Photoelectrochemical dissociation of water at silicon doped n-GaAs electrodes

The photoelectrochemical properties of silicon-doped n-GaAs were studied in aqueous solution of different pH values. The photosensitivity is higher in alkaline than in acidic solutions. However, visual photocorrosion, and deterioration of photocurrent could be observed after few hours of illumination in 0.1 M NaOH solution. The corrosion was decreased by coating the GaAs electrode with a 50 Å thick gold layer. If GaAs was used as an anode in an electrochemical cell, and illuminated with visible light (4200 Å < λ < 6000 Å), photocurrent was observed due to the generation of H₂ over a Pt counter electrode. The photocurrent generated in 0.1 M NaOH solution has an onset potential of −1.1 V (NHE). Furthermore, it saturated at a potential of −0.3 V (NHE). Both the rate of H₂-production and photocurrent varied linearly with light intensity. The quantum efficiency for the hydrogen production is 0.4 hydrogen atom per second per photogenerated electron-hole pair. Our results are explained in the light of the band model of the semiconductor-solution interface.     

Determination of the equilibrium constant and standard free energy of the over-potentially deposited hydrogen for the cathodic H2 evolution reaction at the Pt–Rh alloy electrode interface using the phase-shift method

The Langmuir adsorption isotherm of the over-potentially deposited hydrogen (OPD H) for the cathodic H₂ evolution reaction (HER) at the Pt–Rh (Pt:Rh; 80:20 wt%) alloy/0.5 MH₂SO₄ aqueous electrolyte interface has been studied using cyclic voltammetric and ac impedance techniques. The behavior of the phase shift (0°−φ90°) for the optimum intermediate frequency can be linearly related to that of the fractional surface coverage (1θ0) of the OPD H for the cathodic HER at the interface. The phase-shift profile (−φ vs. E) for the optimum intermediate frequency, i.e., the phase-shift method, can be used as a new electrochemical method to determine the Langmuir adsorption isotherm (θ vs. E) of the OPD H for the cathodic HER at the interface. At the Pt–Rh alloy electrode interface, the equilibrium constant (K) and the standard free energy (ΔG_ads) of the OPD H are 2.2×10⁻⁴ and 20.9 kJ/mol, respectively. At the steady state, the behaviors of the cyclic voltammogram and the Langmuir adsorption isotherm of the OPD H for the cathodic HER at the Pt–Rh alloy electrode interface are similar to those of the pure Pt electrode interfaces. At the steady state, the effect of Rh on the OPD H for the cathodic HER can be neglected at the Pt–Rh (Pt:Rh; 80:20 wt%) alloy/0.5 MH₂SO₄ aqueous electrolyte interface.     

Thermodynamic evaluation of water splitting by a cation-excessive (Ni, Mn) ferrite

Water-splitting potential by cation-excessive (Ni, Mn) Ferrite, Ni_{0.5(1 + )}Fe_{1.99(1 + )}O₄ was evaluated using the standard Gibbs free energy change (ΔG°) for the cation-excessive ferrite formation in different O₂ partial pressures. The cation-excessive degree ranged from 0.026 to 0.16 in pO₂ values of 7.9 × 10⁻⁷ to 1.0 × 10⁻¹. From the relation between value of (Ni, Mn) ferrite and oxygen partial pressure, equilibrium constant K(th) was determined. Furthermore ΔH°s for O₂ releasing and water-splitting reactions with cation-excessive (Ni, Mn) ferrite were evaluated from the van't Hoff plot and compared with that for magnetite-wüstite system; where ΔH°s were assumed to be the same values for both (Ni, Mn) ferrite and magnetite-wüstite system: +300 kJ for O₂ releasing and −35 −63 kJ for water-splitting. ΔG°s evaluated for water-splitting with cation-excessive (Ni, Mn) ferrite and wüstite were −38 kJ and −35 kJ, respectively, at 298K. It suggests that water splitting with cation-excessive (Ni, Mn) ferrite proceed easily compared with that with wüstite. ΔS°s for water-splitting are −0.93 kJ K⁻¹ for the former and −0.83 kJ K⁻¹ for the latter. H₂ generation rates by reaction with H₂O for (Ni, Mn) ferrite were studied at temperatures of 573 K-1073 K. It reached the maximum at 1000 K while it proceeds preferentially below 830 K from thermodynamics.     

