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.     

Cycle stabilities of the La0.7Mg0.3Ni2.55−xCo0.45Mx (M = Fe, Mn, Al; x = 0, 0.1) electrode alloys prepared by casting and rapid quenching

In order to improve the cycle stability of La–Mg–Ni system (PuNi₃-type) hydrogen storage alloy, Ni in the alloy was partly substituted by Fe, Mn and Al, and the electrode alloys La_0.7Mg_0.3Ni_2.55−xCo_0.45M_x (M = Fe, Mn, Al; x = 0, 0.1) were prepared by casting and rapid quenching. The effects of the substitution of Fe, Mn and Al for Ni and rapid quenching on the microstructures and electrochemical properties of the alloys were investigated in detail. The results obtained by XRD, SEM and TEM indicate that element substitution has no influence on the phase compositions of the alloys, but it changes the phase abundances of the alloys. Particularly, the substitution of Al and Mn obviously raises the amount of the LaNi₂ phase. The substitution of Al and Fe leads to a significant refinement of the as-quenched alloy's grains. The substitution of Al strongly restrains the formation of an amorphous in the as-quenched alloy, but the substitution of Fe is quite helpful for the formation of an amorphous phase. The effects of the substitution of Fe, Mn and Al on the cycle stabilities of the as-cast and quenched alloys are different. The positive influence of the substitution elements on the cycle stabilities of the as-cast alloys is in proper order Al > Fe > Mn, and for as-quenched alloys, the order is Fe > Al > Mn. Rapid quenching engenders an inappreciable influence on the phase composition, but it markedly enhances the cycle stabilities of the alloys.     

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.     

Structure and Electrochemical Properties of Rapidly Quenched Mm0.3Ml0.7Ni3.55Co0.75Mn0.4Al0.3 Hydrogen Storage Alloy

The as-cast Mm_0.3Ml_0.7Ni_3.55Co_0.75Mn_0.4Al_0.3 alloy has been treated using rapid-quenching technique at different quenching speeds to improve the electrochemical hydrogen storage properties of the alloys. The morphologic and microstructural characterizations of alloys were studied using x-ray diffraction and transmission electron microscopy. It is observed that the quenched alloy is composed of two main phases, LaNi₅ and LaNi₃, and one minor phase of La₂Ni₃. The microstructures of the alloys vary with the quenching speeds, as well as contain microcrystalline, nanocrystalline, and amorphous structures. The electrochemical hydrogen storage properties were measured using a battery test system. The results indicate that the discharge capacity of the alloy increases initially and then decreases with the rising quenching speeds. The quenched alloy at a speed of 15 m/s exhibits the maximum discharge capacity (388 mAh/g), which is much higher than that of the AB₅-type rare earth-based hydrogen storage alloy reported in previous studies. However, the stability of the electrochemical cycle of the quenched alloy exhibits inverse trends compared with the discharge capacity. The best electrochemical cyclic stability of the quenched alloy can be obtained at a speed of 25 m/s.     

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.     

An investigation on hydrogen storage kinetics of nanocrystalline and amorphous Mg2Ni1−xCox (x = 0-0.4) alloy prepared by melt spinning

In order to improve the hydrogen storage kinetics of the Mg₂Ni-type alloys, Ni in the alloy was partially substituted by element Co, and melt-spinning technology was used for the preparation of the Mg₂Ni_1−xCo_x (x = 0, 0.1, 0.2, 0.3, 0.4) hydrogen storage alloys. The structures of the as-cast and spun alloys are characterized by XRD, SEM and TEM. The hydrogen absorption and desorption kinetics of the alloys were measured by an automatically controlled Sieverts apparatus. The electrochemical hydrogen storage kinetics of the as-spun alloys is tested by an automatic galvanostatic system. The hydrogen diffusion coefficients in the alloys are calculated by virtue of potential-step method. The electrochemical impedance spectrums (EIS) and the Tafel polarization curves are plotted by an electrochemical workstation. The results show that the substitution of Co for Ni notably enhances the glass forming ability of the Mg₂Ni-type alloy. Furthermore, the substitution of Co for Ni, instead of changing major phase Mg₂Ni, leads to forming secondary phases MgCo₂ and Mg. Both the melt spinning treatment and Co substitution significantly improve the hydrogen absorption and desorption kinetics. The high rate discharge ability, the hydrogen diffusion coefficient and the limiting current density of the alloys significantly increase with raising both the spinning rate and the amount of Co substitution.     

