Hydrogen generation through rolling using Al–Sn alloy

Mechanically treated aluminum-tin (Al–Sn) alloy, a novel hydrogen-generating material, was fabricated and found to react directly and immediately with water at room temperature. The maximum yield of hydrogen per unit volume of alloy was 2259 mL/cm³ (0.202 g/cm³). The mass ratio of the generated hydrogen and the Al–Sn alloy material was 4.86%. This percentage is much higher than that of traditional hydrogen storage alloys and can compete with metal hydrides. The combination of Al–Sn alloy powder and carbon nanotubes (CNTs) produced a new kind of Al–Sn/CNT composite that also reacts with water at room temperature. Al–Sn/CNT composites were synthesized using a high temperature and high-pressure method. When CNT content was held constant, composites with single-walled CNTs had higher reaction rates than those with multi-walled CNTs. The effects of mechanical treatment and CNT addition on enhancing the reaction between Al–Sn alloys or Al–Sn/CNTs and water were also analysed.     

A methanol – Tolerant carbon supported Pt–Sn cathode catalysts

Carbon supported Pt–Sn bimetallic electrocatalysts with a Pt:Sn 90:10 atomic ratio were prepared by impregnation method and then heat treated at 300 and 500 °C under Helium atmosphere. The purpose of this work is to investigate the effect of tin addition to platinum for methanol tolerant oxygen reduction reaction. In this sense, structure and morphological properties of supported bimetallic catalysts were correlated to the catalytic performance. Powder X-ray diffraction (XRD) and transmission electron microscopy (TEM) characterizations confirm the formation of Pt–Sn bimetallic electrocatalysts with a Pt single-phase material alloy and revealed an increase in the average particle size after heat treatment. The electrocatalytic activities of these samples for the oxygen reduction reaction (ORR) were examined in acidic medium using both a rotating disk (RDE) and a rotating ring disk (RRDE) electrodes. Compared with the Pt/C, Pt–Sn/C bimetallic catalysts show superior electrocatalytic activity towards ORR with an approaching four electron pathway leading to water formation. The specific and mass activity for ORR follow the order of Pt–Sn/C-500 ≈ Pt–Sn/C-300 > Pt–Sn/C > Pt/C. Furthermore, it is found that among the three Pt–Sn samples, Pt–Sn/C-500 exhibits the highest methanol tolerance. These experimental observations indicate that the addition of Sn into Pt is favorable to maximize the ORR performances of platinum and further the heat treatment is beneficial to improve the methanol tolerance behavior. On this basis, the novel Pt–Sn catalysts can be considered as potential candidates to be used as cathodes in Direct Methanol Fuel Cells.     

Preparation of Sn–Co alloy electrode for lithium ion batteries by pulse electrodeposition

Sn–Co alloy films for Li-ion batteries were prepared by pulse electrodeposition on the copper foils as current collectors. Nanocrystalline Sn–Co alloy electrodes produced by using a solution containing cobalt chloride and tin chloride at constant electrodeposition conditions (pulse on-time t_on at 5 ms and pulse off-time t_off at 5 ms) with varying peak current densities, Jp have been investigated. The structures of the electroplated Sn–Co alloy thin films were studied to reveal film morphology current density relationships and the effect of the current density parameters on the electrochemical properties. X-Ray Diffractometer (XRD), Scanning Electron Microscopy (SEM), Brunauer–Emmett–Teller (BET) surface area analyzer and Energy-Dispersive X-ray Spectroscopy (EDS) facilities were used for determination the relationships between structure and experimental parameters. Cyclic voltammetry (CV) tests were carried out to reveal reversible reactions between cobalt–tin and lithium. Galvanostatic charge/discharge (GC) measurements were performed in the cells formed by using anode composite materials produced by pulse electro co-deposition. The discharge capacities of these cells were cyclically tested by a battery tester at a constant current in the different voltage ranges between 0.02 V–1.5 V. The results have shown that Sn–Co alloy yielded promising reversible discharge capacities with a satisfactory cycle life for an alternative anode material to apply for the Li-ion batteries.     

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.     

