LiPF6–EC–EMC electrolyte for Li-ion battery

We studied the effect of salt concentration and solvent ratio on the cycling performance of LiMn₂O₄ cathode and graphite anode in LiPF₆–ethylene carbonate (EC)–ethyl methyl carbonate (EMC) electrolytes. The results show that solvent ratio has negligible impact on the performance of both electrodes but does affect the issues of thermal compatibility and ionic conductivity. Salt concentration affects the performance in two reverse ways: LiMn₂O₄ cathode requires low concentration, while graphite anode requires high concentration. It is observed that, during the first cycle, both electrodes produce irreversible capacity and form a solid electrolyte interface (SEI) film on their surface. From the view point of operation at low temperatures, 1 M LiPF₆ 3:7 EC–EMC is recommended for Li-ion cells.     

Phase-separated Ce–Co–O catalysts for CO oxidation

As a major gas pollutant, the control of CO gas emission from chemical industry and vehicle exhausts has aroused global attention in the past years and it is extremely essential to develop efficient, low-cost and environmental friendly catalysts for CO conversion and removal. In this work, we report the facile synthesis of Ce–Co–O catalysts through a simple ultrasonic spray pyrolysis process and investigate their application for low-temperature CO oxidation. The Ce–Co–O catalysts comprising of separated CeO₂ and Co₃O₄ phases show superior CO oxidation capability below 473 K (200 °C) without the assistance of any other co-catalyst or noble metal. With the increase of Co₃O₄ concentration, the CO oxidation temperature of Ce–Co–O catalysts decreases quickly and reaches a complete conversion temperature of 410 K (137 °C) in the case of the optimized Co content. Microstructure analysis using high-resolution transmission electron microscope reveals that the tiny CeO₂ and Co₃O₄ phases assembled into porous particles are well crystallized and show high chemical purity. The porous feature of Ce–Co–O catalysts synthesized from feasible ultrasonic spray pyrolysis makes them more competitive and promising towards gaseous environmental pollution processing including CO oxidation, TWCs, SCR, etc.     

Alkaline composite PEO–PVA–glass-fibre-mat polymer electrolyte for Zn–air battery

An alkaline composite PEO–PVA–glass-fibre-mat polymer electrolyte with high ionic conductivity (10⁻² S cm⁻¹) at room temperature has been prepared and applied to solid-state primary Zn–air batteries. The electrolyte shows excellent mechanical strength. The electrochemical characteristics of the batteries were experimentally investigated by means of ac impedance spectroscopy and galvanostatic discharge. The results indicate that the PEO–PVA–glass-fibre-mat composite polymer electrolyte is a promising candidate for application in alkaline primary Zn–air batteries.     

Multifunctional Co–B–O@CoxB catalysts for efficient hydrogen generation

The development of efficient and non-noble catalyst is of great significance to hydrogen generation techniques. Three surface-oxidized cobalt borides of Co–B–O@Co_xB (x = 0.5, 1 and 2) have been synthesized that can functionalize as active catalysts in both alkaline water electrolysis and the hydrolysis of sodium borohydride (NaBH₄) solution. It is discovered that oxidation layer and low boron content favor the oxygen evolution reaction (OER) activity of Co–B–O@Co_xB in alkaline water electrolysis. And surface-oxidized cobalt boride with low boron content is more active toward hydrolysis of NaBH₄ solution. An alkaline electrolyzer fabricated using the optimized electrodes of Co–B–O@CoB₂/Ni as cathode and Co–B–O@Co₂B/Ni as anode can deliver current density of 10 mA cm⁻² at 1.54 V for overall water splitting with satisfactory stability. Meanwhile, Co–B–O@Co₂B affords the highest hydrogen generation rate of 3.85 L min⁻¹ g⁻¹ for hydrolysis of NaBH₄ at 25 °C.     

Solar–hydrogen energy system for Egypt

A model for a solar–hydrogen energy system for Egypt has been developed by obtaining relationships for and between the main energy and energy related parameters. The magnitude and trends of the parameters, with and without hydrogen introduction, have been investigated over a period of time. The results indicate that the fossil fuel resources in Egypt could be exhausted within one to two decades. They also indicate that adopting the solar–hydrogen energy system would extend the availability of fossil fuel resources, reduce pollution, and establish a permanent energy system for Egypt. They show that Egypt could become an exporter of hydrogen. © 1999 International Association for Hydrogen Energy.     

