Activation characteristics and microstructure of composite hydrogen storage alloys prepared by two-step re-melting

In the present work, novel composites (x=0,5,10,30) for hydrogen storage were prepared by two-step re-melting and their activation characteristic and microstructure were investigated. The influence of Mg₂Ni content on the activation characteristics was analyzed by electrochemical method. With the increasing content of Mg₂Ni, activation characteristics and maximum discharge capacities of composites increase first and then decrease. The composite with 5% Mg₂Ni has the least cycle number for activation and the highest discharge capacity. It is activated after only 6 cycles (C_n=6) at room temperature and its maximum discharge capacity (C_max) reaches 274.4 mAh/g. However, the composite contained 30 wt% Mg₂Ni is difficult to be activated at room temperature. It is also found that it is easier to be activated for the composites at and than that at and , but their discharge capacity decay slightly at the condition of and . The XRD and SEM analysis show that, with the increasing Mg₂Ni content, the microstructure of the composites varies gradually from lamellar (x=5), acicular (x=10) to massive (x=30), and the activity of the composite declines as a result of the grain size of phase Mg₂Ni grows up.     

Preparation of thin films by sulfurizing sol–gel deposited precursors

Cu₂ZnSnS₄ (CZTS) thin films were prepared by sulfurizing precursors deposited by the sol–gel method. Copper (II) acetate monohydrate, zinc (II) acetate dihydrate and tin (II) chloride dihydrate were used as the starting materials of the sol–gel method, and 2-methoxyethanol and monoethanolamine were used as the solvent and the stabilizer, respectively. The solution was spin coated on soda lime glass substrates and dried at . The coated glasses were sulfurized by annealing at in a hydrogen sulfide-containing atmosphere. The annealed thin films showed X-ray diffraction peaks attributed to the single phase CZTS. The chemical composition of the films was almost stoichiometric and the band gap energy was at room temperature.     

Dye-sensitized solar cell using natural dyes extracted from rosella and blue pea flowers

Dye-sensitized solar cells (DSSCs) were fabricated using natural dyes extracted from rosella, blue pea and a mixture of the extracts. The light absorption spectrum of the mixed extract contained peaks corresponding to the contributions from both rosella and blue pea extracts. However, the mixed extract adsorbed on TiO₂ does not show synergistic light absorption and photosensitization compared to the individual extracts. Instead, the cell sensitized by the rosella extract alone showed the best sensitization, which was in agreement with the broadest spectrum of the extract adsorbed on TiO₂ film. In case that the dyes were extracted at , using water as extracting solvent, the energy conversion efficiency (η) of the cells consisting of rosella extract alone, blue pea extract alone and mixed extract was 0.37%, 0.05% and 0.15%, respectively. The sensitization performance related to interaction between the dye and TiO₂ surface is discussed. The explanations are supported by the light absorption of the extract solution compared to extracts adsorbed on TiO₂ and also dye structures. The effects of changing extracting temperature, extracting solvent and pH of the extract solution are also reported. The efficiency of rosella extract sensitized DSSC was improved from 0.37% to 0.70% when the aqueous dye was extracted at instead of and pH of the dye was adjusted from 3.2 to 1.0. Moreover, DSSC stability was also improved by the changes in conditions. However, the efficiency of a DSSC using ethanol as extracting solvent was found to be diminished after being exposed to the simulated sunlight for a short period.     

Microcrystalline silicon deposited at high rate on large areas from pure silane with efficient gas utilization

Microcrystalline silicon thin film deposited by RF-PECVD and integrated in a tandem structure is a promising material for low cost photovoltaic solar cells compared to solar cells based on crystalline silicon. However, in order to allow a cost-effective mass production of solar cells based on this material, deposition processes should fulfill several conditions such as high deposition rate, good uniformity over large area and efficient gas utilization. In this work, it is shown that the atomic hydrogen density can be high enough to form microcrystalline thin films even from a pure silane RF discharge and that the pure silane regime is more efficient in terms of gas utilization. In situ Fourier transform infrared absorption and ex situ Raman spectroscopy measurements have been used to determine the fraction of dissociated silane in the discharge and the crystallinity of the deposited layers. Results have shown that microcrystalline silicon can be deposited uniformly on a large area substrate with a deposition rate of more than with a low powder formation and an input power density of from a pure silane discharge.     

