Crystallographic and electrochemical characteristics of melt-spun Ti–Zr–Ni–Y alloys

Ti₄₅Zr₃₀Ni₂₅Y_x (x = 1, 3, 5 and 7) alloys were prepared by melt-spinning at wheel velocity of 20 m s⁻¹. The effect of additive Y on phase structure and electrochemical performance of melt-spun alloys was investigated. Ti₄₅Zr₃₀Ni₂₅Y_x melt-spun alloys were composed of I-phase and amorphous phase. The amorphous phase increased with increasing x value, indicating amorphous forming ability improved with increasing Y content. The maximum discharge capacity and high-rate dischargeability decreased with increasing x value, which may be ascribed to the decrease of nickel content. Cycling stability first increased with increasing x from 1 to 3, and then decreased when x increased to 7, which was resulted from the combined effect of the decrease of nickel content and the increase of amorphous phase.     

Enhanced reversible hydrogen storage properties of a Mg–In–Y ternary solid solution

A Mg(In, Y) ternary solid solution was successfully synthesized by two-step method, namely sintering the elemental powders and subsequent milling. The formation of Mg(In, Y) indicates that the solubility of Y in the Mg lattice is expanded due to the existence of In. The as-synthesized Mg₉₀In₅Y₅ solid solution transformed to MgH₂, YH₃, In₃Y and MgIn compound upon hydrogenation, the hydrogenated products except for the YH₃ recovered to Mg(In, Y) solid solution after dehydrogenation. The Mg₉₀In₅Y₅ solid solution exhibited a decreased reaction enthalpy of 62.9 kJ/(mol H₂), reduction by ca. 5 kJ/(mol H₂) or 12 kJ/(mol H₂) than the Mg₉₅In₅ binary solid solution and pure Mg, respectively. The working temperature as well as the activation energies for the hydriding and dehydriding were also decreased in comparison with those of Mg(In) binary solid solution, which are attributed to the reduced reaction enthalpy and the catalytic role of YH₃. Our work indicates that the thermodynamic and kinetic tuning of MgH₂ are realized in the Mg(In, Y) ternary solid solution.     

Superior electrochemical hydrogen storage properties of binary Mg–Y thin films

Mg–Y thin films capped with Pd have been prepared by direct current magnetron co-sputtering system. It is found that Mg alloyed with Y in film state forms ultrafine nanocrystalline intermetallic compounds. The structure together with the catalytic effect of Y gives rise to a high electrochemical hydrogen storage capacities and superior activation properties. It is worthy to note that Mg₇₈Y₂₂ film achieves a high discharge capacity of 1590 mAh g⁻¹ without requiring activation process. Moreover, Mg alloyed with Y effectively improves the cyclic stability of Mg-based films ascribing to the anti-corrosion role of Y. For Mg₃₇Y₆₃ film, more than 92％ of the maximum discharge capacity can be maintained after 100 charge–discharge cycles.     

Hydrogen storage property improvement of La–Y–Mg–Ni alloy by ball milling with TiF3

Ball milling the powders of Mg-based alloys with transition metal compounds is effective for improving their hydrogen storage performances. In this experiment, the alloys of La_1.7Y_0.3Mg₁₆Ni + x wt.% TiF₃ (x = 0–10) were prepared through mechanical milling technology. XRD, SEM, HRTEM and granulometry were used to measure the composition and microstructure of alloys. The isothermal hydrogen storage property was measured by a Sievert apparatus. The results reveal that the TiF₃ additive in ball-milled samples transforms into MgF₂ and TiH₂ after the first hydrogen absorption. Adding TiF₃ enhances the crystallinity and reduces the average particle and crystallite sizes of alloys, which is beneficial to accelerating hydriding and dehydriding kinetics. Adding 7 wt% TiF₃ into alloy decreases the dehydrogenation activation energy from 72.2 to 64.0 kJ/mol and improves the hydrogen absorption rate at low temperatures, absorbing 3.50 wt% H in 0.5 min at 323 K.     

High glass forming ability correlated with microstructure and hydrogen storage properties of a Mg–Cu–Ag–Y glass

Thermal characterization of an as-cast Mg₅₄Cu₂₈Ag₇Y₁₁ bulk metallic glass revealed that this alloy exhibits excellent glass forming ability. High-resolution X-ray diffraction study and transmission electron microscopy show that heating and isothermal annealing treatment results in the nucleation of nanocrystals of several phases. The average size of these nanocrystals (∼15–20 nm) only slightly varies with prolonged annealing, only their volume fraction increases. High-pressure calorimetry experiments indicate that the as-cast fully amorphous alloy exhibits the largest enthalpy of hydrogen desorption, compared to partially and fully crystallized states. Since the fully crystallized alloy does not desorb hydrogen, it is assumed that hydrogen storage capacity correlates only with the crystalline volume fraction of the partially crystallized Mg₅₄Cu₂₈Ag₇Y₁₁ BMG and additional parameters (crystalline phase selection, crystallite size, average matrix concentration) do not play a significant role.     

