Effects of rapid quenching on microstructures and electrochemical properties of La0.7Mg0.3Ni2.55Co0.45Bx（x=O-0.2） hydrogen storage alloy

In order to improve the electrochemical performances of La-Mg-Ni based electrode alloys with PuNi3-type structure, a trace of boron was added in La0.7Mg0.3Ni2.55Co0.45 alloy. The La0.7Mg0.3Ni2.55Co0.45Bx（a=0, 0.05, 0.1, 0.15 and 0.2） alloys were prepared by casting and rapid quenching. The electrochemical performances and microstructures of the as-cast and quenched alloys were investigated. The effects of rapid quenching on the microstructures and electrochemical performances of the above alloys were investigated. The results show that the as-cast and quenched alloys are composed of （La, Mg）Ni3 phase, LaNi5 phase and LaNi2 phase. A trace of the Ni2B phase exists in the as-cast alloys containing boron, and the Ni2B phase in the B-contained alloys nearly disappears after rapid quenching. Rapid quenching increases the amount of the LaNi2 phase in the B-free alloy, but it decreases the amount of the LaNi2 phase in the boron-containing alloys. The effects of rapid quenching on the capacities of the boron-containing and boron-free alloys are different. The capacity of the B-free alloy monotonously decreases with increasing quenching rate, whereas the capacities of the B-contained alloys have a maximum value with the change of the quenching rate. The rapid quenching can improve the stability of La-Mg-Ni based electrode alloy but lowers the discharge plateau voltage and decreases the plateau length. The effect of rapid quenching on the activation capabilities of the alloys was complicated.     

Influences of the substitution of Fe for Ni on structures and electrochemical performances of the as-cast and quenched La0.7Mg0.3Co0.45Ni2.55−xFex (x = 0–0.4) electrode alloys

In order to improve the cycle stability of the La–Mg–Ni system PuNi₃-type hydrogen storage electrode alloys, Ni in the alloy was partially substituted by Fe. The La_0.7Mg_0.3Co_0.45Ni_2.55−xFe_x (x = 0, 0.1, 0.2, 0.3, 0.4) hydrogen storage alloys were prepared by casting and rapid quenching. The effects of the substitution of Fe for Ni on the structures and electrochemical performances of the as-cast and quenched alloys were investigated in detail. The results of the electrochemical measurement indicate that the substitution of Fe for Ni obviously decreases the discharge capacity, high rate discharge capability (HRD) and discharge potential of the as-cast and quenched alloys, but it significantly improves their cycle stabilities, and its positive impact on the cycle life of as-quenched alloy is much more significant than on that of the as-cast one. The microstructure of the alloys analyzed by XRD, SEM and TEM show 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 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 increase.     

Investigation on the structures and electrochemical performances of La0.75−xZrxMg0.25Ni3.2Co0.2Al0.1 (x = 0–0.2) electrode alloys prepared by melt spinning

In order to improve the electrochemical cycle stability of the La–Mg–Ni system A₂B₇-type electrode alloys, La in the alloy was partially substituted by Zr and the melt-spinning technology was used for preparing La_0.75−xZr_xMg_0.25Ni_3.2Co_0.2Al_0.1 (x = 0, 0.05, 0.1, 0.15, 0.2) electrode alloys. The microstructures and electrochemical performances of the as-cast and quenched alloys were investigated in detail. The results obtained by XRD, SEM and TEM showed that the as-cast and quenched alloys have a multiphase structure which is composed of two main phases (La, Mg)Ni₃ and LaNi₅ as well as a residual phase LaNi₂. The substitution of Zr for La leads to an obvious increase of the LaNi₅ phase in the alloys, and it also helps the formation of a like amorphous structure in the as-quenched alloy. The results of the electrochemical measurement indicated that the substitution of Zr for La obviously decreased the discharge capacity of the as-cast and quenched alloys, but it significantly improved their cycle stability. The discharge capacity of the alloys (x ≤ 0.1) first increased and then decreased with the variety of the quenching rate. The cycle stability of the alloys monotonously rose with increasing quenching rate.     