Nafion/PTFE/silicate membranes for high-temperature proton exchange membrane fuel cells

Fuel cell performance of membrane electrode assemblies (MEAs) prepared from poly(tetrafluoroethylene)/Nafion/silicate (PNS) membrane and Nafion-112 membrane were investigated. Due to the low conductivity of PTFE and silicate, PNS had a higher proton resistance than Nafion-112. However, in this work we show that PNS performs better than Nafion-112 for a high current density operation with a low inlet gas humidity. As the PEMFCs were operated at with 100% RH, the results showed the maximum power density (PD_max) of PNS was: at with both H₂ and O₂ flow rates of 300 ml/min, and at with H₂ flow rate of 360 ml/min and O₂ flow rate of 600 ml/min, which were much higher than the at of Nafion-112 with both H₂ and O₂ flow rates of 300 ml/min. The PD_max of PNS was: , , and at as the operating temperature and inlet gas humidity were set at with 67.7% RH, with 46.8% RH, and with 33.1% RH, respectively. However, no output power was detected for Nafion-112 MEA when the cell was operated at a temperature higher than and an inlet gas humidity lower than 67.7% RH. The high PEMFC performance of PNS at high current density and low humidity is attributed to the presence of silicate in the PNS membrane, which enhances water uptake and reduces electro-osmosis water loss at a high current density.     

Mass production of alloy bulk by isothermal evaporation casting process

An innovative method, isothermal evaporation casting process (IECP), is developed to produce Mg₂Ni alloy for mass production in this work. In the past, high vapor pressure of Mg was considered as a disadvantage for producing pure Mg₂Ni alloy. However, this characteristic was used to develop a refinement procedure to separate primary Mg₂Ni alloy from Mg/Mg₂Ni eutectic matrix. Characteristics of as-cast specimens measured by X-ray diffraction (XRD), inductively coupled plasma-atomic emission spectroscopy (ICP-AES) and electron probe X-ray microanalyzer (EPMA) reveal that mass production of single phase Mg₂Ni alloy was successfully fabricated by IECP. For every 4.0 kg of raw materials, alloy bulk was extracted at a yield of about 65%. The hydrogen storage capacity of the well-activated Mg₂Ni alloy reaches 3.58 wt% at 300 °C under 40 atm H₂ atmosphere which is close to the theoretical capacity of 3.6 wt%.     

Carrier collection in Cu(In,Ga)Se2 solar cells with graded band gaps and transparent ZnO:Al back contacts

Cu(In,Ga)Se₂ Solar cells with graded band gap and efficiencies up to 13% have been fabricated on transparent ZnO:Al back contacts. The back contact structure includes a transparent 10 nm thin Mo interlayer with NaF precursor between the ZnO:Al and the Cu(In,Ga)Se₂ absorber that transforms the blocking ZnO:Al/Cu(In,Ga)Se₂ interface into an Ohmic back contact. To investigate the electronic quality of the back contact, the cells are analyzed by internal quantum efficiency measurements under illumination from front and back side. A new semianalytical model for the quantum efficiency of graded band gap absorbers yields quantitative information about the back contact recombination velocity as well as optical and electronic material parameters of the absorber layer. Band gap grading significantly increases carrier collection. However, in the immediate vicinity of the back contact carrier collection is limited by a high ratio of back contact recombination velocity and diffusion constant .     

Flow channeling in a single fracture induced by shear displacement

The effect on the transport properties of a fracture of a shear displacement between its complementary surfaces is investigated experimentally and numerically. The shear displacement induces an anisotropy of the fracture aperture field with a correlation length scaling of , which is significantly larger in the direction perpendicular to . This reflects the presence of long fluid flow channels perpendicular to the shear displacement, resulting in a higher effective permeability in that direction. Such channels will have a strong influence on the transport characteristics of a fracture, such as, for instance, its thermal exchange area, crucial for geothermal applications. Miscible displacement fronts in shear-displaced fractures obtained experimentally display a self-affine geometry with a characteristic exponent directly related to that of the fracture surfaces. We present a simple model, based on the channeling of the aperture field, which reproduces the front geometry when the mean flow is parallel to the channels created by the shear displacement.     

