage performance of Ti24Cr17.5V50Fe8.5Cex(x=0, 0.5at.%, 0.8at.% and 1.0at.%) alloys was studied by X-ray diffraction, scanning electron microscopy and P-C-isotherm measurements.The results indicated that Ce addition was a useful way to improve the flatness of the plateau and increase hydrogen storage capacity of Ti24Cr17.5V50Fe8.5 alloy.It was indicated that both homogenization of composition and increase of hydrogen diffusion coefficient were the main reasons for improving the hydrogen storage performance of Ti24Cr17.5V50Fe8.5Cex alloys.
基金supported by Hi-Tech Research and Development Program (863) of China (2006AA11A159)
文摘Surface-treated MmNi3.55Co0.75Mn0.4Al0.3 alloy as negative electrode material of nickel-metal hydride battery was employed to improve the high-rate dischargeability. Surface treatment was realized by dipping and stirring the alloy into a HCl aqueous solution with various concentrations at room temperature. The microstructure of the alloy before and after surface treatment was analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The electrochemical properties before and after surface treatment were compared, and the alloy treated in 0.025 mol/L HCl solution showed the optimal high-rate dischargeability.
基金supported by the National Natural Science Foundation of China (50471011, 50525101)
文摘The effects of rapid solidification on the microstructure and electrochemical properties of Nd0.8Mg0.2(Ni0.8Co0.2)3.8 alloy were systematically investigated.The microstructure of alloys was characterized by scanning electron microscopy(SEM),X-ray diffractometer(XRD) and transmission electron microscopy(TEM).It was found that the melt-spun Nd0.8Mg0.2(Ni0.8Co0.2)3.8 ribbons became thinner and the average grain size of the ribbons became smaller with increasing wheel speed.A fraction of amorphous phase was obs...