Effect of Al content on the structural and electrochemical properties of A2B7 type La–Y–Ni based hydrogen storage alloy

LaY_1.9Ni_10.2−xAl_xMn_0.5 (x = 0–0.6) hydrogen storage alloys have been prepared using a vacuum induction-quenching furnace and annealed at 1148 K for 16 h. The alloys are composed of Ce₂Ni₇- and Gd₂Co₇-type phases and an extra Pr₅Co₁₉-type phase appears when x = 0.6. Aluminum tends to enter the inner AB₅ slabs of Ce₂Ni₇- and Gd₂Co₇-type phases and promotes the generation of new AB₅ slabs. The maximum discharge capacity of the alloy electrodes is stable at approximate 375 mA h/g as x increases from 0 to 0.4 and then decreases to 364.2 mA h/g (x = 0.6). The cycling capacity retention rate at the 300^th cycle is 59.4%, 62.0%, 62.7% and 58.7% for x = 0, 0.2, 0.4 and 0.6, respectively, indicating that the function of aluminum on improving the cyclic stability of the alloy electrodes is limited. The main reason is that the similar pulverization degrees of the alloys are presented during the charge/discharge cycles.     

Study on the characteristics of evaporation–atomization–combustion of biodiesel

A great deal of research is being carried out on renewable diesel fuels. The number of raw materials (especially waste, animal, and vegetable oils), production technologies, and additives of biodiesel is increasing. In our work, a evaporation–atomization–combustion system consisting of a biomass liquid fuel was designed to produce a laminar premixed flame for studying the combustion–emission characteristics of biodiesel. The combustion characteristics of biodiesel including flame height, flame front area, flame speed, and OH total signal intensity were studied by planar laser-induced fluorescence of OH (OH-PLIF). The emission characteristics of biodiesel (CO, CO₂, and NO) were studied with a flue gas analyzer. The experimental results showed that the flame height, flame front area, flame speed, and the OH total signal intensity changed with the equivalence ratio (Φ). The relationship between the OH radical intensity and the emission of CO/CO₂ was obtained from the OH-PLIF average signal intensity. The [CO]/[CO₂] ratio decreased with the OH-PLIF average signal intensity. Finally, we obtained the relationship between the OH-PLIF average signal intensity and the NO emissions.     

Determination of kinetic parameters and hydrogen desorption characteristics of MgH2-10 wt% (9Ni–2Mg–Y) nano-composite

Hydrogen desorption kinetic parameters of MgH₂ compounds were measured and compared with published gas solid reaction models. The compounds investigated in this study were as-received MgH₂, ball milled MgH₂, and MgH₂ ball milled with 9Ni–2Mg–Y catalyst compound. It was determined that different models were necessary to fit the hydrogen desorption data collected at different temperatures on the same sample, indicating that desorption mechanisms changed with respect to temperature. Addition of (9Ni–2Mg–Y) alloy as a catalyst to MgH₂ increased the hydrogen desorption capacity of MgH₂ from zero (for as-received MgH₂) to about 5 wt% at 350 °C within 500 s. The activation energy value was determined as 187 kJ/mol H₂ for the as-received MgH₂, 137 kJ/mol H₂ for 20 h ball milled MgH₂, and 62 kJ/mol H₂ for 20 h ball milled MgH₂-10 wt% (9Ni–2Mg–Y) nano-composite by the Arrhenius and Kissinger methods. Moreover, the integral heat of H₂ desorption for the MgH₂-10 wt% (9Ni–2Mg–Y) nano-composite was measured to be about 78 ± 0.5 kJ/mol H₂ by adsorption micro-calorimetry consistent with the results of the Arrhenius and Kissinger methods.     

Nanoindentation of palladium–hydrogen

Nanoindentation has been utilised to track the mechanical effects of hydrogen on palladium foils over a range of hydrogen concentrations. The miscibility gap in the palladium–hydrogen system yields discrete phases over a range of compositions. It is shown that nanoindentation can measure the extent of hydrogen-induced phase transformations across the film thickness after hydrogen removal, with the α → β → α phase transformations yielding a ∼50% increase in local hardness. Interstitial hydrogen was observed to promote work hardening in β phase regions, and a ∼75% increase in hardness was observed in regions where the α phase was saturated with hydrogen.     

