Effect of Heat-Treatment Process on Properties of Rare Earth Mg-Based System Hydrogen Storage Alloys with AB_3-Type

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.

Study on Nanocrystalline Rare Earth Mg-Based System Hydrogen Storage Alloys with AB_3-Type

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).

Hydrogen Absorption Thermodynamic Properties of Rare Earth Based Hydrogen Storage Alloy in Benzene

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.

Phase Structure and Electrochemical Properties of Rare Earth Based Hydrogen Storage Alloys

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.

Study on Particle Size and Electrochemical Properties of Rare Earth Based Hydrogen Storage Alloys

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.

Low-Co rare-earth-based hydrogen storage alloy

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. \[

Development of Strip Casting Technology in Rare Earth Permanent Magnet Alloys and Hydrogen Storage Alloys in China

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.

Effect of Annealing on Rare Earth Based Hydrogen Storage Alloys

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.

Study on Phase Structure and PCT Characteristics of Rare Earth Based Hydrogen Storage Alloys

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.

Development of Rare Earth Hydrogen Storage Alloys: Correlation Between Structure, Stability, and Hydrating Properties

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.

A review of classical hydrogen isotopes storage materials

Hydrogen storage alloys(HSAs)are attracting widespread interest in the nuclear industry because of the generation of stable metal hydrides after tritium absorption,thus effectively preventing the leakage of radioactive tritium.Commonly used HSAs in the hydrogen isotopes field are Zr2M(M=Co,Ni,Fe)alloys,metallic Pd,depleted U,and ZrCo alloy.Specifically,Zr2M(M=Co,Ni,Fe)alloys are considered promising tritium-getter materials,and metallic Pd is utilized to separate and purify hydrogen isotopes.Furthermore,depleted U and ZrCo alloy are well suited for storing and delivering hydrogen isotopes.Notably,all the aforementioned HSAs need to modulate their hydrogen storage properties for complex operating conditions.In this review,we present a comprehensive overview of the reported modification methods applied to the above alloys.Alloying is an effective amelioration method that mainly modulates the properties of HSAs by altering their local geometrical/electronic structures.Besides,microstructural modifications such as nano-sizing and nanopores have been used to increase the specific surface area and active sites of metallic Pd and ZrCo alloys for enhancing de-/hydrogenation kinetics.The combination of metallic Pd with support materials can significantly reduce the cost and enhance the pulverization resistance.Moreover,the poisoning resistance of ZrCo alloy is improved by constructing active surfaces with selective permeability.Overall,the review is constructive for better understanding the properties and mechanisms of hydrogen isotope storage alloys and provides effective guidance for future modification research.

Rare earth alloy nanomaterials in electrocatalysis

With the rapid development of society and economy, the excessive consumption of fossil energy has led to the global energy and environment crisis. In order to explore the sustainable development of new energy, research based on electrocatalysis has attracted extensive attention in the academic circle. The main challenge in this field is to develop nano-catalysts with excellent electrocatalytic activity and selectivity for target products. The state of the active site in catalyst plays a decisive role in the activity and selectivity of the reaction. In order to design efficient and excellent catalysts, it is an effective means to adjust the electronic structure of catalysts. Electronic effects are also called ligand effects. By alloying with rare earth(RE) elements, electrons can be redistributed between RE elements and transition metal elements, achieving accurate design of the electronic structure of the active site in the alloy. Because of the unique electronic structure of RE, it has been paid attention in the field of catalysis. The outermost shell structure of RE elements is basically the same as that of the lower shell, except that the number of electrons in the 4f orbital is different, but the energy level is similar, so their properties are very similar. When RE elements form compounds, both the f electrons in the outermost shell and the d electrons in the lower outer shell can participate in bonding. In addition, part of the 4f electrons in the third outer shell can also participate in bonding.In order to improve the performance of metal catalysts, alloying provides an effective method to design advanced functional materials. RE alloys can integrate the unique electronic structure and catalytic behavior of RE elements into metal materials, which not only provides an opportunity to adjust the electronic structure and catalytic activity of the active component, but also enhances the structural stability of the alloy and is expected to significantly improve the catalytic performance of the catalyst. From the perspective of electronic and catalytic activity, RE elements have unique electronic configuration and lanthanide shrinkage effect. Alloying with RE elements will make the alloy have more abundant electronic structure, activity, and spatial arrangement, effectively adjusting the reaction kinetics of the electrochemical process of the catalyst. In this paper, the composition,structure, synthesis of RE alloys and their applications in the field of electrocatalysis are summarized, including the hydrogen evolution reaction, the oxygen evolution reaction, the oxygen reduction reaction, the methanol oxidation reaction, the ethanol oxidation reaction, and other catalytic reactions. At the same time, the present challenges of RE alloy electrocatalytic materials are summarized and their future development direction is pointed out. In the field of electrocatalysis, the cost of catalyst is too high and the stability is not strong. Therefore, the testing process should be related to the actual application, and the test method should be standardized, so as to carry forward the field of electrocatalysis.