Ethylene carbonate-based organic electrolytes for high performance aluminium electrolytic capacitors

The utilization of ethylene carbonate (EC)-based solutions has been examined as the electrolyte of aluminium electrolytic capacitors. The electrolytic conductivities of alkylammonium salts in the solutions containing propylene carbonate (PC), γ-butyrolactone (BL) or sulfolane (S) as a co-solvent varied with both the solvent composition and the ion size of the salt. The maximum conductivity of 0.5 M tetraethylammonium hydrogen maleate (TEAM), 9.8 × 10⁻³ S cm⁻¹, was obtained in a 20 mol% EC+80 mol% BL composition. The thermal stability of the electrolyte solution varied also with the electrolyte composition; the solutions containing higher mol% EC tended to be unstable towards thermal stimulation. The anodic behaviour of the formation of aluminium oxide was briefly examined in the EC-based electrolytes containing small amounts of water. The oxide films formed in the TEAM solutions were highly resistant to corrosion, suggesting that the present electrolyte system has a high ability for the oxide film restoration in the capacitor.     

Decomposition of nitrous oxide at medium temperatures

Flow reactor experiments were done to study the decomposition of N₂O at atmospheric pressure and in a temperature range of 600–1000°C. Dilute mixtures of N₂O with H₂, CH₄, CO with and without oxygen with N₂ as carrier gas were studied. To see directly the relative importance of the thermal decomposition versus the destruction by free radicals (i.e.: H, O, OH) iodine was added to the reactant mixture suppressing the radicals’ concentrations towards their equilibrium concentrations. The experimental results were discussed using a detailed chemistry model. This work shows that there are still some uncertainties regarding the kinetics of the thermal decomposition and the reaction between N₂O and the O radical. Using the recommendations applied in this work for the reaction N₂O + M ↔ N₂ + O + M and for N₂O + O ↔ products, a good agreement with the experimental data can be obtained over a wide range of experimental conditions. The reaction between N₂O and OH is of minor importance under present conditions as stated in latest literature. The results show that N₂O + H ↔ N₂ + OH is the most important reaction in the destruction of N₂O. In the presence of oxygen it competes with H + O₂ + M ↔ HO₂ + M and H + O₂ ↔ O + OH, respectively. The importance of the thermal decomposition (N₂O + M ↔ N₂ + O + M) increases with residence time. Reducing conditions and a long residence time lead to a high potential in N₂O reduction. Especially mixtures of H₂/N₂O and CO/H₂O/N₂O in nitrogen lead to a chain reaction mechanism causing a strong N₂O reduction.     

Plasma catalytic reforming of methane

Thermal plasma technology can be efficiently used in the production of hydrogen and hydrogen-rich gases from methane and a variety of fuels. This article describes progress in plasma reforming experiments and calculations of high temperature conversion of methane using heterogeneous processes. The thermal plasma is a highly energetic state of matter that is characterized by extremely high temperatures (several thousand degrees Celsius), and a high degree of dissociation and a substantial degree of ionization. The high temperatures accelerate the reactions involved in the reforming process. Hydrogen-rich gas (40% H₂, 17% CO₂ and 33% N₂, for partial oxidation/water shifting) can be efficiently made in compact plasma reformers. Experiments have been carried out in a small device (2–3 kW) and without the use of efficient heat regeneration. For partial oxidation/water shifting, it was determined that the specific energy consumption in the plasma reforming processes is 16 MJ/kg H₂ with high conversion efficiencies. Larger plasmatrons, better reactor thermal insulation, efficient heat regeneration and improved plasma catalysis could also play a major role in specific energy consumption reduction and increasing the methane conversion. A system has been demonstrated for hydrogen production with low CO content (1.5%) with power densities of 30 kW (H₂ HHV)/l of reactor, or 10 m³/h H₂ per liter of reactor. Power density should further increase with increased power and improved design.     

