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.     

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...     

Effect of TiMn1.5 alloying on the structure,hydrogen storage properties and electrochemical properties of LaNi3.8Co1.1Mn0.1 hydrogen storage alloys

A series of experiments were performed to investigate the effect of TiMn_1.5 alloying on the structure, hydrogen storage properties and electrochemical properties of LaNi_3.8Co_1.1Mn_0.1 hydrogen storage alloys at 303 K. For simple, A, B, and C are used to represent alloys (x = 0 wt %, x = 4 wt % and x = 8 wt %) respectively. The results of XRD and SEM show that LaNi_3.8Co_1.1Mn_0.1?xTiMn_1.5 hydrogen storage alloys have LaNi₅ phase and (NiCo)₃Ti phase. Based on the results of PCT curves, the hydrogen storage capacities of LaNi_3.8Co_1.1Mn_0.1?xTiMn_1.5 hydrogen storage alloys are about 1.28 wt % (A), 1.16 wt % (B) and 1.01 wt % (C) at 303 K. And the released pressure platform and the pressure hysteresis decrease with the increase of TiMn_1.5 content. Meanwhile the activation curves show that LaNi_3.8Co_1.1Mn_0.1?xTiMn_1.5 hydrogen storage alloy electrodes can be activated in three times and the maximum discharge capacity is 343.74 mA h/g at 303 K. In addition, with the increase of TiMn_1.5 content, the cyclic stability of the hydrogen storage alloy electrodes decreases obviously and the capacity retention decreases from 76.70% to 70.00% when TiMn_1.5 content increases from A to C. It also can be seen that LaNi_3.8Co_1.1Mn_0.1?xTiMn_1.5 hydrogen storage alloy electrode C and B have the best self-discharge ability and the best high-rate discharge ability from self-discharge curves and high-rate discharge curves.     

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.     

Preparation and electrochemical hydrogen storage of boron nitride nanotubes

Boron nitride (BN) nanotubes were synthesized through chemical vapor deposition over a wafer made by a LaNi5/B mixture and nickel powder at 1473 K. Scanning electron microscopy, transmission electron microscopy, energy-dispersive spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy were performed to characterize the microstructure and composition of BN nanotubes. It was found that the obtained BN nanotubes were straight with a diameter of 30-50 nm and a length of up to several microns. We first verify that the BN nanotubes can storage hydrogen by means of an electrochemical method, though its capacity is low at present. The hydrogen desorption of nonelectrochemical recombination in cyclic voltammograms, which is considered as the slow reaction at BN nanotubes, suggests the possible existence of strong chemisorption of hydrogen, and it may lead to the lower discharge capacity of BN nanotubes. It is tentatively concluded that the improvement of the electrocatalytic activity by surface modification with metal or alloy would enhance the electrochemical hydrogen storage capacity of BN nanotubes.     

Preparation and hydrogen storage properties of nanostructured Mg2Cu alloy

We successfully synthesized Mg₂Cu alloys from the metal nanoparticles, which are produced from hydrogen plasma-metal reaction method, in two ways. One is under 0.1 MPa argon at 673 K and the other is under 4.0 MPa hydrogen at 673 K. The structure, morphology and reaction mechanism were studied. The hydrogen absorption and the pressure-composition isotherm properties of the obtained Mg₂Cu alloy under hydrogen were studied. The van’t Hoff equation and the formation enthalpy and entropy of the resulting hydride (MgH₂+MgCu₂) were obtained from the equilibrium plateau pressures of the desorption isotherms. Nanostructured Mg₂Cu shows excellent hydrogen storage properties because nanostructured materials have more surface area and more defects, which means more nucleation sites with hydrogen, and smaller particles, which means shorter diffusion distance for hydrogen in the alloys particles.     