Hydrogen storage properties of as-cast and annealed low-Co La<Subscript>1.8</Subscript>Ti<Subscript>0.2</Subscript>MgNi<Subscript>8.9</Subscript>Co<Subscript>0.1</Subscript> alloys

Low-Co La_1.8Ti_0.2MgNi_8.9Co_0.1 alloys were prepared by magnetic levitation melting followed by annealing treatment. The effect of annealing on the hydrogen storage properties of the alloys was investigated systematically by X-ray diffraction (XRD), pressure-composition isotherm (PCI), and electrochemical measurements. The results show that all samples contain LaNi₅ and LaMg₂Ni₉ phases. LaCo₅ phase appears at 1,000 °C. The enthalpy change of all hydrides is close to ?30.6 kJ·mol^?1 H₂ of LaNi₅ compound. Annealing not only increases hydrogen capacity and improves cycling stability but also decreases plateau pressure at 800 and 900 °C. After annealing, the contraction of cell volume and the increase of hydride stability cause the high rate dischargeability to reduce slightly. The optimum alloy is found to be one annealed at 900 °C, with its hydrogen capacity reaching up to 1.53 wt%, and discharge capacity remaining 225.1 mAh·g^?1 after 140 charge–discharge cycles.     

Electrochemical performances of as-cast and annealed La0.8.xNdxMg0.2Ni3.35Al0.lSi0.05 （x = 0-0.4） alloys applied to Ni/metal hydride （MH） battery

The La–Mg–Ni-based A₂B₇-type La_0.8-x Nd _x Mg_0.2Ni_3.35Al_0.1Si_0.05 (x = 0, 0.1, 0.2, 0.3, and 0.4) electrode alloys were prepared by casting and annealing. The influence of the partial substitution of Nd for La on the structure and electrochemical performances of the alloys was investigated. The structural analysis of X-ray diffraction and scanning electron microscopy reveals that the experimental alloys consist of two major phases: (La,Mg)₂Ni₇ with the hexagonal Ce₂Ni₇-type structure and LaNi₅ with the hexagonal CaCu₅-type structure as well as some residual phases of LaNi₃ and NdNi₅. The electrochemical measurements indicate that an evident change of the electrochemical performance of the alloys is associated with the substitution of Nd for La. The discharge capacity of the alloy first increases then decreases with the growing Nd content, whereas their cycle stability clearly grows all the time. Furthermore, the measurements of the high rate discharge ability, the limiting current density, and hydrogen diffusion coefficient all demonstrate that the electrochemical kinetic properties of the alloy electrodes first augment then decline with the rising amount of Nd substitution.     

Studies on the hydrogen absorption properties of LaNi5−xSnx and La0.95Ni4.6Sn0.3 alloys using magnetic and thermoelectric power measurement

Magnetic and thermoelectric power (TEP) measurements are used to quantify hydrogen availability, absorption, and desorption in materials for nickel-hydride batteries and hydrogen storage. The effect of the concentration of conduction electrons is introduced and used to investigate hydride properties of these alloys. To investigate hydrogenation properties the calculated average number ofd-band electrons in hydrogen storage material is related to the measured thermoelectric power. Also, a thermodynamic exprssion of equilibrium is applied to demonstrate the relationship between the TEP and the activity of hydrogen for hydrogen adsorption. Magnetization decreases with increasing absorbed hydrogen in the stoichiometric LaNi_4.78Sn_0.22 alloy. However, magnetization increases with increasing hydrogen content in the nonstoichiometric La_0.95Ni_4.6Sn_0.3 alloy. The TEP for the stoichiometric LaNi_4.78Sn_0.22 alloy monotonically increases as a function of hydrogen content. However, the TEP of the nonstoichiometric La_0.95Ni_4.6Sn_0.3 alloy decreases as hydrogen content increases.     

快淬对低钻贮氢合金的电化学性能影响

为改善低钴贮氢合金的综合电化学性能，对其进行不同速度的快淬处理。结果表明：合适的快淬速度不仅可以大幅度的提高放电容量，而且明显的改善合金的循环稳定性和放电电压特性。18m／s快淬低钴合金具有较好的综合电化学性能。但快淬使得合金的活化性能有所降低。利用X射线衍射、扫描电镜对铸态及快淬合金进行微观分析，讨论了快淬对低钴贮氢合金电化学性能的影响机理。     

快淬对低钴贮氢合金的电化学性能影响

为改善低钴贮氢合金的综合电化学性能,对其进行不同速度的快淬处理。结果表明,合适的快淬速度不仅可以大幅度的提高放电容量,而且明显的改善合金的循环稳定性和放电电压特性。18 m/s快淬低钴合金具有较好的综合电化学性能,但快淬使合金的活化性能有所降低。利用X射线、扫描电镜对铸态及快淬合金进行微观分析。分析了快淬对低钴贮氢合金电化学性能的影响机理。     

Gaseous and electrochemical hydrogen storage kinetics of nanocrystalline Mg2Ni-type alloy prepared by rapid quenching

