Syntheses and catalytic performances of Ag–Ni bi-metals

Ag–Ni bi-metal nanocrystals were prepared by a novel solution method, in which ethanol was first taken as a green solvent with no use of any external toxic reducing agents. The as-prepared bi-metal nanocrystals were spherical and constructed by an aggregation of tiny crystals with particle size of about 12 nm. Infrared data indicated that the surfaces of the as-prepared nanocrystals were free of organic contaminants. The obtained bi-metal nanocrystals showed great potential as the additive in promoting the decomposition of ammonium perchlorate (AP), the key component of composite solid propellants. They were also initiated as the anode material of solid oxide fuel cells (SOFCs) which showed a maximum power density of 52.34 mW cm⁻² for single cell at 800 °C.     

Elaboration and electrochemical characterization of Mg–Ni hydrogen storage alloy electrodes for Ni/MH batteries

Mg–Ni hydrogen storage alloy electrodes with composition of Mg–33, 50, 67 Ni at. % in amorphous phase were prepared by means of mechanical alloying (MA) process using a planetary ball mill. The electrochemical hydrogen storage characteristics and mechanisms of these electrodes were investigated by electrochemical measurements, X–ray diffraction (XRD) and scanning electron microscope (SEM) analyses. The relationship between alloy composition and electrochemical properties was evaluated. In addition, optimum milling time and composition of Mg–Ni hydrogen storage alloy with acceptable electrochemical performance were determined. XRD results show that the alloys exhibit dominatingly amorphous structures after milling of 20 h. The electrochemical measurements revealed that the discharge capacity of Mg₃₃Ni₆₇ and Mg₆₇Ni₃₃ alloy electrodes reached a maximum when alloys were prepared after 20 h of milling time (260 and 381 mAhg^?1, respectively). The maximum discharge capacity of Mg₅₀Ni₅₀ alloy was observable after 40 h milling (525 mAhg^?1). It was also found that the cyclic stability of the alloys increased with increasing Ni content. Among these alloys, the amorphous Mg₅₀Ni₅₀ alloy presents the best overall electrochemical performance. In this paper, electrode process kinetics of Mg₅₀Ni₅₀ alloy electrode was also studied by means of electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements. The impedance spectra of electrodes were measured at different depths of discharge (DODs). The observed spectra were fit well with the equivalent circuit model used in the paper. The electrochemical parameters calculated from electrochemical impedance were also compared. The electrochemical discharge and cyclic performance of 20, 40 and 60 h milled Mg₅₀Ni₅₀ alloy electrodes were demonstrated by the fitted charge transfer resistance and Warburg impedance obtained at various DODs. It was further observed that the controlling-step of the discharge process changed from a mixed rate-determining process at lower DODs to a mass-transfer controlled process at higher DODs. The fitted results demonstrated that charge–transfer resistance (R_ct) increased with DOD. The R_ct of 40 h milled Mg₅₀Ni₅₀ alloy (29.27 Ω) was lower than that of 20 h (41.89 Ω) and 60 h milled alloys (92.43 Ω) at fully discharge state.     

Structure and hydrogen permeability of V–15Ni alloy

The structure of the V–15Ni at.% alloy before and after hydrogen permeability tests was investigated by means of XRD and SEM with EDS analysis. We have found that decomposition of supersaturated V-based solid solution with variable Ni content occurred during testing. The volume fraction of the solid solution decreased and the fraction of V₃Ni phase increased during permeability testing, thus bringing the alloy to nearly equilibrium. The membrane without Pd coating showed satisfactory hydrogen fluxes with a significant impact of the surface dissociation rate of hydrogen. The shape of hydrogen permeation curves at the downstream side of the membrane at various temperatures was unusual. We attribute it to the high concentration of dissolved hydrogen in the metal lattice and its effect on the hydrogen diffusivity and solubility. In addition, the multiphase structure with non-uniform distribution of nickel both between the phases and within the BCC solid solution (and, consequently, different hydrogen concentrations) may cause dilatation or compressing effect on neighbouring micro-volumes of the alloy.     