An optimal operating window for the Bunsen process in the I–S thermochemical cycle

We searched for the optimal compromised operating conditions for the Bunsen reaction of IS thermochemical water splitting, considering the key concerns of the IS cycle: the liquid–liquid equilibrium (LLE) phase separation performance, the characteristics of water distribution between the sulfuric acid (SA) phase and the poly-hydroiodic acid (HI_x) phase, side reaction occurrence, and the effect on operating costs. Experimental data available from a literature survey were combined, and common trends were examined through a series of parametric studies. Based on the results, the optimal operating point and allowable operating window for the Bunsen reaction have been proposed: the optimal point is represented by 4 mol of excess iodine and 11 mol of excess water in the stoichiometry at temperature of 330 K, while the allowable window ranges over for the excess iodine, for the excess water, and for the temperature. After the Bunsen reaction and LLE phase separation, 5 mol of the excess water is distributed to the SA phase and to the HI_x phase. Operating within this window makes it possible to avoid the side reaction and iodine solidification, to increase the HI concentration well above the azeotropic point in the HI_x section, and to minimize operating costs arising from excess iodine and water.     

Studies on synthesis and dehydrogenation behavior of magnesium alanate and magnesium–sodium alanate mixture

Magnesium alanate (Mg(AlH₄)₂) has been synthesized by mechanochemically activated metathesis reaction involving MgCl₂ and NaAlH₄. Its dehydrogenation kinetics and storage capacity has been studied by using Sievert's type apparatus. We have obtained dehydrogenation capacity of 2.7 wt% H₂ from Mg(AlH₄)₂+2NaCl during the first decomposition step at and 1.1 wt% H₂ during second step decomposition at . Efforts were carried out to reduce NaCl content from the product using Soxhlet extraction technique. The Soxhlet extracted product gives the total dehydrogenation capacity of 4.7 wt% H₂. To enhance the storage capacity, we have synthesized a complex hydride consisting of mixture: xMg(AlH₄)₂+yNaAlH₄ (0<x<1,y1). In the alanate mixture 0.5Mg(AlH₄)₂+NaAlH₄, the dehydriding temperature of NaAlH₄ gets lowered by (from to ) with 4 times faster desorption kinetics. The total hydrogen liberated in 180 min from NaAlH₄+0.5Mg(AlH₄)₂(+NaCl) mixture at has been observed to be 3.7 wt% H₂.     

Ex situ investigation of the proton exchange membrane chemical decomposition

The durability of Nafion^® polymer electrolyte membranes (PEMs) with potential application in PEM fuel cells has been investigated using accelerated durability tests to understand their degradation mechanism. After the attack by Fenton radicals, the Nafion^®111 membranes and the solution produced were collected for analysis. The existence of F ions in the solution indicated the chemical decomposition of the Nafion^® membranes during radical attacks. The F^- emission rate (FER) was about , corresponding to 0.024 wt% of F released from the membrane per hour. The NMR and FTIR spectrums demonstrated the polymer fragments mostly existed as whole side chains of the Nafion^® membrane. This result revealed that the degradation was originated from the decomposition of polymer main chain. Furthermore, the reflectance-FTIR revealed that the degradation of the PEMs was from the decomposition of the repeating units in the polymer main chains. With the increased loss of repeating units, small bubbles with the diameter of several microns started to form in Nafion^® membrane. These bubbles made the membrane vulnerable to hazards of gas crossover, which further led a catastrophic failure of the proton exchange membrane.     