Structure and electrochemical properties of the Fe substituted Ti–V-based hydrogen storage alloys

To elucidate the effects of Fe on the Ti–V-based hydrogen storage electrode alloys, the Ti_0.8Zr_0.2V_2.7−xMn_0.5Cr_0.8Ni_1.0Fe_x (x = 0.0–0.5) alloys were prepared and their structures and electrochemical properties were systematically investigated. XRD results show that all the alloys consist of a C14 Laves phase with hexagonal structure and a V-based solid solution phase with bcc structure. With increasing Fe content, the abundance of the C14 Laves phase gradually decreases from 43.4 wt% (x = 0.0) to 28.5 wt% (x = 0.5), on the contrary, that of the V-based solid solution phase monotonously increases from 56.6 wt% to 71.5 wt%. In addition, SEM observation finds that the grain size of the V-based solid solution phase is first gradually reduced and then enlarged with increasing x. Electrochemical investigations indicate that the substitution of Fe for V markedly improves the cycling stability and the high rate dischargeability of the alloy electrodes, but decreases the maximum discharge capacity and the activation performance. Further electrochemical impedance spectra, the linear polarization curve and the potentiostatic step discharge measurements reveal that the electrochemical kinetics of the alloy electrodes should be jointly controlled by the charge-transfer reaction rate on the alloy surface and the hydrogen diffusion rate in the bulk of the alloys. For the alloy electrodes with the lower Fe content (x = 0.0–0.2), the hydrogen diffusion in the bulk of the alloys should be the rate-determining step of its discharge process, and while x increases from 0.3 to 0.5, the charge-transfer reaction on the alloy surface becomes to the rate-determining step, which induces that the electrochemical kinetics of the alloy electrodes is firstly improved and then decreased with increasing Fe content.     

Structural and electrochemical properties of TixZr7−xNi10

Simple ternary alloys with formula Ti_xZr_7−xNi₁₀ (x between 0 and 2.5) were studied as a potential replacement for Laves phase alloys used in the negative electrodes of nickel metal hydride batteries. The samples were prepared by arc-melting and were not annealed. The samples retained a high degree of disorder, which contributed positively to activation and other electrochemical properties. Before hydrogenation, the alloys have a Zr₇Ni₁₀ orthorhombic structure mixed with some C15 and ZrO₂ secondary phases. The amount of C15 secondary phase is important to the bulk diffusion of hydrogen and the surface electrochemical kinetics. That is, the diffusion coefficient and the exchange current both increase in the presence of C15 secondary phase. The proportion of C15 secondary phase is controllable by stoichiometry design. For instance, a slightly higher Zr content reduces the C15 content. Further, as the titanium substitution level increases: (1) the lattice constants decrease; (2) the PCT plateau pressure increases; (3) activation becomes easier; and (4) the high rate dischargeability improves.     

Cycle stability of La0.7Mg0.3Ni2.55-xCo0.45Cux （x=0-0.4） electrode alloys

La0.7Mg0.3Ni2.55-xCo0.45Cux（x=0, 0.1, 0.2, 0.3, 0.4） electrode alloys were prepared by casting and rapid quenching. Ni in the alloy was partially substituted by Cu in order to improve the cycle stability of La-Mg-Ni system （PuNi3-type） hydrogen storage alloy. The effects of substituting Ni with Cu on the microstructures and cycle stability of the alloys were investigated in detail. The results obtained by XRD, SEM and TEM show that the substitution of Cu for Ni is favourable for the formation of an amorphous in the as-quenched alloy, and this leads to an obvious refinement of the as-quenched alloy grains and a growth of the lattice constants and cell volumes of the as-cast and quenched alloys. The results obtained by the electrochemical measurement indicate that the cycle stability of the alloys significantly rises with the incremental variety of Cu content. When Cu content changes from 0 to 0.4, the cycle lives of the as-cast and quenched （30 m/s） alloys are enhanced from 72 to 88 cycles and from 100 to 121 cycles, respectively.     