Signal analysis and processing method of transmission optical fiber hydrogen sensors with multi-layer Pd–Y alloy films

To detect hydrogen leakage as soon as possible, researchers try their best to improve the sensitivity and response speed of the hydrogen sensor. However, the sensitivity and response speed are two contradictive parameters. It is hard to improve them simultaneously. The transmission optical fiber sensor with multi-layer films is the only structure which can increase the response speed and enhance sensibility simultaneously. However, because of its special structure, the output signal of the sensor often drifts. This paper designed an in-situ observation system to study the reason why the sensor drifts. The in-situ observation system found a periodic oscillation pattern for the transmission spectrum which depends on the wavelength of the light source. The transmission spectrum patterns of the sensor with multi-layer Palladium–Yttrium (Pd–Y) alloy films under different hydrogen concentrations were analyzed. The source of drift error induced by the wavelength shift of the light source was confirmed. By using a moving average algorithm, the error characteristics of the sensor were analyzed and simulated. The results show that the increased sweep width of the laser can effectively restrain the signal drift of sensors. Particularly, when the sweep width of the laser just is the integer multiples of the period of the transmission spectrum, the suppression of the oscillation was optimal. A sensor with a wavelength-swept laser was implemented. For the sweep width of 1.1 nm, the maximum wavelength sensitivity of the sensor is only 0.046 mv/pm. The wavelength drift error is significantly less than that without signal processing. The sensor has achieved a detection limit of 0.05% which is identical to the sensor with the frequency-stabilized laser. Finally, a design principle was proposed to optimize the light source parameters and structure parameters of the probe for the high stability of the optical fiber hydrogen sensor.     

Function of Al on the cycling behavior of the La–Mg–Ni–Co-type alloy electrodes

The cycling behavior of the _{La0.7Mg0.3Ni2.65-xCo0.75Mn0.1Alx}${\mathrm{La}}_{0.7}{\mathrm{Mg}}_{0.3}{\mathrm{Ni}}_{2.65-x}{\mathrm{Co}}_{0.75}{\mathrm{Mn}}_{0.1}{\mathrm{Al}}_x$(x=0,0.3)$(x=0,0.3)$ alloy electrodes was systematically investigated by XRD, SEM, EIS, XPS and AES measurements, and the function of Al in the La–Mg–Ni-based alloys and the reasons for the improvement of the cycling stability of the alloy electrode with Al were discussed. Results show that the cycling behavior of the _{La0.7Mg0.3Ni2.35Co0.75Mn0.1Al0.3}${\mathrm{La}}_{0.7}{\mathrm{Mg}}_{0.3}{\mathrm{Ni}}_{2.35}{\mathrm{Co}}_{0.75}{\mathrm{Mn}}_{0.1}{\mathrm{Al}}_{0.3}$ alloy electrode can be divided into three stages, i.e., the pulverization and Mg oxidation stage, the Mg oxidation and La and/or Al oxidation stage, and the La and Al oxidation and Al oxide film protection stage. The improvement of the cycling stability of the alloy electrode with Al can be ascribed to two factors. One is the decrease in the pulverization of the alloy particles during charge/discharge cycling due to the alloy with Al undergoes a smaller cell volume expansion and contraction. The other is the increase in the anti-oxidation/corrosion due to the formation of a dense Al oxide film during cycling, which is believed to be the most important reason for the improvement of the cycling stability of the La–Mg–Ni–Co–Mn–Al-type alloy electrodes.     

Effect of Mo–Ni treatment on electrochemical kinetics of La–Mg–Ni-based hydrogen storage alloys

In order to improve kinetic properties of La–Mg–Ni-based hydrogen storage alloys, Mo–Ni treatment was applied to La_0.88Mg_0.12Ni_2.95Mn_0.10Co_0.55Al_0.10 alloy powders. FESEM results showed that after Mo–Ni treatment some network-shaped substance with nano-size formed on the surface of the alloy particles. The EDS results revealed increase in Ni content and emerge of Mo element. EIS and Linear polarization showed that charge-transfer resistance decreased and exchange current density increased for the treated alloy electrode, and the high rate dischargeability (HRD) was consequently improved. HRD at 1500 mA/g increased from 22.5% to 39.5%. Mo- and Ni-single treatments were performed compared with the Mo–Ni treatment, and the results showed that the single treatment improved HRD slightly, far less than the Mo–Ni treatment.     

Effects of hydrogen concentration on premixed laminar flames of hydrogen–methane–air

The unstretched laminar burning velocities and Markstein numbers of spherically propagating hydrogen–methane–air flames were studied at a mixture pressure of 0.10 MPa and a mixture temperature of 350 K. The fraction of hydrogen in the binary fuel was varied from 0 to 1.0 at equivalence ratios of 0.8, 1.0 and 1.2. The unstretched laminar burning velocity increased non-linearly with hydrogen fraction for all the equivalence ratios. The Markstein number varied non-monotonically at equivalence ratios of 0.8 and 1.0 and increased monotonically at equivalence ratio of 1.2 with increasing hydrogen fraction. Analytical evaluation of the Markstein number suggested that the trends could be due to the effective Lewis number, which varied non-monotonically with hydrogen fraction at equivalence ratios of 0.8 and 1.0 and increased monotonically at 1.2. The propensity of flame instability varied non-monotonically with hydrogen fraction at equivalence ratios of 0.8 and 1.0.     