Correlation between composition and hydrogen storage behaviors of the Li2NH-MgNH combination system

Hydrogen storage performances of a Li(2)NH-xMgNH combination system (x = 0, 0.5, 1 and 2) are investigated for the first time. It is found that the hydrogenated samples with MgNH exhibit a significant reduction in the dehydrogenation temperatures. Mechanistic investigations reveal that there is a strong dependence of the hydrogen storage reaction process on the molar ratio between MgNH and Li(2)NH. As a consequence, tuning of thermodynamics is achieved for hydrogen storage in the Li(2)NH-xMgNH system by changing the reaction routes, which is ascertained to be the primary reason for the reduction in the operating temperature for hydrogen desorption. Specifically, it is found that under 105 atm hydrogen (140-280 °C) 5.6 wt% hydrogen is reversibly stored in the Li(2)NH-0.5MgNH combination system, which is greater than in the well-investigated Mg(NH(2))(2)-2LiH system.     

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)     

Structural analysis of La-Mg-Ni-based new hydrogen storage alloy

The structural analysis of new hydrogen storage alloys, La₅Mg₂Ni₂₃ and La₃MgNi₁₄, was performed using HRTEM. As a result, these ternary system alloys were found to be mainly composed of stacked RNi₅ (CaCu₅ type) and R₂Ni₄ (Laves type) structure subunits in a superstructure arrangement. La₅Mg₂Ni₂₃ alloy is composed of the primitive cell of three LaNi₅ units and the primitive cell of two La₂Mg₂Ni₄ units. La₃MgNi₁₄ alloy is composed of four LaNi₅ and two La₂Mg₂Ni₄ unit cells.     

Solution-phase synthesis and electrochemical hydrogen storage of ultra-long single-crystal selenium submicrotubes

Ultra-long single-crystalline trigonal selenium submicrotubes were synthesized using a facile one-step solution-phase approach with the assistance of nonionic surfactant Polyoxyethylene(20)sorbitan monolaurate (Tween-20), which turned out to be significant for the formation of ultra-long Se submicrotubes. XRD, Raman, SEM, and TEM were adopted to characterize the morphology, structure and phase composition of the as-prepared Se products. It was found that the length of the obtained Se submicrotubes was over 100 microm. By variation of the experimental parameters, the t-Se spheres, nanowires, and broken microtubes can be prepared. The possible growth mechanism of the ultra-long selenium submicrotubes was explained. In addition, we have also demonstrated that the synthesized ultra-long t-Se submicrotubes using the Tween-20-assisted approach can electrochemically charge and discharge with the high capacity of 265 mAh/g (corresponding to 0.97 wt % hydrogen in SWNTs) under normal atmosphere at room temperature. Cyclic voltammetry was adopted to investigate the adsorption-oxidation behavior of ultra-long selenium submicrotubes. It was observed that the morphology of the synthesized selenium products had a remarkable influence on their capacity of electrochemical hydrogen storage. These differences in hydrogen storage capacity are likely due to the size and density of tubes as well as the microcosmic morphology of different Se samples. The as-obtained ultra-long Se submicrotubes are expected to find wide applications in hydrogen storage, high-energy batteries, and optoelectronic, biologic, and catalytic fields as well as in the studies of structure-property relationships. This simple Tween-assisted approach might be extended to the preparations of one-dimensional nanostructures of tellurium and other anisotropic materials.     

The electrochemical performance of AB3-type hydrogen storage alloy as anode material for the nickel metal hydride accumulators

For the purpose of lowering the cost of metal hydride electrode, the La of LaY₂Ni₉ electrode was replaced by Ce. The electrochemical performances of the CeY₂Ni₉ negative electrode, at a room and different temperatures, were compared with the parent alloy LaY₂Ni₉. At room temperature during a long cycling, the evolution of the electrochemical capacity—the diffusivity indicator (\( \frac{D_{\mathrm{H}}}{a^2} \))—the exchange current density, and the equilibrium potential were determined. At different temperatures, the electrochemical characterization of this alloy allowed the estimation of the enthalpy, the entropy, and the activation energy of the hydride formation. The evolution of the high-rate dischargeability was also evaluated at different temperatures. Compared with the parent LaY₂Ni₉ alloy, CeY₂Ni₉ exhibits an easy activation and good reaction reversibility. This alloy also conserves a good lifetime during a long-term cycling. A lower activation energy determined for this alloy corresponds to an easy absorption of hydrogen into this new alloy.     