Photocatalytic hydrogen evolution over CuCrO2

We have been studying the technical feasibility of a photochemical H₂ evolution based on a dispersion of CuCrO₂ powder in aqueous electrolytes containing various reducing agents (S²⁻, and ). The title oxide combines a fair resistance to corrosion with an optimal band gap E_g of 1.32 eV. The intercalation of a small amount of oxygen should be accompanied by a partial oxidation of Cu⁺ into Cu²⁺ implying a p-type semiconductivity. The S²⁻ oxidation inhibits the photocorrosion and the H₂ evolution increases parallel to polysulfides formation. Most of H₂ is produced when p-CuCrO₂ is connected to n-Cu₂O formed in situ. H₂ liberation proceeds mostly on CuCrO₂ while the oxidation of S²⁻ takes place over Cu₂O surface and the hetero system Cu₂O/CuCrO₂ is optimized with respect to some physical parameters. The photoactivity is dependent on preparation conditions and lowering the synthesis temperature through nitrate route leads to an increase in specific surface area S_sp. The photoelectrochemical H₂ production is a multistep process where the rate determining step is the arrival of electrons at the interface because of their low mobility. Prolonged irradiation (>80 min) leads to a pronounced decrease of the photoactivity; the tendency toward saturation is due to the undesired back reduction of polysulfides in a closed system and to their strong absorption in the visible region (λ_max = 520 nm).     

Investigation on microstructures and electrochemical performances of hydrogen storage alloys

In order to improve the cycle stability of La–Mg–Ni system (A₂B₇-type) alloy electrode, a small amount of Co was added in the La_0.75Mg_0.25Ni_3.5 alloy. The effects of Co content on the microstructures and electrochemical performances of the alloys were investigated in detail. The results by XRD and SEM show that the alloys have a multiphase structure which is composed of the LaNi₅, (La,Mg)₂Ni₇ two major phases and a small amount of the LaNi₂ phase. The cell volumes of the LaNi₅ and phases enlarge with the increasing Co content in the alloys. With the increasing Co content, some electrochemical properties and kinetic parameters of the alloy, involving the discharge capacity, high-rate discharge ability (HRD), the polarization resistance (R_p), the loss angle (ψ) and the limiting current density (I_L), first increase and then decrease. The addition of Co slightly improves the cycle stabilities of the alloy electrodes. The mechanism of the efficiency loss of the experimental alloy was investigated by means of SEM and X-ray photoelectron spectroscopy (XPS). The results indicate that the fundamental reasons for the capacity decay of the La_0.75Mg_0.25Ni_3.5Co_x (x=0,0.2,0.4,0.6) alloy electrodes are the pulverization of the alloy particle and corrosion/oxidation of La and Mg in alkaline electrolyte.     

Plasma-enhanced chemical vapor deposition of zinc oxide at atmospheric pressure and low temperature

The plasma-enhanced chemical vapor deposition of aluminum-doped zinc oxide has been demonstrated for the first time at 800 Torr and under 250 °C. A film resistivity of and a transparency of 95% from 375 to 2500 nm was obtained for deposition at 20-mTorr diethylzinc, 1.0 Torr CO₂, 799 Torr He, a TMAl/DEZn ratio of 1:100, RF power, and 225 °C. The average aluminum concentration in the ZnO film was . It was found that, while the growth rate did not change with substrate temperature, both the resistivity and optical absorption coefficient declined with increasing temperature.     

Testing solar collectors as an energy source for a heat pump

The article presents the experimental study of a heat pump possessing solar collectors as an energy source. A method to test the combined work of collectors delivering heat to the evaporator of a heat pump was devised. The layout of the test facility is shown and the system construction with the measurement equipment is described. The planning experiment to test the installation was chosen. The medium fluid condenser temperature , the fluid condenser mass flow rate and the medium fluid evaporator temperature were chosen as experiment factors to determine both objective functions—the coefficient of performance (COP) of the heat pump and the efficiency of the system η_s. The reverberation of both objective functions is shown.     