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.     

Oxidation behavior of NixFe1−x(OH)2 in Cl-containing solution

The addition of Ni leads to the formation of protective rust layer on steel and subsequently high corrosion resistance of steel in Cl⁻-containing environment. α-FeOOH, β-FeOOH, γ-FeOOH and Fe₃O₄ are formed mainly on steels exposed to Cl⁻-containing atmosphere. It is expected that systematic investigation of the effect of Ni(II) on the formation process of each oxide in solution should lead to elucidation of the role of Ni in the formation of anticorrosive oxide layer. This study reports the oxidation behavior of Ni_xFe_1−x(OH)₂ in Cl⁻-containing solution at two different pH regions (condition I under which solution pH is allowed to decrease and condition II under which solution pH is maintained at 8) where γ-FeOOH and Fe₃O₄ are predominantly formed, respectively, upon the oxidation of Fe(OH)₂. In the presence of Ni(II) in the starting solution, the formation of Ni(II) doped β-FeOOH with very low crystalline was facilitated and the formation of γ-FeOOH was suppressed with increasing Ni(II) content and with increasing oxidation rate of Fe(II). Ni(II) was found to have Fe₃O₄-suppressing effect under condition II.     

Investigation of hydrogen absorption/desorption properties of ZrMn0.85−xFe1+x alloys

The crystal structures and hydrogen absorption/desorption properties of the ZrMn_0.85−xFe_1+x alloys (x = 0, 0.2, 0.4) were investigated systematically. The pressure–composition (PC) isotherms and absorption kinetics were measured at 273–333 K by the volumetric method. Besides the crystal structure, the plateau pressure and the hydrogen intake capacity, this article also discussed the absorption kinetics, the pulverization resistance and the thermodynamic properties. XRD patterns revealed that ZrMn_0.85Fe and ZrMn_0.65Fe_1.2 were formed as hexagonal C14 laves phase structure while ZrMn_0.45Fe_1.4 possessed cubic C15 laves phase structure. With the increase of Fe and decrease of Mn, the plateau pressure increased while the hydrogen intake capacity lowered and the hydrogen absorption kinetics degraded. On the other hand, the hysteresis alleviated, the pulverization resistance improved and the stability of the hydrides decreased. The decomposition pressure was increased to more than 160 times for ZrMn_0.85Fe and more than 2500 times for ZrMn_0.65Fe_1.2 compared with that of the ZrMn₂ alloy.     

Fe替代Co对AB5型贮氢合金循环稳定性的影响

用铸造及快淬的方法制备了稀土基AB5型Mm（NiMnSiAl）4．3Co0.6-xFex（x=0，0．1，0．2，0．3，0．4，0．5，0．6）贮氢合金，用XRD。TEM及SEM观测了铸态及快淬态的微观结构，测试了合金在铸态及快淬态下的电化学循环稳定性。研究了Fe替代Co对铸态及快淬态贮氢合金微观结构及循环稳定性的影响。研究结果表明，Fe替代Co对铸态及快淬态合金的相结构没有明显影响，但对合金的循环稳定性产生显著影响。Fe替代Co能不同程度地改善铸态及快淬态合金的循环稳定性，但对快淬态合金循环寿命的改善更加显著，导致这一结果的主要原因是Fe替代Co使快淬态合金的微观组织显著细化。     

快淬纳米晶/非晶Mg2-xLaxNi (x=0~0.6)合金的电化学贮氢性能

用铸造及快淬工艺制备Mg2Ni型Mg2-xLaxNi(x=0,0.2,0.4,0.6)贮氢合金。用XRD、SEM、HRTEM分析铸态及快淬态合金的微观结构。结果发现,在快淬无La合金中没有出现非晶相,但快淬含La合金显示了以非晶相为主的结构。用DSC研究快淬合金的热稳定性,表明La的含量及快淬对非晶相的晶化温度影响很小。电化学测试结果表明,铸态合金的放电容量随La含量的增加而增加,快淬态合金的放电容量随La含量的变化有极大值。La替代Mg显著地提高了铸态及快淬态合金的循环稳定性。     

The compositional range of amorphous phase formation and thermal stability of Al90−xFe5Ni5Cex