The nanocrystalline Mg₂Ni-type Mg₂Ni_1−xCu_x (x = 0, 0.1, 0.2, 0.3, 0.4) alloys were synthesized by direct melt quenching technique. The structures of the as-cast and quenched alloys were investigated by XRD, SEM and HRTEM. The gaseous hydrogen storage kinetics of the alloys was measured using an automatically controlled Sieverts apparatus. The electrochemical hydrogen storage kinetics of the alloys was tested by using constant current to charge and discharge the electrode. The results indicate that the substitution of Cu notably rendered the grain refinement of the as-cast alloys without altering the major phase Mg₂Ni. All the as-quenched alloys exhibit a nanocrystalline structure without the presence of any amorphous phase. It is found that the substitution of Cu for Ni and rapid quenching significantly ameliorated the gaseous and electrochemical hydrogen storage kinetics of the nanocrystalline Mg₂Ni_1−xCu_x (x = 0-0.4) alloys. Furthermore, both the rapid quenching treatment and the Cu substitution results in a notable increase in the hydrogen diffusion coefficient (D) as well as the limiting current density (I_L) but an obvious decline in the electrochemical impedance.     

Influence of rapid quenching on hydrogen storage characteristics of nanocrystalline Mg2Ni-type alloys

Nanocrystalline Mg2Ni-type alloys with nominal compositions of Mg20Ni10–xCux(x=0,1,2,3,4,mass fraction,%) were synthesized by rapid quenching technique.The microstructures of the as-cast and quenched alloys were characterized by XRD,SEM and HRTEM.The electrochemical hydrogen storage performances were tested by an automatic galvanostatic system.The hydriding and dehydriding kinetics of the alloys were measured using an automatically controlled Sieverts apparatus.The results show that all the as-quenched alloys hold the typical nanocrystalline structure and the rapid quenching does not change the major phase Mg2Ni.The rapid quenching significantly improves the electrochemical hydrogen storage capacity of the alloys,whereas it slightly impairs the cycling stability of the alloys.Additionally,the hydrogen absorption and desorption capacities of the alloys significantly increase with rising quenching rate.     

Electrochemical hydrogen storage characteristics of as-cast and annealed La0.8-xNdxMg0.2Ni3.15Co0.2Al0.1Si0.05 (x=0–0.4) alloys

The La-Mg–Ni–based A₂B₇-type La_0.8-xNd_xMg_0.2Ni_3.15Co_0.2Al_0.15 (x=0, 0.1, 0.2, 0.3, 0.4) electrode alloys were prepared by casting and annealing. The influences of partial substitution of Nd for La on the structure and electrochemical performance of the as-cast and annealed alloys were investigated. It was found that the experimental alloys consist of two major phases, (La, Mg)₂Ni₇ phase with the hexagonal Ce₂Ni₇-type structure and LaNi₅ phase with the hexagonal CaCu₅-type structure, as well as some residual phase LaNi₃ and NdNi₅. The discharge capacity and high rate discharge ability (HRD) of the as-cast and annealed alloys first increase and then decrease with Nd content growing. The as-cast and annealed alloys (x=0.3) yield the largest discharge capacities of 380.3 and 384.3 mA·h/g, respectively. The electrochemical cycle stability of the as-cast and annealed alloys markedly grows with Nd content rising. As the Nd content increase from 0 to 0.4. The capacity retaining rate (S₁₀₀) at the 100th charging and discharging cycle increases from 64.98% to 85.17% for the as-cast alloy, and from 76.60% to 96.84% for the as-annealed alloy.     

Hydrogen storage characteristics of nanocrystalline and amorphous Mg2Ni-type alloys prepared by melt spinning

In order to improve the hydrogen storage characteristics of the Mg₂Ni-type alloys, Ni in the alloy is partially substituted by element Mn, and melt-spinning technology is used for the preparation of the Mg₂Ni_1−xMn_x (x = 0, 0.1, 0.2, 0.3, 0.4) hydrogen storage alloys. The microstructures of the as-cast and spun alloys are characterized by XRD, SEM and HRTEM. The hydrogen absorption and desorption kinetics of the alloys are measured by an automatically controlled Sieverts apparatus. The electrochemical performances are tested by an automatic galvanostatic system. The results show that the as-spun Mn-free alloy holds typical nanocrystalline structure, whereas the as-spun alloys containing Mn displays a nanocrystalline and amorphous structure. The hydrogen absorption and desorption capacities and kinetics of the alloys increase with rising spinning rate. Additionally, melt spinning markedly improves the electrochemical hydrogen storage capacity and cycle stability of the alloys containing Mn. With an increase in the spinning rate from 0 (As-casts is defined as spinning rate of 0 m/s) to 30 m/s, the discharge capacity of the (x = 0.3) alloy mounts up from 92.3 to 211.1 mAh/g, and its capacity retaining rate at 20th charging and discharging cycle grows from 36.21% to 76.02%.     