Methodology for predicting sequences of mean monthly clearness index and daily solar radiation data in remote areas: Application for sizing a stand-alone PV system

In this paper, a suitable adaptive neuro-fuzzy inference system (ANFIS) model is presented for estimating sequences of mean monthly clearness index () and total solar radiation data in isolated sites based on geographical coordinates. The magnitude of solar radiation is the most important parameter for sizing photovoltaic (PV) systems. The ANFIS model is trained by using a multi-layer perceptron (MLP) based on fuzzy logic (FL) rules. The inputs of the ANFIS are the latitude, longitude, and altitude, while the outputs are the 12-values of mean monthly clearness index . These data have been collected from 60 locations in Algeria. The results show that the performance of the proposed approach in the prediction of mean monthly clearness index is favorably compared to the measured values. The root mean square error (RMSE) between measured and estimated values varies between 0.0215 and 0.0235 and the mean absolute percentage error (MAPE) is less than 2.2%. In addition, a comparison between the results obtained by the ANFIS model and artificial neural network (ANN) models, is presented in order to show the advantage of the proposed method. An example for sizing a stand-alone PV system is also presented. This technique has been applied to Algerian locations, but it can be generalized for any geographical position. It can also be used for estimating other meteorological parameters such as temperature, humidity and wind speed.     

Measurement of effective oxygen diffusivity in electrodes for proton exchange membrane fuel cells

This paper describes a novel method to measure directly effective diffusivity in electrodes as a function of temperature and relative humidity (RH) at conditions that are relevant for proton exchange membrane fuel cells (PEMFCs). The efficacy of this method to measure effective oxygen diffusivity is demonstrated with measurements of a series of electrodes of varying the ionomer-to-carbon weight ratio (I/C ratio). The measured decreases sharply with increasing I/C ratio from 0.5 to 1.5 at the same RH, and reduces gradually with increasing RH from 0% to 100% at the same I/C ratio. The measured is considerably smaller than the calculated one using the Bruggeman correction, indicating the Bruggeman correction drastically underestimates the tortuosity with increasing I/C ratio in PEMFC electrodes.     

Development of a 700 W anode-supported micro-tubular SOFC stack for APU applications

A 700 W anode-supported micro-tubular solid-oxide fuel cell (SOFC) stack for use as an auxiliary power unit (APU) for an automobile is fabricated and characterized in this study. For this purpose, a single cell was initially designed via optimization of the current collecting method, the brazing method and the length of the tubular cell. Following this, a high-power single cell was fabricated that showed a cell performance of at 0.7 V and using H₂ (fuel utilization=45%) and air as fuel and oxidant gas, respectively. Additionally, a fuel manifold was designed by adopting a simulation method to supply fuel gas uniformly into a single unit cell. Finally, a 700 W anode-supported micro-tubular SOFC stack was constructed by stacking bundles of the single cells in a series of electrical connections using H₂ (fuel utilization=49%) and air as fuel and oxidant gas, respectively. The SOFC stack showed a high power density of ; moreover, due to the good thermo-mechanical properties of the micro-tubular SOFC stack, the start-up time could be reduced by 2 h, which corresponds to 6/min.     

Efficient organic tandem cell combining a solid state dye-sensitized and a vacuum deposited bulk heterojunction solar cell

In this letter, we report on an efficient organic tandem solar cell combining a solid state dye-sensitized with a ZnPc/C₆₀-based, vacuum deposited bulk heterojunction solar cell. Due to an effective serial connection of both subcells and to the complementary absorption of the dyes used, a power conversion efficiency of η_p=(6.0±0.1)% was achieved under simulated AM 1.5 illumination. The device parameters are , and FF=(54±1)%.     

Cyclic hydrogen absorption–desorption characteristics of TiCrV and alloys

The cyclic hydrogen absorption–desorption characteristics of TiCrV and Ti_0.8Cr_1.2V alloys are investigated. Experimental results show that the cyclic hydrogen capacity increases with increasing hydrogen-desorption temperature for both TiCrV and Ti_0.8Cr_1.2V alloys. The Ti_0.8Cr_1.2V and TiCrV alloys can maintain steady cyclic hydrogen capacities of about 2.5 wt% and 2.0 wt%, respectively, even after 15 cycles with hydrogen absorption at and hydrogen desorption at . The hydrogenation for both TiCrV and Ti_0.8Cr_1.2V alloys includes the processes of first saturated solid-solution and then forming TiCr_1.8H_5.3 and TiH₂ hydrides. The TiCr_1.8H_5.3 hydride has better reversibility than TiH₂ hydride during the hydrogen absorption–desorption.