Influence of Pd addition on the electrochemical performance of Mg–Ni–Ti–Al-based metal hydride for Ni–MH batteries

Amorphous Mg_0.9Ti_0.1NiAl_0.05 and Mg_0.9Ti_0.1NiAl_0.05Pd_0.1 alloys were prepared by high energy ball milling and evaluated as metal hydride electrodes for Ni–MH batteries. The Mg_0.9Ti_0.1NiAl_0.05Pd_0.1 alloy showed a much higher cycle life with a capacity retention of 72% after 100 cycles (C_100th = 288 mAh g⁻¹) compared to 26% for the Pd-free alloy (C_100th = 117 mAh g⁻¹). This was mainly attributed to the improvement of the alloy oxidation resistance in KOH electrolyte with Pd addition, as confirmed by cyclic voltammetry experiments and X-ray diffraction analyses on cycled electrodes. In addition, in situ acoustic emission (AE) measurements revealed that the energy of the AE signals related to the particle cracking is lower for the Mg_0.9Ti_0.1NiAl_0.05Pd_0.1 electrode, suggesting that the cracks are smaller in size than with the Pd-free alloy. The Mg_0.9Ti_0.1NiAl_0.05Pd_0.1 electrode also displayed a higher discharge rate capability than the Mg_0.9Ti_0.1NiAl_0.05 electrode. On the basis of their respective electrochemical pressure–composition isotherm, it was shown that the presence of Pd in the alloy decreases the thermodynamic stability of the metal hydride. Through a comparative analysis of discharge polarization curves, it was also shown that Pd addition decreases substantially the H-diffusion resistance in the alloy whereas its positive effect on the charge-transfer resistance is limited.     

Hydrogenation of Mg and two chosen Mg–Ni alloys

Structure changes during hydrogenation are observed in pure Mg, Mg₂Ni intermetallic (I) and Mg eutectic alloy – 23.5 wt.% Ni (E). Samples were prepared by (i) ball-milling and compacting (alloys I and E) and (ii) by mould casting (Mg and alloy E). Phase composition was checked by SEM and XRD. It was found that the hydrogenated cast alloy I and ball-milled alloy I hydrogenated below the transition temperature T_tr = 508 K contained a much higher amount of low-temperature un-twinned phase LT1 than the ball-milled alloy I hydrogenated above T_tr. It was shown that micro-twinned phase LT2 slows down the rate of hydrogen desorption. Persistent changes of morphology were observed in all materials after the first hydrogen charging cycle which may explain the so-called activation of Mg-based hydrogen-storage materials described in the literature.     

The effect of the absence of Ni,Co, and Ni–Co catalyst pretreatment on catalytic activity for hydrogen production via oxidative steam reforming of ethanol

This article presents a study of the catalytic performance of Ni, Co, and Ni–Co–Mg–Al mixed oxides obtained from hydrotalcite precursors for the oxidative steam reforming of ethanol (OSRE) when no pretreatment (pre-reduction) is accomplished. Two catalysts (a Ni-based monometallic and an equimolar Ni–Co-based catalyst) achieve in situ reduction over shorter time periods compared with the other bimetallic catalysts and also, exhibit the best catalytic activity. On the contrary, the monometallic Co catalyst did not exhibit good catalytic performance, likely because of the existence of resistant spinel phases to soft reduction processes and/or to the re-oxidation of Co. The equimolar presence of Ni and Co generates a synergistic effect evidenced by the increase in the reducibility, basicity, and mobility of electrophilic oxygen species of the solid. The results yield important information for better understanding the catalytic system under study.     

Hydrogen production from steam reforming of bioethanol using Cu/Ni/K/γ-Al2O3 catalysts. Effect of Ni

Hydrogen to be used as a raw material in fuel cells or even as a direct fuel can be obtained from steam reforming of bioethanol. The key aim of this process is to maximize hydrogen production, discouraging at the same time those reactions leading to undesirable products, such as methane, acetaldehyde, diethyl ether or acetic acid, that compete with H₂ for the hydrogen atoms. Cu–Ni–K/γ-Al₂O₃ catalysts are suitable for this reaction since they are able to produce acceptable amounts of hydrogen working at atmospheric pressure and a temperature of 300°C. The effect of nickel content in the catalyst on the steam-reforming reaction was analyzed. Nickel addition enhances ethanol gasification, increasing the gas yield and reducing acetaldehyde and acetic acid production.     