Biomolecule-assisted synthesis and electrochemical hydrogen storage of Bi2S3 flowerlike patterns with well-aligned nanorods

Bi2S3 flowerlike patterns with well-aligned nanorods were synthesized using a facile solution-phase biomolecule-assisted approach in the presence of L-cysteine (an ordinary and cheap amino acid), which turned out to serve as both the S source and the directing molecule in the formation of bismuth sulfide nanostructures. Emphatically, no nauseous scent (H2S) appeared in our experiments, which could not be avoided in other previous reports. The morphology, structure, and phase composition of the as-prepared Bi2S3 products were characterized using various techniques (scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, selected area electron diffraction, and high-resolution transmission electron microscopy). The formation mechanism for the bismuth sulfide flowerlike assemblies with well-arranged nanorods was also discussed. In addition, other Bi2S3 homogeneous nanostructures (e.g., networklike nanoflakes, nanorod-based bundles, and nanoflakes) were obtained through varying the experimental parameters. Interestingly, we have found that these synthesized bismuth sulfide nanostructures using the biomoleucle-assisted approach could electrochemically charge and discharge with the capacity of 142 (mA h)/g (corresponding to 0.51 wt % hydrogen in single-walled carbon nanotubes) under normal atmosphere at room temperature. A novel two-plateau phenomenon was observed in the synthesized Bi2S3 nanostructures, suggesting that there were two independent steps in the charging process. It has been demonstrated that the bismuth sulfide's morphology and the constant charge-discharge current density had a noticeable influence on their capacity of electrochemical hydrogen storage. These differences in hydrogen storage capacity are likely due to the size and density of space/pores as well as the morphology of different Bi2S3 nanostructures. The novel Bi2S3 nanomaterials may find potential applications in hydrogen storage, high-energy batteries, luminescence, optoelectronic and catalytic fields, as well as in the studies of structure-property relationships. This facile, environmentally benign, and solution-phase biomolecule-assisted method can be potentially extended to the preparation of other metal chalcogenides including FeS, CuS, NiS, PbS, MnS, and CoS nanostructures.     

Mg1.8La0.2Ni-xNi nanocomposites for electrochemical hydrogen storage

Mg1.8La0.2Ni hydrogen storage alloy was ball-milled with Ni powder, leading to the formation of a nanocrystalline and amorphous microstructure with particle sizes less than 50 nm in diameter. Each sample was examined by transmission electron microscopy (TEM), energy-dispersive spectroscopy (EDS), and X-ray diffraction (XRD). This structure was beneficial for the reduction of electrochemical impedance, as well as significant improvement of its discharge capacity, cycle life, and rate capability for electrochemical hydrogen storage in an alkaline solution. When the molar ratio (x) of Ni over Mg1.8La0.2Ni was equal to 2, the dehydriding capacity reached 2.55 wt % from electrochemical pressure-temperature isotherms (P-C-T). It was in good agreement with its initial discharge capacity, 716 mA*h/[g of (Mg1.8La0.2Ni)], observed from the electrochemical charge and discharge process. After 50 cycles, its discharge capacity still reached 381 mA*h/[g of (Mg1.8La0.2Ni)]. Further results showed that this composite had a promising high rate capability. At the current density of 1200 mA/g its discharge capacity reached 48% of its initial capacity.     

In situ electrochemical dehydrogenation of ultrathin Co(OH)2 nanosheets for enhanced hydrogen evolution