铸态和快淬态Mm(NiCoMnAl)5合金的电化学性能及相结构

本文研究了铸态和快淬态MmNi3．7Co0．6Mn0．4Al0.3贮氢合金的电化学性能和相结构。电化学测试结果表明：快淬态合金的活化性能比铸态合金差，淬速为10m／s和16m／s的快淬态合金的最大放电容量高于铸态合金，放电电压平台更为平坦。淬速为22m／s和28m／s的快淬态合金的最大放电容量低于铸态合金。随着淬速的增加，合金电极的循环稳定性提高。X射线衍射结果表明：铸态和快淬态合金均由CaCu5型主相和一个第二相组成，快淬使得第二相衍射峰减弱。合金成分更为均匀。快淬态合金的晶格参数大于铸态合金。晶格参数的增加是快淬合金具有良好循环稳定性的一个重要原因。     

Effects of rapid quenching on structure and electrochemical characteristics of La0.5Ce0.2Mg0.3Co0.4Ni2.6-xMnx （x=0-0.4） electrode alloys

The La-Mg-Ni system PuNi3-type La0.5Ce0.2Mg0.3Co0.4Ni2.6-xMnx (x=0, 0.1, 0.2, 0.3, 0.4) hydrogen storage alloys were prepared by casting and rapid quenching. The effects of the rapid quenching on the structure and electrochemical characteristics of the alloys were studied. The results obtained by XRD, SEM and TEM indicate that the as-cast and quenched alloys mainly consist of two major phases, (La,Mg)Ni3 and LaNi5, as well as a residual phase LaNi. The rapid quenching does not exert an obvious influence on the phase composition of the alloys, but it leads to an increase of the LaNi5 phase and a decrease of the (La, Mg)Ni3 phase. The as-quenched alloys have a nano-crystalline structure, and the grain sizes of the alloys are in the range of 20-30 nm. The results by the electrochemical measurements indicate that both the discharge capacity and the high rate discharge(HRD) ability of the alloy first increase and then decrease with the variety of quenching rate and obtain the maximum values at the special quenching rate which is changeable with the variety of Mn content. The rapid quenching significantly improves the cycle stabilities of the alloys, but it slightly impairs the activation capabilities of the alloys.     

Investigation on Gaseous and Electrochemical Hydrogen Storage Kinetics of As-Quenched Nanocrystalline Mg2Ni-type Alloys

为了改善Mg2Ni型合金气态及电化学贮氢动力学性能,用Cu部分替代合金中的Ni,用快淬技术制备Mg2Ni1-xCux(x=0,0.1,0.2,0.3,0.4)合金,用XRD、SEM、HRTEM分析铸态及快淬态合金的微观结构;用自动控制的Sieverts设备测试合金的气态贮氢动力学性能,用程控电池测试仪测试合金的电化学贮氢动力学.结果表明,所有快淬态合金均具有纳米晶结构,无非晶相形成.Cu替代Ni不改变合金的主相Mg2Ni,但使合金的晶粒显著细化.快淬处理及Cu替代均显著地提高合金的气态及电化学贮氢动力学性能.当淬速从0m/s(铸态被定义为淬速0 m/s)增加到30 m/s时,Mg2Ni0.8Cu0.3合金在5 min内的吸氢饱和率从57.2％增加到92.87％,20 min的放氢率从21.6％增加到49.6％,高倍率放电能力(HRD)从40.6％增加到73.1％,氢扩散系数(D)从1.02×10-11 cm2/s增加到4.08×10 -11 cm2/s,极限电流密度(IL)从113.0 mA/g增加到715.3 mA/g.     