One-step potentiostatic electrodeposition of Ni–Se–Mo film on Ni foam for alkaline hydrogen evolution reaction

Exploring efficient, abundant, low-cost and stable materials for hydrogen evolution reaction (HER) is highly desired but still a challenging task. Herein, Ni–Se–Mo electrocatalysts supported on nickel foam (NF) substrate were synthesized by a facile one-step electrodeposition method. The Ni–Se–Mo film presents high electrocatalytic activity and stability toward HER, with a low overpotential of 101 mV to afford a current density of 10 mA cm⁻² in 1.0 M KOH medium. Such excellent HER performance of Ni–Se–Mo film induced by the synergistic effects from Mo-doped Ni–Se film leads to the fast electron transfer. This work provides the validity of interface engineering strategy in preparing highly efficient transition metal chalcogenides based HER electrocatalysts.     

Hydrogen absorption characteristics of mechanically alloyed Ti–Zr–Ni and Ti–V–Ni powders

A first investigation into the production of amorphous and nanostructured Ti-based alloys with nominal compositions Ti_41.5Zr_41.5Ni₁₇, Ti₆₁Zr₂₂Ni₁₇, Ti_41.5V_41.5Ni₁₇ and Ti₆₁V₂₂Ni₁₇ by mechanical alloying (MA) technique is presented. This technique was adopted to produce alloys' powders with high fresh surface area that were active for hydrogen storage. Hydrogen absorption characteristics and structure changes in the alloys after hydrogenation were investigated. Gas phase hydrogenation of the Ti–Zr–Ni alloys, at 573 K and an initial hydrogen pressure of 2 MPa, exhibited good hydriding properties and started at a maximal rate without induction period with a hydrogenation capacity up to 1.2 wt%. However, hydriding of Ti–V–Ni alloys at the same conditions exhibited slower rates. The Ti₆₁V₂₂Ni₁₇ composition showed high hydrogen absorption capacity of 1.8 wt% and exceeded 4 wt% at 345 K. In addition, the Ti–V–Ni alloys showed structure stability after hydrogenation and retained the amorphous structure.     

Electrochemical performance of hydrogen evolution reaction of Ni–Mo electrodes obtained by mechanical alloying

Electro active Ni–Mo electrodes have been prepared by mechanical alloying and pressure-less sintering $\text{(1173}\text{K}\text{)}$ Ni and Mo powders. The electrochemical performance of obtained electrodes has been evaluated in KOH 30% at $\text{343}\text{K}$ as a function of the milling time, applied pressure for green compaction as well as the effect conferred by the addition of a process control agent (PCA). Cathodic slope of the best specimen is $\text{279}\text{mV}\text{/}\text{dec}$. Faster reaction kinetics is observed for the specimens treated with PCA addition. The longer milling time and applied pressure on the specimens the better cathodic response. The activation overpotential, i.e. cathodic-Tafel slopes found at high overvoltages are in the range of 274–$\text{481}\text{mV}\text{/}\text{dec}$, whereas the exchange current density for the hydrogen evolution reaction ranged from 27.3 to $\text{1.4}\text{mA}\text{/}\text{cm}{}^2$.     