Transition metal hydroxides/oxyhydroxides have recently emerged as highly active electrocatalysts for oxygen evolution reaction in alkaline water electrolysis, while have not yet been widely investigated for hydrogen evolution electrocatalysts owing to their unfavorable H*-adsorption, making it difficult to construct an overall-water-splitting cell for hydrogen production. In this work, we proposed a straightforward and effective approach to develop an efficient in-plane heterostructured CoOOH/Co(OH)₂ catalyst via in-situ electrochemical dehydrogenation method, in which the dehydrogenated –CoOOH and Co(OH)₂ at the surface synergistically boost the hydrogen evolution reaction (HER) kinetics in base as confirmed by high-resolution transmission electron microscope, synchrotron X-ray absorption spectroscopy, and electron energy loss spectroscopy. Due to the in-situ dehydrogenation of ultrathin Co(OH)₂ nanosheets, the catalytic activity of the CoOOH/Co(OH)₂ heterostructures is progressively improved, which exhibit outstanding hydrogen-evolving activity in base requiring a low overpotential of 132 mV to afford 10 mA/cm² with very fast reaction kinetics after 60 h dehydrogenation. The gradually improved catalytic performance for the CoOOH/Co(OH)₂ is probably due to the enhanced H*-adsorption induced by the synergistic effect of heterostructures and better conductivity of CoOOH relative to electrically insulating Co(OH)₂. This work will open the opportunity for a new family of transition metal hydroxides/oxyhydroxides as active HER catalysts, and also highlight the importance of using in situ techniques to construct precious metal-free efficient catalysts for alkaline hydrogen evolution.     

Nonlinear dynamic behaviors of electrochemical corrosion of Ti-48Al-2Cr-2Nb alloy at high applied potentials

Journal of Solid State Electrochemistry - Chronoamperometry (CA), phase space reconstruction, correlation dimension, multifractal detrended fluctuation analysis (MFDFA) combining linear sweep...     

Preparation of platinum-decorated porous graphite nanofibers, and their hydrogen storage behaviors

In this work, the hydrogen storage behaviors of porous graphite nanofibers (GNFs) decorated by Pt nanoparticles were investigated. The Pt nanoparticles were introduced onto the GNF surfaces using a well-known chemical reduction method. We investigated the hydrogen storage capacity of the Pt-doped GNFs for the platinum content range of 1.3-7.5 mass%. The microstructure of the Pt/porous GNFs was characterized by X-ray diffraction and transmission electron microscopy. The hydrogen storage behaviors of the Pt/GNFs were studied using a PCT apparatus at 298 K and 10 MPa. It was found that amount of hydrogen stored increased with increasing Pt content to 3.4 mass%, and then decreased. This result indicates that the hydrogen storage capacity of porous carbons is based on both their metal content and dispersion rate.     

Preparation and characterization of ordered porous carbons for increasing hydrogen storage behaviors

We prepared ordered porous carbons (PCs) by using a replication method that had well-organized mesoporous silica as a template with various carbonization temperatures in order to investigate the possibility of energy storage materials. The microstructure and morphologies of the samples are characterized by XRD, TEM, and FT-Raman spectroscopy. N₂ adsorption isotherms are analyzed by the t-plot method, as well as the BET and the H–K method in order to characterize the specific surface area, pore volume, and pore size distribution of the samples, respectively. The capacity of the hydrogen adsorption of the samples is evaluated by BEL-HP at 77 K and 1 bar. From the results, we are able to confirm that the synthesis of the samples can be accurately governed by the carbonization temperature, which is one of the effective parameters for developing the textural properties of the carbon materials, which affects the behaviors of the hydrogen storage.     

Rare earth hydrogen storage alloy used in borohydride fuel cells

Fuel cell using the borohydride as the fuel has attracted much attentions because of high energy density and working potential. In this work, LaNi_4.5Al_0.5 hydrogen storage alloy used as the anodic material to replace noble metals has been investigated. Experimental results showed that H₂ evolution was unavoidable during discharge process because of the hydrolysis of , but the utilization of the fuel increased with the increasing current densities. At high discharge current, the alloy electrode showed the lowest hydrogen generation rate and higher utilization of the fuel because, the generated hydrogen was absorbed and oxidized to produce electric energy similar to the behavior of hydrogen storage alloy in nickel–metal hydride batteries. The reaction mechanism of borohydride on the surface of electrode made of hydrogen storage alloy also has been discussed. Hydrogen storage alloy would be a promising material as the anodic catalyst in borohydride fuel cell.