The effects of Ce-substitution for Al in the Al_90−xFe₅Ni₅Ce_x (x = 0, 2, 5, 7, 8, 9, and 10) system on the mechanical alloying process were investigated. The structural evolution in these powders was characterized by scanning electron microscopy, differential thermal analysis and X-ray diffraction techniques. The compositional range of amorphous forming was obtained and it extended from 5 to 9 at.% Ce. With increasing Ce content, the crystallization temperature of amorphous alloys increases. The crystallization temperature versus concentration of Ce was reproduced well by applying an extension of a relationship between the crystallization temperature and the vacancy formation energy of constituents with smaller atomic radius. The crystallization product phases were analyzed by XRD after annealing the milled powders at temperature over the crystallization temperature.     

La替代Mm对低钴AB5型贮氢合金电化学性能的影响

用XRD和SEM测试了稀土基低钻AB5型LaxMm1-x（NiMnSiAlFe）4．7Co0.2（x=0,1）贮氢合金的微观结构，并全面测试了合金在铸态及快淬态下的电化学性能。研究了La替代Mm对铸态及快淬态低钻贮氢合金微观结构及电化学性能的影响。对合金的电化学性能研究结果表明：La替代Mm使合金的放电容量提高，并使铸态合金的循环寿命由341次提高到370次；La替代Mm使得快淬态合金的循环寿命的增加幅度较小，主要原因是La替代Mm使快淬态合金的晶粒粗化。微观结构测试结果表明：La替代Mm使合金中的第二相消失，并使合金的晶格常数在a轴方向增加，在c轴方向略有减小，晶胞体积增大，这是La替代Mm使合金放电容量提高的主要原因。     

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%.     

Morphology, optical and magnetic properties of Zn1−xNixO nanorod arrays fabricated by hydrothermal method

Zn_1−xNi_xO (x = 0, 0.05, and 0.1) nanorod arrays were prepared by hydrothermal method. Morphology and structure analysis indicate that the nanorods have single-crystalline wurtzite structure, and no metallic Ni or NiO phase exists. Room temperature ferromagnetism (RTFM) was observed in the Zn_0.9Ni_0.1O nanorods. In addtion, photoluminescence spectra of Zn_1−xNi_xO (x = 0, 0.05, 0.1 and 0.2) samples exhibit near band edge UV emissions and orange-red emissions. And the orange-red emission is confirmed to have originated from the interstitial oxygen defects.     

Hydrogenation of CaLi2−xMgx (0 ≤ x ≤ 2) with C14 Laves phase structure

CaLi_2−xMg_x (0 ≤ x ≤ 2) which has the C14-type Laves phase structure has been successfully synthesized and hydrogenated. The C14-type Laves phase structure was kept after hydrogenation of CaLi_2−xMg_x (x = 0.2, 0.5, 1). After hydrogenation of CaLi₂ and CaMg₂, the Laves phase disappeared. The CaH₂ and LiH phases were formed from CaLi₂ and the CaH₂ and Mg phases from CaMg₂, respectively. CaLi_2−xMg_x (0 < x < 2) ternary alloys formed stable hydride phases with the C14-type Laves phase structure in contrast to CaLi₂ and CaMg₂ binary alloys.     

La0.7Mg0.3Ni2.55-xCo0.45Alx(x=0～0.4)贮氢合金的循环稳定性

为了提高La-Mg-Ni系贮氢合金的循环稳定性,以Al部分替代Ni,采铸造及快淬工艺制备了La0.7Mg0.3Ni2.55-xCo0.45Alx(x=0,0.1,0.2,0.3,0.4)电极合金,研究了Al替代量及快淬工艺对合金微观结构及电化学循环稳定性的影响。X射线衍射分析结果表明:铸态及快淬态合金具有多相结构,包括(La,Mg)Ni3相、LaNi5相和一定量的LaNi2相;Al替代使铸态合金中LaNi2相的量显著增加,但对快淬态合金中LaNi2相的相丰度影响不显著。电化学测试结果表明:随Al替代量的增加,合金的循环寿命大幅度提高;快淬处理可以提高合金的循环寿命,但随Al替代量的增加,淬速对循环寿命的影响减小。