Thin electrodes based on rolled Pb–Sn–Ca grids for VRLA batteries

Electrodes 0.5 mm thick (i.e. much thinner than conventional ones) and suitable for lead-acid batteries were prepared by using a special pasting procedure that allows plate thickness to be readily controlled. Novel rolled grids of Pb–Sn–low Ca alloys (0.35 mm thick) were used as substrates. Preliminary galvanostatic corrosion tests of the grids revealed an increased corrosion rate relative to conventional casted grids of Pb–Sn alloys (1 mm thick). Cells made with these thin electrodes were cycled under different discharge regimes and the active material at different charge/discharge cycling stages was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and chemical analysis. At a depth of discharge (DOD) of 100%, the cell exhibited a premature capacity loss after the fifth cycle and delivered only a 20% of its nominal capacity after the 10th. By contrast, cycling performance of the electrode was significantly improved at a DOD of 60%. The capacity loss observed at a DOD of 100% can be ascribed to a rapid growth of PbSO₄ crystals reaching several microns in size. Such large crystals tend to deposit onto the grid surface and form an insulating layer that hinders electron transfer at the active material/grid interface. For this reason, the cell fails after few cycles in spite of the high PbO₂ content in the positive active material (PAM). On the other hand, at 60% DOD the submicronic particles produced after formation of the PAM retain their small size, thereby ensuring reversibility in the PbO₂⇔PbSO₄ transformation.     

Ternary Sn–Sb–Co alloy film as new negative electrode for lithium-ion cells

Ternary Sn–Sb–Co alloy film was successfully prepared by the co-electroplating method using an aqueous solution bath containing SnCl₂·2H₂O, CoCl₂, SbCl₃, Na₂C₄H₄O₆·2H₂O, K₃C₆H₅O₇·H₂O, and gelatine. The alloy composition was found to be mainly controllable by the amount of Na₂C₄H₄O₆·2H₂O and SbCl₃ in the plating bath. The Sn–Sb–Co film electrode with a composition of 75.4% Sn, 6.5% Sb, and 18.1% Co gave an initial discharge capacity of 380 mAh g⁻¹. The capacity gradually increased from the 1st to the 10th cycle and was then stabilized at a larger value of 580 mAh g⁻¹. Furthermore, the electrode was found to give better cycle performance compared to binary Sn–Co and Sn–Sb alloys.     

Nanosized Zn–Sn metal composite oxide: a new anode material for Li ion battery

Abstract

The morphological evolution of nanosized Zn–Sn composite oxides, synthesised by the decomposition of ZnSn(OH)₆ precursor at temperature ranged from 300 to 800°C was investigated by using XRD and high resolution TEM. The precursor was also studied by thermal analysis. The electrochemical performance of Zn–Sn composite oxides as anode materials for Li ion batteries was measured in the form of Li/Zn–Sn composite oxides cells. The results reveal that the samples calcined at low temperatures (300 and 500°C) were amorphous Zn₂SnO₄ and SnO₂, and the samples calcined at high temperatures (720 and 800°C) were crystal Zn₂SnO₄ and SnO₂. All the samples have a high reversible specific capacity of over 800 mAh g^?1, and the first charge specific capacity is up to 903 mAh g^?1 for the sample calcined at 500°C. The charge capacity and cyclability were sensitive to the structure and composition of the electrode active materials; the samples calcined at phase transition temperature rage exhibited relatively worse electrochemical properties.     

Investigation of a carbon-supported quaternary PtRuSnW catalyst for direct methanol fuel cells

An investigation was carried out in the electro-oxidation of methanol on a carbon-supported quaternary PtRuSnW catalyst prepared by a liquid-phase reduction method. As derived by X-ray diffraction and X-ray photoelectron spectroscopy, the catalyst was composed of metallic Pt, microcrystalline RuO₂ and SnO₂ phases and amorphous WO₃/WO₂ species. The electrochemical analysis was carried out in half-cell containing sulfuric acid electrolyte as well as in a liquid methanol-fed solid polymer electrolyte single-cell. The activity of catalyst in the half-cell varied as a function of the methanol concentration, it increased with CH₃OH molarity in the activation-controlled region and showed a maximum in 2 M CH₃OH at high currents. IR-free polarization curves showed that the activity of the quaternary catalyst was superior to Pt metal/C samples having the same Pt amount. The presence of semi-insulating metal oxides such as RuO₂, SnO₂ and WO₃ on the electrode surface exhibited a significant uncompensated resistance. The single-cell performance was lower than that predicted by the half-cell experiments mainly due to the methanol cross-over through the Nafion membrane.     

Microstructure and electrochemical performance of thin film anodes for lithium ion batteries in immiscible Al–Sn system

The immiscible Al–Sn alloy thin films prepared by electron-beam deposition were first investigated as possible negative electrodes for lithium ion batteries. In the complex structure of the Al–Sn thin films, tiny Sn particles dispersed homogeneously in the Al active matrix. Their electrochemical characteristics were tested in comparison with the pure Al and Sn films. Cyclic voltammetry results indicated that the Li⁺-transport rates in these Al–Sn alloy films were significantly enhanced. Charge–discharge tests showed that the Al–Sn alloy film anodes had good cycle performance. The electrode with high Al content (Al–33 wt%Sn) delivered a high initial discharge capacity of 752 mAh g⁻¹ while the electrode with high Sn content (Al–64 wt%Sn) had better cycleability with a stable specific capacity of about 300 mAh g⁻¹ under 0.8 C rate. The good performance of these immiscible Al–Sn alloy film anodes was attributed to their unique microstructure. The mechanism of lithiation and delithiation reaction had been proposed based on cyclic voltammograms and impedance response of the Al–Sn alloy thin film electrodes. Our preliminary results demonstrate that the Al–Sn immiscible alloy is a potential candidate negative material for Li-ion battery.     