Hydrogen generation system using sodium borohydride for operation of a 400 W-scale polymer electrolyte fuel cell stack

Sodium borohydride (NaBH₄) in the presence of sodium hydroxide as a stabilizer is a hydrogen generation source with high hydrogen storage efficiency and stability. It generates hydrogen by self-hydrolysis in aqueous solution. In this work, a Co–B catalyst is prepared on a porous nickel foam support and a system is assembled that can uniformly supply hydrogen at >6.5 L min⁻¹ for 120 min for driving 400-W polymer electrolyte membrane fuel cells (PEMFCs). For optimization of the system, several experimental conditions were changed and their effect investigated. If the concentration of NaBH₄ in aqueous solution is increased, the hydrogen generation rate increases, but a high concentration of NaBH₄ causes the hydrogen generation rate to decrease because of increased solution viscosity. The hydrogen generation rate is also enhanced when the flow rate of the solution is increased. An integrated system is used to supply hydrogen to a PEMFCs stack, and about 465 W power is produced at a constant loading of 30 A.     

Ignition of CO/H2/N2 versus heated air in counterflow: experimental and modeling results

Nonpremixed ignition in counterflowing CO/H₂ vs. heated air jets is experimentally and computationally investigated. The experiments confirm the numerical modeling observation of the existence of three ignition regimes as a function of the hydrogen concentration. In all three regimes, we first detect experimentally the onset of chemiluminescent glow due to excited CO₂ followed by flame ignition, as the temperature of the air jet is raised gradually. The temperature extent of the glow regime, however, is progressively reduced with increasing hydrogen addition; no glow is detected for H₂ concentrations in excess of 73%. The temperatures for glow onset and flame ignition are represented by the boundary air temperatures for each threshold. The variation of these temperatures with system pressure and flow strain rate is explored, for pressures between 0.16 and 5 atm, and strain rates of 100 to 600 s⁻¹. The pressure variation is found to result in three p-T ignition limits, similar to the ignition limits observed in the H₂/O₂ system. This similarity is also observed on the effects of aerodynamic transport on ignition: within the second limit the ignition temperatures are found to be essentially insensitive to flow strain rate, whereas the other two limits are significantly affected by strain. The transport insensitivity is maintained even in the limit of very low H₂ concentrations, where an analogous H₂/N₂ mixture would fail to ignite. This behavior is explained computationally by the replacement of the shift reaction OH + H₂ → H₂O + H with the reaction CO + OH → CO₂ + H, thereby minimizing the effect of diminishing H₂ concentration. The experimental data are found to agree well with the calculated results, although discrepancies are noted in modeling the onset of chemiluminescence and its response to pressure variations.     

Lithium insertion into manganese dioxide electrode in MnO2/Zn aqueous battery: Part I. A preliminary study

The discharge characteristics of manganese dioxide (γ-MnO₂ of electrolytic manganese dioxide (EMD) type) as a cathode material in a Zn–MnO₂ battery containing saturated aqueous LiOH electrolyte have been investigated. The X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) data on the discharged material indicate that lithium is intercalated into the host structure of EMD without the destruction of its core structure. The XPS data show that a layer of insoluble material, possibly Li₂CO₃, is deposited on the cathode, creating a barrier to H₂O, thus preventing the formation of Mn hydroxides, but allowing the migration of Li ions into the MnO₂ structure. The cell could be reversibly charged with 83% of voltaic efficiency at 0.5 mA/cm² current density to a 1.9 V cutoff voltage. The percentage utilization of the cathode material during discharge was 56%.     

Solid oxide fuel cells with dense yttria-stabilized zirconia electrolyte membranes fabricated by a dry pressing process

Dense yttria-stabilized zirconia (YSZ) electrolyte films were successfully fabricated onto anode substrates using a modified dry pressing process. The film thickness was uniform, and could be readily controlled by the mass of the nanocrystalline YSZ powders. The electrolyte films adhered well to the anode substrates by controlling the anode composition. An anode-supported solid oxide fuel cell (SOFC) with a dense YSZ electrolyte film of 8 μm in thickness was operated at temperatures from 700 to 800 °C using humidified (3 vol% H₂O) hydrogen as fuel and air as oxidant. An open circuit voltage of 1.06 V and a maximum power density of 791 mW cm⁻² were achieved at 800 °C. The results indicate that the gas permeation through the electrolyte film was negligible, and that good performance can be obtained by this simple and cost-effective technique which can significantly reduce the fabrication cost of SOFCs.     

