Effect of Cu content on structure,hydrogen storage properties and electrode performance of LaNi4.1-x Co0.6Mn0.3Cu x alloys

The effect of Cu content on structure, hydrogen storage, and electrochemical properties of LaNi_4.1-x Co_0.6Mn_0.3Cu _x alloys has been investigated. For sample, A, B, C, and D are used to represent alloys (x?=?0, 0.15, 0.3, and 0.45), respectively. The results indicate that the four alloys are all single-phase alloy with LaNi₅ phase of CaCu₅ hexagonal structure, the hydrogen storage capacities of the alloy are about 1.49 wt% (A), 1.48 wt% (B), 1.43 wt% (C), and 1.25 wt% (D) at 303 K. With the increase of Cu content (x) from A to D, hydrogen desorption plateau pressure and pressure hysteresis decrease. Alloy electrode A shows better activation property and higher capacity (334.44 mAh/g). The addition of Cu improves the cyclic stability of the alloy electrodes when x?=?0?~?0.45. However, their self-discharge properties and high-rate dischargeability (HRD) decrease with the increase of x. Further, electrochemical kinetics and electrochemical impedance spectroscopy (EIS) analysis show that the reaction of alloy electrode is controlled by charge transfer step, and the adding of Cu benefits the electrode properties in alkaline solution.     

Effect of Co substitution for Ni on the microstructure and electrochemical properties of La-R-Mg-Ni-based hydrogen storage alloys

Hydrogen storage alloys La_0.63Gd_0.2?Mg_0.17Ni_3.35?x Co _x Al_0.15 (x?=?0, 0.1, 0.3, 0.5, 1.0, 1.5, 2.0) were prepared by induction melting followed by annealing treatment in argon atmosphere. The electrochemical properties of La_0.63Gd_0.2?Mg_0.17Ni_3.35?x Co _x Al_0.15 (x?=?0, 0.1, 0.3, 0.5, 1.0, 1.5, 2.0) alloy electrodes depended on the alloy structure type. XRD patterns and EPMA showed that the alloys consisted of Ce₂Ni₇-type (Gd₂Co₇-type), CaCu₅-type, Pr₅Co₁₉-type, and PuNi₃-type phase structure. Pr₅Co₁₉-type and Ce₂Ni₇-type phase increased with the increase of Co content x. However, CaCu₅-type phase firstly decreased then increased as Co content increased. Rietveld analysis showed that the c-axis lattice parameters and cell volumes of the component phases increased with increasing Co content. The electrochemical measurements showed that as the Co content increased, the maximum discharge capacity and the cyclic stability of the annealed alloys both first increased and then decreased. The La_0.63Gd_0.2?Mg_0.17Ni_3.05Co_0.3Al_0.15 alloy electrode exhibited the maximum discharge capacity (392.92 mAh/g), and La_0.63Gd_0.2?Mg_0.17Ni_1.85Co_1.5Al_0.15 alloy electrode showed the best cyclic stability (S₁₀₀?=?96.1 %). The electrochemical kinetics studies indicate that La_0.63Gd_0.2?Mg_0.17Ni_1.85Co_1.5Al_0.15 exhibited a higher rate dischargeability (HRD₉₀₀?=?86.3 %). Electrochemical analyses showed that the control process of alloy electrode reaction is charge-transfer rate in surface film of alloy.     

Phase structure and electrochemical characteristics of CaNi4.7Mn0.3 hydrogen storage alloy by mechanical alloying

Journal of Solid State Electrochemistry - In this paper, we study systematically the effect of ball/powder weight ratio on the morphological, structural, and electrochemical properties of...     

Structural and electrochemical properties of high-capacity Ml-Mg-Ni-based hydrogen storage alloys

The Ml-Mg-Ni-based (Ml = La-rich mixed lanthanide) hydrogen storage alloy Ml_0.88Mg_0.12Ni_3.0-Mn_0.10Co_0.55Al_0.10 was prepared by inductive melting. The micro-structure was analyzed by XRD and SEM. The alloy consists mainly of CaCu₅-type phase, Ce₂Ni₇-type phase and Pr₅Co₁₉-type phase. The electrochemical measurements show that the maximum discharge capacity is 386 mAh/g, 16.3% higher than that of the commercial AB₅-type alloy (332 mAh/g). At discharge current density of 1 100 mA/g, high rate dischargeability is 62%, while that of the AB5-type alloy is only 45%. The discharge capacity decreases to 315 mAh/g after 300 charge/ discharge cycles, 81.5% of the maximum discharge capacity. __________ Translated from Journal of Xi’an Jiao Tong University, 2008, 42(3) (in Chinese)     

The Influence of Mechanical Activation on Hydrogen Absorption by Intermetallic Compound LaNi2.5Co2.4Mn0.1

Russian Journal of Physical Chemistry A - The influence of mechanical activation in a high energy planetary ball mill on hydrogen sorption and structural properties of intermetallic compound...     