DRIFTS study of Cu–Zr–Ce–O catalysts for selective CO oxidation

The effects of different components in Cu₁Zr₁Ce₉O_δ catalyst and the variations of the feed stream on the catalytic performance of selective CO oxidation were investigated by diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS) technique. It is found that the active sites of Cu₁Zr₁Ce₉O_δ catalyst are mainly Cu⁺ species. Formate species is formed through the reaction between CO gas and hydroxyl groups on the reduced cerium surface. CeO₂ in the Cu₁Zr₁Ce₉O_δ catalyst facilitates the formation of Cu⁺ species and improves the amount of CO adsorption whereas it is unfavorable to the deep reduction of Cu⁺ species. ZrO₂ doped into the Cu₁Zr₁Ce₉O_δ catalyst increases the Cu coverage and CO adsorption capacity, while it decreases the adsorption of CO₂ on the catalyst surface. The adsorption capacities of oxygen and CO are associated with the catalytic performance for the selective CO oxidation at lower and higher temperatures, respectively. The presence of CO in the feed stream promotes the reduction of Ce⁴⁺ species and the production of geminal OH group on the reduced ceria surface. Hydrogen in the feed diminishes the CO adsorption ability but stimulates the CO desorption. CO₂ in the feed occupies the active sites and decreases the adsorption of the reactants, thus deteriorates the catalytic performance for the selective CO oxidation.     

Linear stability of Rayleigh–Benard–Poiseuille convection for electrochemical system

The effect of Poiseuille flow on the convective stability of electrochemical system is considered. It is found that the effect is destabilizing in the case of oscillatory instability in the system. It is shown that this effect is caused by the fact that the problem is not self-conjugate, because the system is multicomponent. In addition, it is found that the effect of Reynolds number on the stability of these systems is linear at small Reynolds number, in contrast to the self-conjugate Rayleigh–Benard problem, where the effect is quadratic.     

Optimisation of real-time control for hybrid diesel–PV–battery systems

Hybrid diesel–PV–battery systems are one of the most cost effective options for off-grid power generation. A methodology for the optimal operation of such systems for an off-grid application is proposed in this paper. The methodology is based on the minimisation of an energy cost function. Based on this function, an optimal operating point for the diesel generator is identified, taking into account the characteristics of the diesel generator, battery bank and converter as well as the costs of fuel and battery usage. The operation of the diesel generator at this optimum operating point results in an overall energy cost reduction for the hybrid diesel–battery system. Simulation analysis shows that the proposed control strategy can achieve up to 4% reduction in the levelised cost of energy. This is mostly due to the savings made from the efficient usage of diesel generator and battery.     

Novel cake-like Fe–N–C hybrid for H2 activation

The activation and utilization of hydrogen energy is an effective method to solve the global energy crisis and environmental pollution. Herein, biomass-derived Fe–N–C catalysts for H₂ activation were synthesized via the imitation of sponge cake baking. The sample pyrolyzed at 500 °C (Fe–N–C-500) presented the well-defined cake-like architecture with uniform distribution of Fe₃O₄ nanoparticles (NPs). Doping N species dispersed around metallic NPs in high density. Fe–N–C-500 exhibited excellent performance in the catalytic hydrogenation of nitrobenzene. The activity of Fe–N–C-500 depended on Fe₃O₄ NPs and pyridinic N, rather than Fe–N. The typical core-shell structure deemed vital for H₂ activation in previous reports was not necessary. Notably, water could significantly promote the H₂ activation, which might establish the communication between hydrogen molecules adsorbed on Fe₃O₄ NPs and doping N species through hydrogen bonds. Moreover, low temperature pyrolytic Fe–N–C-500 exhibited excellent stability and provided a promising potential for selective hydrogenation of nitroarenes or alkyne by regulating the reaction condition. This work provides an innovative approach to construct heterogeneous catalysts for H₂ activation.     

Platinum–ceria–zirconia catalysts for hydrogen production in sulfur-iodine cycle

In this study, Pt/Ce_1−xZr_x catalysts with different Zr mole concentration (x = 0, 0.2, 0.5, 0.8, 1) have been tested to evaluate their effects on hydrogen iodide (HI) decomposition for hydrogen production in the sulfur-iodine (SI or IS) cycle at various temperatures. The Pt/Ce_1−xZr_x catalysts strongly enhanced the HI conversion to H₂ by comparison with blank test, especially the Pt/Ce_0.8Zr_0.2 catalyst. BET, XRD, TEM, EDS, TPR were performed for catalysts characterization. It was found that, through introducing ZrO₂ into Pt/CeO₂, a synergistic effect between Pt and CeO₂-ZrO₂ solid solution was different from Pt and CeO₂ yield, such as improvement of the thermal stability and increase of Pt-O-Ce reducibility. Among the three samples containing Zr, the one with 20 mol% displayed the best activity for hydrogen production.     

