Effect of Stoichiometry on Properties of Rare-Earth-Based Hydrogen Storage Alloy for Nickel-Metal Hydride Secondary Battery

Effect of stoichiometry on microstructures, electrochemical properties and PCT characteristics of the alloys MI(Ni0.71Co0.15-Al0.06Mn0.08)x (MI=Lanthanum-rich Michmetal, x=4.6~5.2) have been investigated. The lattice constants a, c, and cellvolumes of non-stoichiometric alloys are bigger than those of the stoichiometric alloy. With the increasing stoichiometry x,the value of a decreases, and the value of c and cell volume increases except for those of the stoichiometric alloy; the plateaupressure of PCT curve, discharge capacity and cycling stability all increase. The alloy with x=5.2 shows the highest dischargecapacity and the best cycling stability among the studied alloys.     

直流法测量钯氢化物电极电阻时的阻值偏移

讨论了直流法在线测量钯氢化物电极电阻时的电化学效应，计算了电解液的共导、测量电流与电解电流引起的浓差电池效应以及电极作为集流体引起的电阻贡献。结果表明：当电极具有高的长度与半径比值、粗糙的表面、高的溶液电导以及大的电解电流时容易引起显著的附加电阻。     

CONSTITUTE AND PROPERTY OFα-Ti AFTER HYDRIDING TREATMENT

研究了氢化处理对退火α-Ti 板材的组织、结构及性能的影响。α-Ti 在室温出现两种结构的氢化物:有序的fctγ相(TiH)和fccδ相(TiH_2)。分析了用X 射线衍射只查觉到δ相的原因。氢化物的数量及形态影响除氢后基体的晶粒组织。控制氢含量可以改善拉伸性能及疲劳性能。     

Influence of the deposition atmosphere on the characteristics of Pd–Mg thin films prepared by pulsed laser deposition

Bilayered palladium (30 nm thick)–magnesium (350 nm thick) thin films were prepared using the pulsed laser deposition technique in the presence of various background gases (Ar, He and a mixture He + H₂) under different partial pressures (47 and 27 Pa). According to the deposition atmosphere, the Pd/Mg interface shows either a sharp or an extended transition. The electrochemical hydriding properties and the mechanical stability upon cycling of the Pd/Mg film are greatly improved when an extended «intermixing» zone between the Pd and Mg layers is present. The Pd–Mg films prepared under pure helium fulfill these conditions.     

Characterization of supported Pd-Pt catalysts by chemical probes

The temperature programmed (palladium) hydride decomposition appeared very effective method for diagnosing the extent of alloying in Pd-Pt/SiO₂ catalysts. Introduction of Pt to Pd catalysts moves the TPHD peak gradually towards lower temperatures and the shift in hydride decomposition peak is accompanied by a decrease in the amount of released hydrogen. The catalysts prepared the direct redox method showed much better alloy homogeneity than the samples prepared by coimpregnation. The results of probing with other techniques, i.e. catalytic probing with hydrodechlorination of CCl₂F₂ and XRD, were in line with TPHD data. The catalytic probing showed the presence of synergistic effect, a clear indication of Pd-Pt mixing. XRD data of post-reaction samples showed carbon incorporation into Pd-rich phase, whereas separate Pt-rich phase did not experience any bulk carbiding.     

氢化物发生原子吸收光谱法测定金属锌中的痕量汞

采用氢化物发生原子吸收光谱法测定金属锌中的痕量汞，研究了金属锌消解的最佳条件，本法简便、快速、重现性好，准确度高，灵敏度为0．73μg/L，检测限为0．22μg/L，相对标准偏差为3．1％，回收率为96％-102％。     

铂与氢、水和苯分子相互作用的量子化学研究

采用量子化学程序Gaussian98(A.9)从头算的B3LYP方法，全优化计算铂对氢、水和苯的化学吸附作用，得到了3种相关络合物PtX、PtXX和Ptxxx(X=H，H2O或C6H6)的平衡几何构型和电子结构信息，并探讨了这些络合物的成键性质，以及苯环与铂原子之间的分子轨道作用性质。结果表明，苯环与铂原子之间有很强的成键作用，并随着游离氢原子和水分子的参与，作用强度有很大变化。苯分子吸附在金属铂上，它的芳香性得到不同程度的降低，苯环被活化，苯环与铂原子之间形成η^2型π键络合物；水参与作用后，苯环与铂原子之间形成σ络合物；氢和水同时参与作用后，苯环与铂原子之间仅有很弱的π轨道作用。     