Reactive and selective redox system of Ni(II)-ferrite for a two-step CO and H2 production cycle from carbon and water

A number of redox systems composed of carbon and bivalent metal-ferrites, MFe₂O₄(M = bivalent metal ions), were studied to find the most reactive and selective working materials for a thermochemical water-decomposition cycle combined with CO production from a carbon compound. Magnetite and Mg(II)-, Mn(II)-, Co(II)-, Ni(II)-, and Zn(II)-ferrites mixed with carbon powder have been screened for reactivity and selectivity in the CO-production step (first step) and subsequent water-decomposition step (second step). The Ni(II)-ferrite showed the most reactivity and selectivity for CO formation from carbon in the first step at temperatures above 700°C. The Ni(II)-ferrite could be completely reduced with carbon to the metallic phase of the Ni---Fe alloy and Ni in the first step although only a small portion of magnetite was reduced to wustite under similar conditions. The ferrites reduced in the first step were oxidized with water vapor to generate H₂ in the second step. The highest conversion of H₂O to H₂ was obtained using the Ni(II)-ferrite. The total amount of evolved H₂ using Ni(II)-ferrite was 10 times larger than for the magnetite at 500°C. The processes could be repeated using the phase transition between Ni(II)-ferrite and Ni---Fe alloy in the temperature range 700–800°C, with the highly efficient net reaction H₂O + C → H₂ + CO.     

Solvent effects on rechargeable lithium cells

The behaviour of several solvents in rechargeable lithium cells employing two different structure type cathodes, ns-V₆O₁₃ a framework oxide, and TiS₂ a layered material, was compared. Excellent cycling behaviour and high energy were obtained for the Li/ns-V₆O₁₃ cell at current densities as high as 5 mA cm⁻² in the temperature range 25 to −40 °C. Cells utilizing an electrolyte of 2 M LiAsF₆ in methyl formate were discharged at a current density of 2 mA cm⁻² at −40 °C with 37% cell efficiency at an energy density of 255 W h kg⁻¹ (based on active material). Use of an LiAsF₆/2-MeTHF electrolyte with ns-V₆O₁₃ resulted in satisfactory cycle-life, but at significantly reduced capacities than observed with the LiAsF₆/MF electrolyte. This is attributed to the lower conductivities of 2-MeTHF solutions.

The results for Li/TiS₂ cells are in direct contrast with those observed for ns-V₆O₁₃. Use of MF solutions with TiS₂ results in extremely low capacities while capacities and cycle life in 2-MeTHF solutions are quite good. These differences are attributed to a combination of factors including solvent co-intercalation, ion salvation, and solvent decomposition.     

A rechargeable lithium battery employing a porous thin film of Cu3+δMo6S7.9

Porous, thin films of copper molybdenum sulfides (Cu_3+δMo₆S_7.9), that have been prepared by the technique of painting and subsequent reaction with mixed H₂/H₂S gases at 500 °C, have been used as a cathode material for lithium secondary batteries. The test cell comprised: Li/2 M LiClO₄ in PC-THF (4:6)/Cu_3+δMo₆S_7.9 (porous, thin film). The discharge reaction proceeded via the intercalation of lithium ions into the structural interstices of the cathode material.

The first discharge curve of the cell showed that the porous film could incorporate up to 18 lithium ions per formula unit. The capacity of the thin film was four times higher than that previously reported for powder or pressed-pellet electrodes. The theoretical energy density was 675 W h kg⁻¹, i.e., higher than that of TiS₂ (455 W h kg⁻¹) which is one of the best materials for high-energy lithium batteries. From X-ray diffraction studies of the lithium incorporated in the thin film at each discharge step, it is suggested that there are four incorporation reactions of lithium ions into the cathode. Finally, cycling tests have been conducted at room temperature.     