Hydriding properties of uranium alloys for purposes of searching for new hydrogen storage materials

Hydriding properties of uranium alloys have been studied to search for new hydrogen storage materials to be applied to hydrogen energy systems. Application of uranium-base hydrogen storage materials can be expected to alleviate the risk, as well as to reduce the cost incurred by globally-stored large amounts of depleted uranium left after uranium enrichment. Various uranium alloys have been examined in terms of hydrogen absorptiondesorption properties, among which UNi Al intermetallic compound showed promising characteristics, such as lower absorption-desorption temperatures and better anti-powdering strength. First principle calculation has been carried out on UNi Al hydride to predict the change of crystal structure and the lattice constant with increasing hydrogen content, which showed this calculation to be promising in predicting candidates for good hydrogen absorbers.

Preparation and Characterization of Rare Earth Metal and Alloy Target Materials for Manufacturing Magneto-Optical Disks

The studies were made on the preparation processes of the rare earth metal and alloy target materials and their characterization. In this work the rare earth metals were prepared by electrolysis of the oxide in molten salt for Nd metal and metallothermic reduction of the fluorides for Gd, Tb, Dy metals. After vacuum refining and distillation purification these rare earth metals were used for manufacturing the element targets, mosaic targets and as the starting materials of preparing the rare earth-transition metal (RE-TM) alloy targets. The four kinds of Dy-FeCo, NdDy-FeCo, Tb-FeCo and GdTb-FeCo alloy targets with diameter of 100 mm and thickness of 3 mm were prepared using powder metallurgical technique. The oxygen content and microstructure of the prepared RE-TM cast alloys and sintered targets were analyzed. The features and requirements of the RE-TM alloy sputtering target materials were also discussed.

Hydrogen Fixation Effect of Rare Earths in Pure Aluminium and Aluminium Alloys

The areal distribution of some elements in the rare earth bearing spheroidal phases in pure aluminium and Al-Mn alloys was studied by SIMS(secondary ion mass spectrometry).The results show that cerium,iron. silicon and hydrogen are significantly segregated in the phases.Thus the existence of hydrogen-rich rare earth bearing eompounds is confirmed.It indicates that the rare earths have a hydrogen fixation effect in aluminium and aluminium alloys.

Microstructural evolution of melt-spun Mg-10Ni-2Mm hydrogen storage alloy

The microstructural evolution of a Mg-10Ni-2Mm（molar fraction,%）（Mm=Ce,La-rich mischmetal） hydrogen storage alloys applied with various solidification rates was studied.The results show that the grain size of melt-spun ribbon is remarkably reduced by increasing the solidification rate.The microcrystalline,nanocrystalline and amorphous microstructures are obtained by applying the surface velocities of the graphite wheel of 3.1,10.5 and 20.9 m/s,respectively.By applying the surface velocity of the graphite wheel of 3.1 m/s,the melt-spun specimen obtains full crystalline with a considerable amount of coarse microcrystalline Mg and Mg2Ni except for some Mm-rich particles.The amount of nanocrystalline phases significantly increases with increasing the surface velocity of the wheel to 10.5 m/s,and the microstructure is composed of a large amount of nanocrystalline phases of Mg and Mg2Ni particles.A mixed microstructure containing amorphous and nanocrystalline phases is obtained at a surface velocity of the wheel of 20.9 m/s.The optimal microstructure with a considerable amount of nanocrystalline Mg and Mg2Ni in an amorphous matrix is expected to have the maximum hydrogen absorption capacity and excellent hydrogenation kinetics.

Effect of praseodymium substitution for lanthanum on structure and properties of La_(0.65-x)Pr_xNd_(0.12)Mg_(0.23)Ni_(3.4)Al_(0.1)(x=0.00–0.20) hydrogen storage alloys

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.

Effect of stoichiometry and Cu-substitution on the phase structure and hydrogen storage properties of Ml-Mg-Ni-based alloys

To improve the electrochemical properties of rare-earth-Mg-Ni-based hydrogen storage alloys, the effects of stoichiometry and Cu-substitution on the phase structure and thermodynamic properties of the alloys were studied. Nonsubstituted Ml0.80Mg0.20（Ni2.90Co0.50-Mn0.30Al0.30）x （x=0.68, 0.70, 0.72, 0.74, 0.76） alloys and Cu-substituted Ml0.80Mg0.20（Ni2.90Co0.50-yCuyMn0.30Al0.30）0.70 （y=0, 0.10, 0.30, 0.50） alloys were prepared by induction melting. Phase structure analysis shows that the nonsubstituted alloys consist of a LaNi5 phase, a LaNi3 phase, and a minor La2Ni7 phase;in addition, in the case of Cu-substitution, the Nd2Ni7 phase appears and the LaNi3 phase vanishes. Ther-modynamic tests show that the enthalpy change in the dehydriding process decreases, indicating that hydride stability decreases with in-creasing stoichiometry and increasing Cu content. The maximum discharge capacity, kinetic properties, and cycling stability of the alloy electrodes all increase and then decrease with increasing stoichiometry or increasing Cu content. Furthermore, Cu substitution for Co ame-liorates the discharge capacity, kinetics, and cycling stability of the alloy electrodes.

Effects of Strip Casting and Annealing on Electrochemical Properties of LPCNi_(3.55)Co_(0.75)Mn_(0.4)Al_(0.3) Hydrogen Storage Alloys

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.

Study on High Rate Discharge Performance and Mechanism of AB_5 Type Hydrogen Storage Alloys

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.