Hydrogen storage properties of Nb–Hf–Ni ternary alloys

The hydrogen storage properties of Nb_xHf_(1−x)/2Ni_(1−x)/2 (x = 15.6, 40) alloys were investigated with respect to their hydrogen absorption/desorption, thermodynamic, and dynamic characteristics. The PCT curves show that all the specimens can absorb hydrogen at 303 K, 373 K, 423 K, 473 K, 523 K, 573 K, and 673 K, but they couldn't desorb hydrogen below 373 K. The maximum hydrogen absorption capacity reaches 1.23 wt.% for Nb_15.6Hf_42.2Ni_42.2 and 1.48 wt.% for Nb₄₀Hf₃₀Ni₃₀ at 303 K at a pressure of 3 MPa. When the temperature was increased, the hydrogen absorption capacities significantly decreased. However, the hydrogen equilibrium pressure increased. When the temperature exceeded 523 K, the hydrogen equilibrium pressure disappeared. When niobium content was increased, the kinetic properties of hydrogen absorption/desorption improved. The results from the microstructure analysis show that both alloys consist of the BCC Nb-based solid solution phase, the B_f-HfNi intermetallic phase, and the eutectic phase {B_f-HfNi + BCC Nb-based solid solution}. When the Nb content was increased, the volume fraction and Nb content in the Nb-based solid solution phase increased. Thus, the improved kinetics is related to the increase in the primary BCC Nb-based solid solution in the Nb₄₀Hf₃₀Ni₃₀ alloy. The kinetic mechanisms of hydrogen absorption/desorption in these two alloys are found to obey the chemical reaction mechanism at all temperatures tested.     

Hydrogenation and electrochemical studies of La–Mg–Ni alloys

La–Mg–Ni alloys are potential candidates for hydrogen storage materials. In this study, mechanical alloying with subsequent annealing under an argon atmosphere at 973 K for 0.5 h, were used to produce La_2-xMg_xNi₇ alloys (x = 0, 0.25, 0.5, 0.75, 1). Shaker type ball mill was used. An objective of the present study was to investigate an influence of amount of Mg in alloy on electrochemical, hydrogenation and dehydrogenation properties of La–Mg–Ni materials. X-ray diffraction analyses revealed formation of material with multi-phase structure. Obtained materials were studied by a conventional Sievert's type device at 303 K. It was observed that electrochemical discharge capacity and gaseous hydrogen storage capacity of La–Mg–Ni alloys increases with Mg content to reach maximum for La_1.5Mg_0.5Ni₇ alloy. Moreover, all of La–Mg–Ni alloys were characterized by improved hydrogen sorption kinetics in comparison to La–Ni alloy.     

Life duration of Ni–MH cells for high power applications

Intensive research and development carried out at SAFT Research [1], [2] has shown that limitation of Ni–MH battery life duration can be directly linked to AB₅ alloy corrosion in the negative electrode. A mathematical model taking into account these results has been developed in order to predict battery life as a function of the conditions of utilisation: cycle and calendar life [3].However, the degradation of the negative electrode is the consequence of two phenomena: surface corrosion of the active alloy and decrepitation of alloy particles during cycling. Up to now, only the kinetic law controlling the evolution of the thickness of the corrosion layer could have been quantified [3]. On the other hand, the kinetic law of decrepitation could not be directly measured, but is only fitted by determining the total amount of corrosion.Thus, an in situ method suitable to quantify the electrochemical surface of the alloy has been developed. Therefore, electrochemical impedance spectroscopy (EIS) has been used to follow the degradation of the negative electrode, as a function of depth of discharge (DOD) during cycling. Alloy corrosion measurements and scanning electron microscope (SEM) analyses have been performed to confirm the validity of the method. It has been found that decrepitation is nearly zero for low levels of low DOD (5%).     

The electrochemical behavior of Ni–MH battery,Ni(OH)2 electrode and metal hydride electrode

In the past years, the nickel–metal hydride rechargeable battery is already been widely used in many application fields, and is now replacing the nickel–cadmium battery. Electrochemical impedance spectroscopy technique is extensively used to reveal the electrode process kinetics, for example, Pb–H₂SO₄ battery, Ni–Cd battery. There are few reports on the EIS of Ni–MH battery. In this paper, an extensive study is focused on the electrochemical impedance spectroscopy of metal hydride electrode, β–Ni(OH)₂ electrode and Ni–MH battery with different states of charge.     