Preparation and performance of high-voltage electrolytes for supercapacitors

采用咪唑类离子液体1-乙基-3-甲基咪唑四氟硼酸盐（EMIBF₄）调制了两款耐压电解液并用于大容量圆柱式超级电容器中,考察了电容器的容量、内阻、循环等性能,分析了高压循环过程中电容器的发热行为。结果表明：相比商用耐压电解液,两款自制电解液均能一定程度提高电容器的能量密度,但是由于内阻的增加而引起功率密度有所下降。商用耐压电解液由于表面温升过快,难以在2.85 V及以上电压正常循环,而两款自制电解液均显著减少了表面温升,改善了电容器的高压循环能力。另一方面,降低电流密度可以有效控制超级电容器的表面温升速度,这使得各款电容器都能维持稳定的3 V限压循环,EMIBF₄/AN电解液甚至可以支持3.2 V上限循环,此时基于超级电容器总重量计算的最大能量密度与最大功率密度分别达到8.62 W·h/kg和16.18 kW/kg。     

MW-assisted synthesis of LiFePO4 for high power applications

LiFePO₄/C was prepared by solid-state reaction from Li₃PO₄, Fe₃(PO₄)₂·8H₂O, carbon and glucose in a few minutes in a scientific MW (microwave) oven with temperature and power control. The material was characterized by X-ray diffraction, scanning electron microscopy and by TGA analysis to evaluate carbon content. The electrochemical characterization as positive electrode in EC (ethylene carbonate)–DMC (dimethylcarbonate) 1 M LiPF₆ was performed by galvanostatic charge–discharge cycles at C/10 to evaluate specific capacity and by sequences of 10 s discharge–charge pulses, at different high C-rates (5–45C) to evaluate pulse-specific power in simulate operative conditions for full-HEV application. The maximum pulse-specific power and, particularly, pulse efficiency values are quite high and make MW synthesis a very promising route for mass production of LiFePO₄/C for full-HEV batteries at low energy costs.     

Optimization of the electrolyte ratio for the vanadium flow battery and its effect on the battery performance

电解液是钒电池能量存储的核心,其组成对电池的能量转化效率、循环稳定性等具有显著影响。本工作针对正负极电解液体积比、电解液价态,较系统地考察了它们对钒电池电化学性能的影响规律。结果表明,保持正极电解液体积不变,单纯增加负极的体积,可提高电池的放电容量,但对电池的能量转换效率影响较小;电解液价态的升高会在一定程度上降低钒电池的放电容量,但其能量转换效率却呈现先升高后降低的抛物线规律;增加负极电解液体积和提高电解液价态均会导致负极活性物质过量,但后者对电池性能的影响更为显著,在后者的基础上前者对能量转换效率的影响也会被放大。     

Charge and discharge characteristics of a commercial LiCoO2-based 18650 Li-ion battery

We studied the charge and discharge characteristics of commercial LiCoO₂-based 18650 cells by using various electrochemical methods, including discharging at constant power, ac impedance spectroscopy, and dc-voltage pulse. At 20 °C, these cells deliver 8.7–6.8 Wh of energy when discharged at a power range of 1–12 W between 2.5 and 4.2 V. Ragone plots show that the effect of discharge power on the energy is significantly increased with decreasing of the temperature. For example, energy of the cell is entirely lost when the temperature downs to −10 °C and the discharge rate still remains at 10 W. Impedance analyses indicate that the total cell resistance (R_cell) is mainly contributed by the bulk resistance (R_b, including electric contact resistance and electrolytic ionic conductivity), solid electrolyte interface resistance (R_sei), and charge-transfer resistance (R_ct). Individual contribution of these three resistances to the cell resistance is greatly varied with the temperature. Near room temperature, the R_b occupies up to half of the cell resistance, which means that the rate performance of the cell could be improved by modifying cell design such as employing electrolyte with higher ionic conductivity and enhancing electric contact of the active material particles. At low temperature, the R_ct, which is believed to reflect cell reaction kinetics, dominates the cell resistance. In addition, galvanosatic cycling tests indicate that the charge and discharge processes have nearly same kinetics. The performance discrepancy observed during charging and discharging, especially at low temperatures, can be attributed to these two factors of: (1) substantially higher R_ct at the discharged state than at the charged state; (2) asymmetric voltage limits pre-determined for the charge and discharge processes.     