缺陷对混合稀土贮氢合金性能的影响

贮氢合金是一种重要的功能材料。在多种贮氢合金中,AB~5型稀土系贮氢合金的应用最为广泛。本文用正电子湮没技术(PAT)对AB~5型混合稀土贮氢合金的缺陷进行了研究,并结合X射线衍射(XRD)测试、循环伏安(CV)测试以及合金容量的测定,对合金的结构及性能进行了研究。结果表明,合金微观缺陷的存在能大幅度提高金的性能。     

Structural and electrochemical properties of TiFe alloys synthesized by ball milling for hydrogen storage

The binary TiFe alloy was synthesized by mechanical alloying (MA) under argon atmosphere at room temperature. The effect of ball to powder weight ratio on the microstructures was characterized by X-ray diffraction (XRD). The effect of milling time on the electrochemical and activation properties was investigated by scanning electron microscope (SEM), galvanostatic charging and discharging, constant potential discharge, and potentiodynamic polarization techniques. Relationships between electrochemical properties, such as polarization, variation of electrochemical discharge capacity, \( \frac{D_{\mathrm{H}}}{a^2} \) ratio exchange current density, and Nernst potential and alloy compositions were evaluated. XRD results showed that with increasing ball to powder weight ratio, the amorphization process is accelerating and powders milled with a ratio of 1:8 have the highest conversion rate to TiFe. SEM observations reveal that particles show cleavage fracture morphology and size distribution is generally normalized. TiFe milled during 40 h was easily activated within 5 cycles and showed the best discharge capacity equal to 147 mAh g^?1. A good cycling was observed after 20 cycles at ambient temperature for the alloy milled for 30 h. A correlation between alloy composition, \( \frac{D_{\mathrm{H}}}{a^2} \) report, exchange current density, and Nernst potential on one hand and the variation of the electrochemical discharge capacity during cycling for different milling times on the other hand was observed.     

Study of the effect of praseodymium substitution on hydrogen storage and electrochemical properties of cerium-rich AB5 alloys

Journal of the Iranian Chemical Society - In order to investigate the hydrogen storage properties of cerium-rich RE-based alloys, series of MmNi5 and Mm(1−x)PrxNi3.55Co0.75Mn0.4Al0.3...     

Dual-modification of Gd2O3 on the high-voltage electrochemical properties of LiNi0.8Co0.1Mn0.1O2 cathode materials via the solid-state method

Journal of Solid State Electrochemistry - In this paper, the dual-modified LiNi0.8Co0.1Mn0.1O2 via Gd2O3 is successfully obtained by the solid-state method. The phenomenon of Li/Ni cation mixing...     

The structure and electrochemical characteristics of La0.67Mg0.33 (Ni0.8Co0.1Mn0.1) x (x=2.5–5.0) multiphase alloys for nickel-metal hydride batteries

This paper presents results concerning structure and electrochemical characteristics of the La_0.67Mg_0.33 (Ni_0.8Co_0.1Mn_0.1) _x (x=2.5–5.0) alloy. It can be found from the result of the Rietveld analyses that the structures of the alloys change obviously with increasing x from 2.5 to 5.0. The main phase of the alloys with x=2.5–3.5 is LaMg₂Ni₉ phase with a PuNi₃-type rhombohedral structure, but the main phase of the alloys with x=4.0–5.0 is LaNi₅phase with a CaCu₅-type hexagonal structure. Furthermore, the phase ratio, lattice parameter and cell volume of the LaMg₂Ni₉phase and the LaNi₅ phase change with increasing x. The electrochemical studies show that the maximum discharge capacity increases from 214.7 mAh/g (x=2.5) to 391.1 mAh/g (x=3.5) and then decreases to 238.5 mAh/g (x=5.0). As the discharge current density is 1,200 mA/g, the high rate dischargeability (HRD) increases from 51.1% (x=2.5) to 83.7% (x=3.5) and then decreases to 71.6% (x=5.0). Moreover, the exchange current density (I ₀) of the alloy electrodes first increases and then decrease with increasing x from 2.5 to 5.0, which is consistent with the variation of the HRD. The cell volume reduces with increasing x in the alloys, which is detrimental to hydrogen diffusion and accordingly decreases the low-temperature dischargeability of the alloy electrodes.     

Structure and electrochemical hydrogen storage behaviors of alloy Co2B

The alloys Co₂B were prepared by two ways of high temperature solid phase process and arc melting, the structure of the alloys was characterized by XRD and SEM. It showed that it was structure of tetragonal Co₂B.The electrochemical experimental results demonstrated that the Co₂B prepared by two means both showed excellent cycling stability. The initial discharge capacity of Co₂B prepared by the high temperature solid phase process was 480.3 mA h g⁻¹, there was no distinct declination after 70 charge–discharge cycles and the capacity kept about 195 mA h g⁻¹. Co₂B prepared by the high temperature solid phase process showed very good electrochemical reversibility in CV curves. The hydrogen storage mechanism was also discussed, it confirmed that the high initial capacity of Co₂B prepared by the high temperature solid phase process was due to the oxidation of Co and B₂O₃, and it was irreversible.     