Preparation and performance of novel Li–Ti–Si–P–O–N thin-film electrolyte for thin-film lithium batteries

Novel Li–Ti–Si–P–O–N thin-film electrolyte was successfully fabricated by RF magnetron sputtering from a Li–Ti–Si–P–O target in N₂ atmosphere at various temperatures. XRD, SEM, EDX, XPS, and EIS were employed to characterize their structure, morphology, composition and electrochemical performances. The films were smooth, dense, uniform, without cracks or voids, and possessed an amorphous structure. Their room temperature lithium-ion conductivities were measured to be from 3.6 × 10⁻⁷ S cm⁻¹ to 9.2 × 10⁻⁶ S cm⁻¹, and the temperature dependence of the ionic conductivities fits the Arrhenius relation. This kind of electrolyte possessed good properties is a promising candidate material for solid-state thin-film lithium batteries.     

Nickel–silica core@shell catalyst for methane reforming

Steam reforming of methane from biogas at a small scale could potentially provide a source of hydrogen for applications such as electricity generation via fuel cells. The efficiency of the reforming process is dependent upon an effective catalyst and thus this work aimed to produce a highly active catalyst for methane reforming which is resistant to deactivation. A nickel–silica core@shell catalyst was synthesized by a deposition–precipitation method. The catalyst was characterized by XRD, SEM, TPR and infrared spectroscopy techniques. TEM analyses of sections of the catalyst embedded in resin confirmed that the catalyst had a core@shell structure. Both forms of nickel phyllosilicate 1:1 and 2:1 were identified in the catalyst structure. The performance of the catalyst in methane steam reforming was investigated. The catalyst showed relatively high methane conversion 85% at 750 °C.     

Microstructure and electrochemical properties of Zr–Ti–V–Ni–Mn–LM alloys for application in Ni–MH secondary battery

A series of multi-component Zr_1−xTi_xV_0.4Ni_1.2Mn_0.4LM_y (x=0.3, 0.4; y=0.0,0.02,0.05,0.1,0.2,0.3, LM; lantanum-rich-mischmetal) alloys are prepared and their crystal structure and P–C–T curves are analyzed. The alloys have been modified by adding LM and their gaseous and electrochemical hydrogenation properties are studied to find out the effect of LM elements. Also, the second phase and initial activation performance are investigated. The Zr_1−xTi_xV_0.4Ni_1.2Mn_0.4LM_y (x=0.3,0.4; y=0.0,0.02,0.05,0.1,0.2,0.3) alloys have C14 Laves phase hexagonal structure, so the volume expansion ratio of lattice parameters with LM has increased. As the amount of LM in alloy has increased, correspondingly the second phase is also increased. The second phase is LM, Ti and V-rich. The second phase improve the activation of La-rich misch-metal, and also the concentration of elements Ti, V〉LM〉 matrix in alloys.The addition of LM in Zr_1−xTi_xV_0.4Ni_1.2Mn_0.4LM_y (x=0.3, 0.4) alloys have increased the activation rate and hydrogen storage capacity significantly, but the plateau pressure and the discharge capacity have been decreased due to the formation of second phase. For more Zr in electrode alloys, the activation of rate becomes slow.     

Zinc–nickel alloy electrodeposits for water electrolysis

Electrodeposited zinc–nickel alloys of various compositions were prepared. A suitable electrolyte and conditions to produce alloys of various compositions were identified. Alloys produced on electroformed nickel foils were etched in caustic to leach out zinc and to produce the Raney type, porous electro catalytic surface for hydrogen evolution. The electrodes were examined by polarization measurements, to evaluate their Tafel parameters, cyclic voltammetry, to test the change in surface properties on repeated cycling, scanning electron microscopy to identify their microstructure and X-ray diffraction. The catalytic activity as well as the life of the electrode produced from 50% zinc alloy was found to be better than others.     

Binary Pt–Pd and ternary Pt–Pd–Ru nanoelectrocatalysts for direct methanol fuel cells

Nano-sized binary and ternary alloys are synthesized by polyol process on Vulcan XC72-R support. Nanostructured binary Pt–Pd/C catalysts are prepared either by co-deposition or by depositing on each other. Ternary Pt–Pd–Ru/C catalysts are prepared by co-deposition. The structural characteristics of the nanocatalysts are examined by TEM and XRD. Their electrocatalytic activity toward methanol oxidation and CO stripping curves were measured by electrochemical measurements and compared with that of commercial Pt/C catalyst. The results show that the binary nanocatalyst prepared by depositing the Pt precursor colloids on Pd-Vulcan XC-72R are more active toward methanol oxidation than that of the co-deposited binary alloy nanocatalyst. The co-deposited ternary Pt–Pd–Ru/C nanocatalyst based membrane electrodes assembly shows higher power density compared to the binary nanocatalysts as well as commercial Pt/C catalyst in direct methanol fuel cell. Significantly higher catalytic activity of the nanocatalysts toward methanol oxidation compared to that of the commercial Pt/C is believed to be due to lower level of catalyst poisoning.     