Fermentative biohydrogen production by a new chemoheterotrophic bacterium Citrobacter sp. Y19

A newly isolated Citrobacter sp. Y19 for CO-dependent H₂ production was studied for its capability of fermentative H₂ production in batch cultivation. When glucose was used as carbon source, the pH of the culture medium significantly decreased as fermentation proceeded and H₂ production was seriously inhibited. The use of fortified phosphate at 60–180 mM alleviated this inhibition. By increasing culture temperatures (25–36°C), faster cell growth and higher initial H₂ production rates were observed but final H₂ production and yield were almost constant irrespective of temperature. Optimal specific H₂ production activity was observed at 36°C and pH 6–7. The increase of glucose concentration (1–20 g/l) in the culture medium resulted in higher H₂ production, but the yield of H₂ production (mol H₂/mol glucose) gradually decreased with increasing glucose concentration. Carbon mass balance showed that, in addition to cell mass, ethanol, acetate and CO₂ were the major fermentation products and comprised more than 70% of the carbon consumed. The maximal H₂ yield and H₂ production rate were estimated to be 2.49 molH₂/mol glucose and 32.3 mmolH₂/gcellh, respectively. The overall performance of Y19 in fermentative H₂ production is quite similar to that of most H₂-producing bacteria previously studied, especially to that of Rhodopseudomonas palustris P4, and this indicates that the attempt to find an outstanding bacterial strain for fermentative H₂ production might be very difficult if not impossible.     

Continuous photosynthetic production of hydrogen peroxide by the blue-green algae Anacystis nidulans R2 as a way to solar energy conversion

Continuous production of hydrogen peroxide by a culture of the blue-green algae Anacystis nidulans R2 is described as a model system for the conversion of solar energy. The redox power from the photolysis of water, promoted by the photosynthetic apparatus of algae, is driven by the redox mediator methyl viologen to oxygen which is reduced, in two successive steps, to superoxide and hydrogen peroxide. Hydrogen peroxide is a chemical compound with a high value since it is extensively used in industry, especially as bleaching agent. Moreover, this product is a powerful source of energy which releases more than 100 kJ per mol upon decomposition into water and oxygen; it is considered a fuel able to drive rockets and engines. Optimum pH and temperature of the photosystem, as well as the effect on H₂O₂ production of the concentration of methyl viologen, amount of cell, and intensity of light have been studied. Under saturation of light and methyl viologen, and and at the temperature of 45°C, a production of hydrogen peroxide higher than 200 μmol/mg Chl · h was reached. In these conditions, 2% of the light energy absorbed by the photosystem is converted in chemical energy as H₂O₂.     

Effect of non-graphitized carbon electrodes on the electrochemical characteristics of a thermocell with a Br2/Br redox couple

Electrodes made from a non-graphitized carbon (Maxsorb) sheet with a large specific surface area greatly improved the electrochemical characteristics of thermocells with a bromine/bromide-ion redox couple and a KBr aqueous electrolyte saturated with Br₂. The Maxsorb electrodes provide a higher open-circuit voltage than graphite (Perma Foil) electrodes and the maximum discharge current density is 2.4 mA/cm² until the voltage reaches 0 V. The Maxsorb electrodes generate 5.68 mV/°C of thermoelectric power at a temperature difference greater than 40°C, which is 2.5 times the power reported previously. The Maxsorb electrodes also improve the cathodic polarization in the presence of a gas-liquid-solid interface in Br₂-free electrolyte, while the graphite electrodes do not. Nevertheless, this improvement is insufficient to observe when the KBr electrolyte is saturated with Br₂. An experimental cell with Maxsorb electrodes maintains a stable voltage up to 2.0 mA/cm² for over 450 h, even though the cell configuration has still to be optimized.