Cell performance of Pd–Sn catalyst in passive direct methanol alkaline fuel cell using anion exchange membrane

Direct methanol alkaline fuel cell (DMAFC) using anion exchange membrane (AEM) was operated in passive condition. Cell with AEM exhibits a higher open circuit voltage (OCV) and superior cell performance than those in cell using Nafion. From the concentration dependences of methanol, KOH in fuel and ionomer in anode catalyst layer, it is found that the key factors are to improve the ionic conductivity at the anode and to form a favorable ion conductive path in catalyst layer in order to enhance the cell performance. In addition, by using home-made Pd–Sn/C catalyst as a cathode catalyst on DMAFC, the membrane electrode assembly (MEA) using Pd–Sn/C catalyst as cathode exhibits the higher performance than the usual commercially available Pt/C catalyst in high methanol concentration. Therefore, the Pd–Sn/C catalyst with high tolerance for methanol is expected as the promising oxygen reduction reaction (ORR) catalyst in DMAFC.     

Endurance study of a solid polymer electrolyte direct ethanol fuel cell based on a Pt–Sn anode catalyst

The performance decay of a solid polymer electrolyte direct ethanol fuel cell (DEFC) based on a Pt₃Sn₁/C anode catalyst during an endurance test has been investigated. The effect of different cell shut-down procedures on the cycled behaviour of the DEFC has been studied. To get specific insights into the degradation mechanism, polarization and ac-impedance spectroscopy studies have been carried out. These analyses have been complemented by post-operation transmission electron microscopy and X-ray diffraction studies. The combination of these techniques has allowed to get information on recoverable and unrecoverable losses. This provides a basis for further improvement of DEFC components.     

Direct Ethanol Fuel Cells: The influence of structural and electronic effects on Pt–Sn/C electrocatalysts

Carbon-supported platinum-tin electrocatalysts (Pt–Sn/C) are known to be the most efficient fuel cell anode material to oxidize ethanol in the so-called Direct Ethanol Fuel Cells (DEFC). However, the platinum-tin binary system presents distinct phases depending on the amount of Sn (i.e., the Pt:Sn ratio) and on the thermal annealing temperatures, as well as the presence of oxides (e.g. SnO₂) whose influence on the performance of DEFCs is not well understood. In this work, Pt–Sn catalysts presenting distinct Pt:Sn ratios were prepared, characterized and tested in a single DEFC. The combined results from DEFC tests and structural characterization techniques showed that increasing the amount of Sn dissolved into the Pt structure enhances DEFC performance but also that Sn content alone does not explain the overall behavior. Microstructural effects on the DEFC response was further investigated by performing a comprehensive study using high intensity X-ray Diffraction and in situ–X-Ray Absorption Spectroscopy provided by synchrotron light on Pt₃Sn₁/C samples subjected to thermal treatments in a reducing H₂ atmosphere at temperatures of 100, 200, 300, 400, and 500 °C. The results showed that best DEFC performance depends on a balance between the amount of Sn dissolved in Pt, the formation of a new phase (PtSn) and also on the presence of tin oxides, yielding a material with an optimized modified 5d-band electronic structure, which was obtained with a thermal treatment at 200 °C.     

Heterogeneous Ir3Sn–CeO2/C as alternative Pt-free electrocatalysts for ethanol oxidation in acidic media

For reducing the Pt usage and driving down the cost of fuel cells, it is urgent to develop alternative Pt-free catalysts with high catalytic performance. In this study, an Ir₃Sn–CeO₂/C heterogeneous catalyst is designed as low-price, alternative Pt-free electrocatalyst towards ethanol oxidation reaction (EOR) in acidic conditions. Owing to the strong synergistic effect among Ir, Sn and CeO₂ components, Ir₃Sn–CeO₂/C heterogeneous catalyst exhibits higher catalytic activity and stability for EOR in comparison with commercial Pt/C, as-prepared Ir/C and Ir₃Sn/C. Additionally, kinetics and mechanisms of EOR are also investigated. It proves that ethanol electrooxidation on Ir₃Sn–CeO₂/C catalyst is a diffusion controlled irreversible process. Meanwhile, the H₂SO₄ and ethanol concentrations can affect the EOR activity. All results demonstrate Ir₃Sn–CeO₂/C heterogeneous catalyst is a promising Pt-free choice for EOR.     