Optimization of the Pd–Sn–GNS nanocomposite for enhanced electrooxidation of methanol

Highly dispersed Pd nanoparticles with varying loadings (15–40 wt%) and (20 − x)%Pd–x%Sn (where x = 1, 2, 3 and 5) nanocomposites are obtained on graphene nanosheets (GNS) by a microwave-assisted ethylene glycol (EG) reduction method for methanol electrooxidation in alkaline solution. The electrocatalysts were characterized by XRD, SEM, TEM, cyclic voltammetry, and chronoamperometry. The study shows that the Pd nanoparticles on GNS are crystalline and follow the face centered cubic structure. Introduction of a small amount of Sn (1–5 wt%) shifts the characteristic diffraction peaks for Pd slightly to a lower angle. The electrocatalytic performance of the Pd/GNS electrodes has been observed to be the best with 20 wt% Pd loading; a higher or lower loading than 20 wt% Pd produces an electrode with relatively low catalytic activity. The apparent catalytic activity of this active electrode at E = −0.10 V is found to improve further by 79% and CO poisoning tolerance by 40% with introduction of 2 wt% Sn. Among the electrodes investigated, the 18%Pd–2%Sn/GNS exhibited the greatest electrocatalytic activity toward methanol electrooxidation.     

A comparative study for synthesis methods of nano-structured (9Ni–2Mg–Y) alloy catalysts and effect of the produced alloy on hydrogen desorption properties of MgH2

9Ni–2Mg–Y alloy powders were prepared by arc melting, induction melting, mechanical alloying, solid state reaction and subsequent ball milling processes. The results showed that melting processes are not suitable for preparation of 9Ni–2Mg–Y alloy due to high losses of Mg and Y. Therefore, 9Ni–2Mg–Y alloy powder was prepared by three methods including: 1) mechanical alloying, 2) mechanical alloying + solid state reaction + ball milling, and 3) mixing + solid state reaction + ball milling. The prepared 9Ni–2Mg–Y alloy powders were compared for their catalytic effects on hydrogen desorption of MgH₂. It is found that 9Ni–2Mg–Y alloy powder prepared by mechanical alloying + solid state reaction + ball milling method has a smaller particle size (1–5 μm) and higher surface area (1.7 m² g⁻¹) than that of other methods. H₂ desorption tests revealed that addition of 9Ni–2Mg–Y alloy prepared by mechanical alloying + solid state reaction + ball milling to MgH₂ decreases the hydrogen desorption temperature of MgH₂ from 425 to 210 °C and improves the hydrogen desorption capacity from 0 to 3.5 wt.% at 350 °C during 8 min.     

Electrochemical hydrogen storage performance of Mg–Ti–Zr–Ni alloys

Mg_1.5Ti_0.5−xZr_xNi (x = 0, 0.1, 0.2, 0.3, 0.4), Mg_1.5Ti_0.3Zr_0.1Pd_0.1Ni and Mg_1.5Ti_0.3Zr_0.1Co_0.1Ni alloys were synthesized by mechanical alloying and their electrochemical hydrogen storage characteristics were investigated. X-ray diffraction studies showed that all the replacement elements (Ti, Zr, Pd and Co) perfectly dissolved in the amorphous phase and Zr facilitated the amorphization of the alloys. When the Zr/Ti ratio was kept at 1/4 (Mg_1.5Ti_0.4Zr_0.1Ni alloy), the initial discharge capacity of the alloy increased slightly at all the ball milling durations. The further increase in the Zr/Ti ratio resulted in reduction in the initial discharge capacity of the alloys. The presence of Zr in the Ti-including Mg-based alloys improved the cyclic stability of the alloys. This action of Zr was attributed to the less stable and more porous characteristics of the barrier hydroxide layer in the presence of Zr due to the selective dissolution of the disseminated Zr-oxides throughout the hydroxide layer on the alloy surface. Unlike Co, the addition of Pd into the Mg–Ti–Zr–Ni type alloy improved the alloy performance significantly. The positive contribution of Pd was assumed to arise from the facilitated hydrogen diffusion on the electrode surface in the presence of Pd. As the Zr/Ti atomic ratio increased, the charge transfer resistance of the alloy decreased at all the depths of discharges. Co and Pd were observed to increase the charge transfer resistance of the Mg–Ti–Zr–Ni alloys slightly.     

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.