Ni-B-C对La0.94Mg0.06Ni3.49Co0.73Mn0.12Al0.20储氢合金电化学性能的影响研究

为提高新型AB₃型储氢合金La_0.94Mg_0.06Ni_3.49Co_0.73Mn_0.12Al_0.20的电化学性能,将球磨法制备的Ni-B-C粉末按不同重量比添加到合金中。采用X-射线粉末衍射仪(XRD)和扫描电子显微镜(SEM)分析合金的相结构和表面形貌,添加Ni-B-C粉末后,合金相结构没有变化,仍由LaNi₅相和La₂Ni₇相两个相组成,但合金表面出现了细小颗粒。添加Ni-B-C粉末后,合金电极的最大放电容量和放电容量保持率均提高。当添加重量百分比为10%的Ni-B-C粉末后,电极的最大放电容量从346 mAh/g增加到363 mAh/g,50个循环后的放电容量保持率从70%提高到77%,交换电流密度I₀与极限电流密度I_L分别为106 mA/g和987 mA/g。动电位极化测试表明,电极的抗腐蚀能力也有所增强。研究结果表明,Ni-B-C可以提高AB₃型储氢合金的综合电化学性能。     

Function of cobalt in the new type rare-earth Mg-based hydrogen storage electrode alloys

The role of cobalt on the structural and electrochemical properties of the La_0.7Mg_0.3Ni_3.4−xMn_0.1Co_x (x=0–1.15) hydrogen storage alloys were investigated systematically. XRD and Rietveld analyses show that all alloys consist mainly of the (La,Mg)Ni₃ phase and the LaNi₅ phase. P–C isotherms illustrate that the equilibrium pressure for hydrogen decreases monotonically with increasing x. Electrochemical studies indicate that the maximum discharge capacity first increases from 397.5 (x=0) to 403.1 mA h/g (x=0.75) and then decreases to 388.2 mA h/g (x=1.15). Moreover, with increasing Co substitution, the cycling durability of the alloy electrodes was markedly improved due to the decrease in the pulverization of the alloy particles and the corrosion of La in KOH solution. The high rate dischargeability, electrochemical impedance spectrum, linear polarization, Tafel polarization and potential-step measurements all indicate that the electrochemical kinetics of the alloy electrodes first increases and then decreases with increasing Co content.     

Effects of Rapid Quenching on Structure and Hydrogen Storage Characteristics of Mg20Ni10-xMnx (x=0-4) Alloys

为了改善Mg2Ni型合金的贮氢性能,用Mn部分替代合金中的Ni,并采用快淬工艺制备Mg20Ni10-xMnx(x=0, 1, 2, 3, 4)合金。用XRD和HRTEM分析了铸态及快淬合金的微观结构,用自动控制Sieverts设备测试合金的吸放氢动力学,并采用程控电池测试仪测试合金的电化学性能。结果表明,当淬速为20 m/s时,快淬(x=4)合金中出现非晶相,且非晶化程度随淬速的增加而增加。合金的吸放氢量及动力学性能随淬速的增加而增加。此外,快淬显著地改善了合金的电化学性能,包括放电容量及含Mn合金的循环稳定性。     

铸态和快淬态Mm(NiCoMnAl)_5B_x(x=0~0.2)贮氢合金的相结构与电化学性能

用铸造及快淬工艺制备了低钴AB5型Mm(NiCoMnAl)5Bx(x=0~0.2)贮氢合金,测试了合金的微观结构及电化学性能,研究了B含量及快淬工艺的变化对合金晶格常数、热力学参数、微观结构及电化学性能的影响。结果表明:合金的晶格常数、晶胞体积及标准生成焓均随B含量的增加而增大;在一定的淬速范围内,快淬处理可以提高合金的放电容量,但淬速超过某一临界淬速时,快淬合金的容量低于铸态合金;合金的循环寿命随淬速的增加而单调增加。     

Influences of Ti substitution on the structure and electrochemical properties of Mg1-xTixNi（x=0,0.1, 0.2, and 0.3） hydrogen storage alloys

MgNi-based hydrogen storage alloys Mg_1−x Ti _x Ni (x = 0, 0.1, 0.2, and 0.3) were prepared by means of mechanical alloying. Mg in the alloy was partially substituted by Ti to improve the cycle stability of the alloys. The effects of the substitution of Ti for Mg on the microstructure and electrochemical performances of the alloys were investigated in detail. The results indicate that the substitution of Ti for Mg obviously decreases the discharge capacity, but it significantly improves their cycle stabilities. The microstructure of the alloys analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM) shows that the alloys have a dominatingly amorphous structure. The substitution of Ti for Mg helps to improve the anti-oxidation/corrosion ability of the MgNi alloy but demolishes the electrochemical kinetics of hydrogenation/dehydrogenation. The Mg_0.9Ti_0.1Ni alloy electrode milled for 80 h exhibits the best integrative capability, which has the maximal discharge capacity of 331.66 mAh/g and the C ₃₀/C _max of 63.65%.