Effects of Cu substrate morphology and phase control on electrochemical performance of Sn–Ni alloys for Li-ion battery

The influence of substrate morphology and ageing on the charge–discharge performance of a Sn–Ni alloy anode electrodeposited on a Cu substrate are examined. The Sn–Ni alloy (Sn 82 at.%–Ni 18 at.% anode) shows a high capacity of around 480 mAh g⁻¹ up to 12 cycles, but its capacity rapidly fades with cycling. The initial capacity and the cyclic properties of the alloy electrode are significantly improved when the surface morphology of the Cu substrate is changed from smooth-type to nodule-type. Optimized ageing treatment leads to further enhancement in the charge–discharge performance of the anode. The increase in the capacity and better cyclic properties are attributed to stronger adhesion between the Si–Ni anode and the Cu substrate. This is induced by inter-locking of the nodule-type Cu substrate and a buffering effect of Cu–Sn intermetallic compounds formed during ageing.     

One-step electrodeposition of cauliflower-like Ni–Fe–Sn particles as a highly-efficient electrocatalyst for the hydrogen evolution reaction

Herein, a Ni–Fe–Sn coating was synthesized in-situ on Ni mesh by one-step electrodeposition at different durations. The Ni–Fe–Sn60 electrode obtained after 1 h deposition exhibits cauliflower-like morphology and the best electrocatalytic properties for the hydrogen evolution reaction (HER) compared to other electrodes. The electrode requires an overpotential of 43 mV at a current density of 10 mA cm⁻² and a small Tafel slope of 70 mV dec⁻¹ in a 1 M KOH solution. Moreover, the electrode shows outstanding stability in prolonged electrolysis and overall water splitting performance, generating a current density of 93 mA cm⁻² at 1.8 V, which is thrice that of an industry electrode. This electrocatalytic activity is ascribed to the high active surface area produced by the cauliflower-like Ni–Fe–Sn particles and the synergistic interaction of Ni, Fe and Sn. The simple synthesis method and excellent performance endow this electrode with great potential for large-scale applications.     

Effect of decreasing platinum amount in Pt–Sn–Ni alloys supported on carbon as electrocatalysts for ethanol electrooxidation

Literature describes the influence of morphological and structural electrocatalysts characteristics, on the catalytic activity toward ethanol electrooxidation. Thus, in this work Pt and ternary Pt–Sn–Ni alloys nanoparticles, supported on Vulcan carbon, were obtained by impregnation/reduction method. The aim of this work was to evaluate the influence of the decrease of platinum and increase of nickel content of the electrocatalysts obtained. The electrocatalysts were characterized by Rutherford backscattering spectroscopy, X-ray diffraction, transmission electronic microscopy, cyclic voltammetry and electrochemical impedance spectroscopy. The results obtained showed that it was possible to obtain Pt–Sn–Ni nanoparticles with a uniform size distribution in a narrow particle size range with a composition control. Moreover, the simultaneous addition of Sn and Ni to Pt did not affect reticular lattice a value, but the crystallite size decreases significantly. Besides, electrochemical results suggest that the substitution of platinum by nickel, in the electrocalatyst alloys studied, does not compromise the catalytic activity toward ethanol eletrooxidation.     

Influence of Mg, Al, Co, Sn and Sb on the electrical performance of doped β-lead dioxide

The relationship between the hydrogen content of the crystal lattice of PbO₂ and the capacity of PAM is still a subject of interest. The present paper concerns the effect of the doping of β-lead dioxide on the composition of PAM gel zones and its relationship to battery performance.Differential scanning calorimetry (DSC) and thermogravimetry (TG) as well as X-ray diffraction analysis were used as techniques of investigation in this study. The results showed that the quantity of water present in the gel zones and PAM discharge capacity are mainly dependant of the nature of the dopant.     

磁控溅射Sn/Cu/ZnS预置层后硫化法制备Cu_2ZnSnS_4薄膜及其性能研究

采用磁控溅射法制备Sn/Cu/ZnS金属预置层,结合硫化热处理制备Cu_2ZnSnS_4薄膜。利用X射线衍射仪(XRD)、拉曼光谱仪(Raman)、扫描电子显微镜(SEM)、紫外-可见分光光度计(UV-VIS)和霍尔测试系统等一系列测试方法对样品结构、各组分含量、表面形貌、光学带隙及电学性能进行表征及计算。研究结果表明Sn/Cu/ZnS金属预置层经490和540℃硫化热处理后的薄膜均为单一Cu_2ZnSnS_4相,其中,540℃硫化热处理后的薄膜结晶度较高,且薄膜表面平整致密,禁带宽度约为1.58 eV,呈现P型导电。