Synergistic catalysis of MCM-41 immobilized Cu–Ni nanoparticles in hydrolytic dehydrogeneration of ammonia borane

Bimetallic Cu–Ni nanoparticles (NPs) were successfully immobilized in MCM-41 using a simple liquid impregnation-reduction method. All the resulting composites Cu–Ni/MCM-41 catalysts with various contents of Cu–Ni, and in particular Cu_0.2Ni_0.8/MCM-41 sample, outperform the activity of monometallic Cu and Ni counterparts and pure bimetallic Cu_0.2Ni_0.8 NPs in hydrolytic dehydrogeneration of ammonia borane (AB) at room temperature. The Cu_0.2Ni_0.8/MCM-41 catalyst exhibits excellent catalytic activity with a total turnover frequency (TOF) value of 10.7 mol H₂ mol catalyst⁻¹ min⁻¹ and a low activation energy value of 38 kJ mol⁻¹ at room temperature. In addition, Cu_0.2Co_0.8/MCM-41 also exhibits excellent activity with a TOF value as high as 15.0 mol H₂ mol catalyst⁻¹ min⁻¹. This obtained activity represents the highest catalytic active of Cu-based monometallic and bimetallic catalysts up to now toward the hydrolytic dehydrogeneration of ammonia borane (AB). The unprecedented excellent activity has been successfully achieved thanks to the strong bimetallic synergistic effects among the Cu–Ni (or Co) NPs of the composites.     

Kinetics of hydrogen evolution reaction on stabilized Ni,Pt and Ni–Pt nanoparticles obtained by an organometallic approach

Both (Ni, Pt) and bimetallic (Ni_xPt; x = 1, 2, 3) nanoparticles have been synthesized by hydrogenation of Ni(cod)₂ ad Pt₂(dba)₃ in the presence of a weak coordinating ligand, hexadecylamine (CH₃(CH₂)₁₅NH_2, HDA). These nanostructures were characterized by different techniques (Fourier Transform-Infrared Spectroscopy (FT-IR), High-Resolution Transmission Electron Microscopy (HRTEM)), and were evaluated as Hydrogen Evolution Reaction electrocatalysts in 0.5 M sulfuric acid. The effects of varying the platinum amount during the synthesis were systematically studied by Cyclic Voltammetry (CV), polarization measurements and electrochemical impedance spectroscopy (EIS) techniques. HRTEM shows that the bimetallic nanostructures display a different morphology compared to that observed for pure Ni and Pt ones. The process of hydrogen adsorption–desorption in the as-prepared electrodes seems to occur in (110) and (100) facets. It was found that the increase in the activity for the HER is due to an increased electrochemical active surface area (ECSA) and/or stabilization in the case of elemental electrode materials; and to the effect of Pt amount in the case of the Ni–Pt nanostructures (synergistic effect leads to lower overpotential). It has been established that the main pathway for the HER is Volmer–Heyrovsky.     

CO2 reforming of methane over Ni/SBA-15 prepared with β-cyclodextrin – Role of β-cyclodextrin in Ni dispersion and performance

Ni/SBA-15-CD(1/X) catalysts were prepared by the impregnation of a certain amount of Ni(NO₃)₂ and various contents of β-cyclodextrin (CD), in which 1/X indicates the molar ratio of CD to Ni. The physicochemical properties of the catalysts were characterized by BET, XRD, TEM, TPR and TGA, and their catalytic performance in the CO₂ reforming of methane to syngas was evaluated using a fixed-bed quartz reactor. The characterization results revealed that Ni/SBA-15-CD(1/X) prepared with n(CD)/n(Ni) ratios in the range of 1/66–1/33 possessed smaller NiO particles and exhibited stronger interactions between NiO and SBA-15, whereas NiO particles were not well-dispersed on Ni/SBA-15-CD(1/X) catalysts prepared with further CD addition (1/X = 1/8 and 1/1). The reaction results indicated that the better-dispersed Ni/SBA-15-CD(1/X) catalysts, such as Ni/SBA-15-CD(1/66), Ni/SBA-15-CD(1/50) and Ni/SBA-15-CD(1/33), exhibited higher conversions and stronger abilities to resist carbon deposition. Regarding the role of CD in dispersing Ni particles, it could be speculated that complexes were formed between CD and Ni²⁺, as well as NO₃⁻, which would change the state of Ni species during the impregnation and heat treatment processes.