电化学方法研究贮氢电极合金的P—C—T曲线

根据电化学和热力学的基础理论,考虑了氢气的逸度、碱液中水的活度以及碱液中水蒸汽的分压等影响因素,精确计算了金属氢化物电极反应的能斯特方程。结合三电极测试体系,建立了一套贮氢电极合金的P-C-T曲线电化学测定方法,并给出实验操作及相关参数确定的细节。该方法适用于涉及到大量实验工作的贮氢电极合金的成分优化及工艺研究。     

Ni添加对Ti0.4Zr0.1V1.1Mn0.5Cr0.1合金的相结构和电化学性能的影响

本文通过XRD、SEM、EDS研究了Ti0.4Zr0.1V1.1Mn0.5Cr0.1Nix(x=0,0.2,0.4,0.6,0.8)合金的相结构和电化学性能.该合金系由BCC结构的V基固溶体主相和六方结构的C14 Laves第二相组成,Ni能够促进第二相的生成,Ni含量的增加导致了各相中的化学组成和晶格参数的变化,并通过电化学方法研究了Ni含量对Ti0.4Zr0.1V1.1Mn0.5Cr0.1合金电极的最大放电容量、自放电性能、高倍率放电性能、循环稳定性能等的影响.     

Effect of LiH on electrochemical hydrogen storage properties of Ti55V10Ni35 quasicrystal

The electrochemical hydrogen storage properties and mechanisms of the Ti₅₅V₁₀Ni₃₅ quasicrystal + xLiH(x = 3, 6 and 9 wt.%) system are investigated and discussed in this paper. A composite material in the Ti₅₅V₁₀Ni₃₅ quasicrystal and system has been synthesized moderately by means of mechanical milling under an argon atmosphere, which can avoid reaction of releasing of hydrogen during the process of milling. The results indicate that the addition of LiH significantly improves the electrochemical characteristics of composite material. The maximum discharge capacity increases from 220.1 mAh/g to 292.3 mAh/g on Ti₅₅V₁₀Ni₃₅ + 6 wt.% LiH, and the cycling stability is also enhanced too. In addition, the high rate dischargeability (HRD) is ameliorated remarkably, and the value of HRD value at 240 mA/g rises by 78.1%–87.8% for Ti₅₅V₁₀Ni₃₅ + 6 wt.% LiH alloy electrodes. The improvement of characteristics of the electrochemical hydrogen storage characteristics may be attributed to LiH, which has excellent electrochemical activity.     

Effect of overdischarge (overlithiation) on electrochemical properties of LiNi0.5Mn1.5O4 samples of different origin

Journal of Solid State Electrochemistry - Overreaching certain minimum allowable voltage upon discharging a lithium-ion battery (overdischarge) leads to the insertion of an overstoichiometric...     

Effect of cerium on electrochemical and mechanical properties of aluminum-iron alloys

Effect of cerium on the corrosion-electrochemical and mechanical properties of aluminum alloys with an iron content of up to 3% was studied in order to use secondary aluminum in development of sacrificial formulations.     

Preparation and characterization of novel structure Co–B hydrogen storage alloy

The Co–B alloy was prepared by the chemical reduction method and the annealing method. The structural and morphological characterizations were performed using TEM and XRD. The Electrochemical Measurements were performed using LAND battery test instrument. After annealing treatment,the initial Co–B alloy decomposes to crystalline Co and B with a kind of coating sphere structure. The excellent electrochemical hydrogen storage properties are also obtained.     

Probing the structure, stability and hydrogen storage properties of calcium dodecahydro-closo-dodecaborate

Calcium borohydride can reversibly store up to 9.6 wt% hydrogen; however, the material displays poor cyclability, generally associated with the formation of stable intermediate species. In an effort to understand the role of such intermediates on the hydrogen storage properties of Ca(BH₄)₂, calcium dodecahydro-closo-dodecaborate was isolated and characterized by diffraction and spectroscopic techniques. The crystal structure of CaB₁₂H₁₂ was determined from powder XRD data and confirmed by DFT and neutron vibrational spectroscopy studies. Attempts to dehydrogenate/hydrogenate mixtures of CaB₁₂H₁₂ and CaH₂ were made under conditions known to favor partial reversibility in calcium borohydride. However, up to 670 K no notable formation of Ca(BH₄)₂ (during hydrogenation) or CaB₆ (during dehydrogenation) occurred. It was demonstrated that the stability of CaB₁₂H₁₂ can be significantly altered using CaH₂ as a destabilizing agent to favor the hydrogen release.     

The properties of some zirconium-based gettering alloys for hydrogen isotope storage and purification

Non-volatile getter alloys, which have been extensively used for a long time in the traditional field of vacuum technology, have recently been proposed for more advanced applications related to plasma physics, controlled nuclear fusion and general tritium-handling systems. Heat pumps and hydrogen storage devices, where pure hydrogen must be used, may also need purification systems based on these gettering alloys. Some zirconium-based alloys, which are commercially available with different compositions, are good candidates for getter materials in such applications. The equilibrium laws which govern the solution of the hydrogenic species in these alloys up to gas concentrations higher than those usually involved in vacuum applications have been investigated and are discussed together with the main physicochemical properties of the alloys.