Electrochemical investigation of the iron-containing and no iron-containing AB5-type negative electrodes

The electrochemical behaviour of LaNi_3.55Mn_0.4Al_0.3Co_0.75−xFe_x (x = 0, 0.15, 0.55, 0.75) intermetallic compounds has been studied and presented [C. Khaldi, H. Mathlouthi, J. Lamloumi, A. Percheron-Guégan, Int. J. Hydrogen Energy 29 (2004) 307–311; C. Khaldi, H. Mathlouthi, J. Lamloumi, A. Percheron-Guégan, J. Alloys Compd. 360 (2003) 266–271; C. Khaldi, H. Mathlouthi, J. Lamloumi, A. Percheron-Guégan, J. Alloys Compd. 384 (2004) 249–253]. It has been deduced that the LaNi_3.55Mn_0.4Al_0.3Co_0.4Fe_0.35 compound has interesting electrochemical properties. In this paper we present the electrochemical study of LaNi_3.55Mn_0.4Al_0.3Co_0.4Fe_0.35 compound properties compared with the parent LaNi_3.55Mn_0.4Al_0.3Co_0.75 compound. Several techniques, such as, the chronopotentiometry, the constant potential discharge (CPD), the cyclic voltammetry (CV) and the linear polarization (LP) were applied to characterize these electrochemical properties. The electrochemical discharge capacity of the LaNi_3.55Mn_0.4Al_0.3Co_0.75 alloy increases to reach 294 mAh g⁻¹ after few cycles only (five cycles). However, the activation of the LaNi_3.55Mn_0.4Al_0.3Co_0.4Fe_0.35 alloy takes more than 20 cycles to be achieved and the obtained maximum discharge capacity is 194 mAh g⁻¹. The hydrogen diffusion coefficient D_H was determined by constant potential discharge and cyclic voltammetry techniques. The obtained values of the LaNi_3.55Mn_0.4Al_0.3Co_0.75 and LaNi_3.55Mn_0.4Al_0.3Co_0.4Fe_0.35 compounds are 6.29 × 10⁻¹¹ and 7.62 × 10⁻¹¹, and 2 × 10⁻⁸ and 7.5 × 10⁻⁸ cm² s⁻¹ by CPD and CV techniques, respectively. The exchange current density values, determined by a linear polarization technique, are 44 and 27 mA g⁻¹, respectively, for LaNi_3.55Mn_0.4Al_0.3Co_0.75 and LaNi_3.55Mn_0.4Al_0.3Co_0.4Fe_0.35 alloys.     

Activation of hydrogen storage materials in the Li–Mg–N–H system: Effect on storage properties

We investigate the thermodynamics, kinetics, and capacity of the hydrogen storage reaction: Li₂Mg(NH)₂ + 2H₂  Mg(NH₂)₂ + 2LiH. Starting with LiNH₂ and MgH₂, two distinct procedures have been previously proposed for activating samples to induce the reversible storage reaction. We clarify here the impact of these two activation procedures on the resulting capacity for the Li–Mg–N–H reaction. Additionally, we measure the temperature-dependent kinetic absorption data for this hydrogen storage system. Finally, our experiments confirm the previously reported formation enthalpy (ΔH), hydrogen capacity, and pressure–composition–isotherm (PCI) data, and suggest that this system represents a kinetically (but not thermodynamically) limited system for vehicular on-board storage applications.     

Theoretical analysis of β-LaNi5Hx(5≤x≤8): structure and energetics

The calculations of total energy, band structure, and electronic density of states and Mulliken population analysis of β-LaNi5 Hx (5≤x≤8) were performed by adopting the method of total energy based on the density functional theory. The augmented plane wave function was selected as the basis set in combination with ultra-soft pseudo-potential technology. The influence of the amount of H absorbed in alloys was discussed in terms of geometry, electronic structure and thermodynamic derived from calculated results. The results show that the amount of H absorbed and the preferred site occupation of the absorbed hydrogen atoms were controlled by the position of Hbands and the energy gap between H-bands and conduction bands. The β-phase hydrides of LaNi5 are most stable when hydrogen atom capacity coating in the range of 6 - 7.