Fast hydriding Mg–Zr–Mn–Ni alloy compositions for high capacity hydrogen storage application

Hydrogen is one of the best alternative to petroleum as an energy carrier. However, the development of a Hydrogen-based economy requires commercialization of safe and cost-effective Hydrogen storage system. In this paper, alloys belonging to Mg–Zr–Mn–Ni alloy system are synthesized using high energy ball milling method. The particle size evolution, chemical analysis and nano-scaled structures were characterized by using SEM, EDXS and XRD techniques, respectively. The optimized - highest hydrogen storing - alloy has particle size of about 8.36 ± 1.17 μm with crystallite size 16.99 ± 5.48 nm. Hydrogen absorption-desorption measurement is carried out on the principle of pressure reduction method. The alloy coded with MZ1 shows uptake of greater than 7 mass % H₂ at a charging temperature of 200 °C, indicating high gravimetric hydrogen storage capacity at relatively lower hydriding temperature. The optimized Mg–Zr–Mn–Ni alloy also shows considerably enhanced hydriding – dehydriding kinetics, compare to pure Mg.     

Ni–Fe–B catalysts for NaBH4 hydrolysis

A series of Ni–Fe–B catalysts with different Fe/(Fe + Ni) molar ratios, used for the hydrolysis of NaBH₄, were prepared by chemical reduction of NiCl₂ and FeCl₃ mixed solution with NaBH₄. The measurements revealed that the catalysts with the molar ratio of Fe/(Fe + Ni) (30%) exhibited the highest catalytic activity, and the optimal reduction temperature is 348 K. In addition, the effects of the concentration of NaBH₄, NaOH and the hydrolytic temperature of NaBH₄ were discussed in detail. The results show that the reaction rate of hydrolysis first rises up and then goes down subsequently with the increase of NaBH₄ concentration, as well as the concentration of NaOH. The activation energy of the hydrolysis for Ni–Fe–B catalysts is fitted to 57 kJ/mol. The maximum value of hydrogen generation is 2910 ml/(min g) at 298 K.     

An exergy–cost–energy–mass analysis of a hybrid copper–chlorine thermochemical cycle for hydrogen production

An exergoeconomic assessment using exergy–cost–energy–mass (EXCEM) analysis is reported of a copper–chlorine (Cu–Cl) thermochemical water splitting cycle for hydrogen production. The quantitative relation is identified between capital costs and thermodynamic losses for devices in the cycle. A correlation detected in previous assessments, suggesting that devices in energy systems are configured so as to achieve an overall optimal design by appropriately balancing thermodynamic (exergy-based) and economic characteristics of the overall system and its components, is observed to apply for the Cu–Cl cycle. Exergetic cost allocations and various exergoeconomic performance parameters are determined for the overall cycle and its components. The results are expected to assist ongoing efforts to increase the economic viability and to reduce product costs of potential commercial versions of this process. The impacts of these results are anticipated to be significant since thermochemical water splitting with a copper–chlorine cycle is a promising process that could be linked with nuclear reactors to produce hydrogen with no greenhouse gases emissions, and thereby help mitigate numerous energy and environment concerns.     

Characterisation of as cast model Mn–Si–Cr–Ni steels for reactor pressure vessel applications

Abstract

Initial results are reported from a study aimed to investigate the role and influence of the elements Cr, Ni, Mn and Si on the radiation stability of reactor pressure vessel steels. Twelve as cast model ferritic steels with basic composition typical of those used in Russian WWER-1000 and Western PWR reactor pressure vessel materials were subjected to Charpy impact, magnetic Barkhausen noise (MBN), Vickers hardness tests and SEM examination. Higher Cr content in model steels was found generally to give increased RMS values independent of Mn and Si contents. The ductile–brittle transition temperatures (DBTT) and hardness values of the model steels were found to be independent of composition. Two steels, with low concentration of Ni and high concentration of Cr or vice versa , showed high transition temperatures (?16 and ?42°C respectively). An additional heat treatment to improve the properties is being considered for these compositions. The correlation between DBTT and MBN results has potential for rapid determination of the effect of composition and irradiation on the steel properties. The next stage of the assessment will investigate the effect of irradiation of the model steels to accumulated neutron fluences of ～10¹⁹ cm^?2.