Understanding structure-function relationship in hybrid Co3O4-Fe2O3/C lithium-ion battery electrodes

A range of high-capacity Li-ion anode materials (conversion reactions with lithium) suffer from poor cycling stability and limited high-rate performance. These issues can be addressed through hybridization of multiple nanostructured components in an electrode. Using a Co3O4-Fe2O3/C system as an example, we demonstrate that the cycling stability and rate performance are improved in a hybrid electrode. The hybrid Co3O4-Fe2O3/C electrode exhibits long-term cycling stability (300 cycles) at a moderate current rate with a retained capacity of approximately 700 mAh g(-1). The reversible capacity of the Co3O4-Fe2O3/C electrode is still about 400 mAh g(-1) (above the theoretical capacity of graphite) at a high current rate of ca. 3 A g(-1), whereas Co3O4-Fe2O3, Fe2O3/C, and Co3O4/C electrodes (used as controls) are unable to operate as effectively under identical testing conditions. To understand the structure-function relationship in the hybrid electrode and the reasons for the enhanced cycling stability, we employed a combination of ex situ and in situ techniques. Our results indicate that the improvements in the hybrid electrode originate from the combination of sequential electrochemical activity of the transition metal oxides with an enhanced electronic conductivity provided by percolating carbon chains.

Rechargeable Zn/PEDOT battery with an imidazolium-based ionic liquid as the electrolyte

 A non-aqueous secondary battery has been constructed by using Zn metal as the anode and chemically synthesised PEDOT as the cathode, with a 1-ethyl-3-methylimidazolium dicyanamide ionic liquid as the electrolyte, which avoids dendritic growth processes on the Zn surface upon charge/discharge cycling. The novel Zn/PEDOT rechargeable cell shows high efficiency and cycling ability, performing over 320 cycles with no indication of short circuit. Both the Zn and PEDOT surfaces showed minimal signs of degradation, suggesting that a Zn/PEDOT electrochemical device would be capable of extended cycle life under numerous charge/discharge cycles.

Synthesis of an indium oxide nanoparticle embedded graphene three-dimensional architecture for enhanced lithium-ion storage

Indium oxide nanoparticles were synthesised by using a facile and scalable strategy. The as-prepared nanoparticles (20-40 nm) were in situ and homogeneously distributed in a three-dimensional (3D) graphene architecture subsequently during the fabrication process. The obtained nanocomposite acts as a high capacity anode material for lithium-ion batteries and demonstrates good cycle stability. A drastically enhanced capacity of 750 mA h g^-1 in comparison with that of bare In2O3 nanoparticles can be maintained after 100 cycles, along with an improved high rate performance (210 mA h g^-1 at 1 A g^-1 and 120 mA h g^-1 at 2 A g^-1). The excellent performance is linked with the indium oxide nanoparticles and the unique 3D interconnected porous graphene structure. The highly conductive and porous 3D graphene structure greatly enhances the performance of lithium-ion batteries by protecting the nanoparticles from the electrolyte, stabilizing the nanoparticles during cycles and buffering the volume expansion upon lithium insertion.

Advanced N-doped mesoporous molybdenum disulfide nanosheets and the enhanced lithium-ion storage performance

With the increasing interest in two-dimensional van der Waals materials, molybdenum disulfide (MoS2) has emerged as a promising material for electronic and energy storage devices. It suffers from poor cycling stability and low rate capability when used as an anode in lithium ion batteries. Here, N-doped MoS2 nanosheets with 2-8 atomic layers, increased interlayer distance, mesoporous structure and high surface area synthesised by a simple sol-gel method show an enhanced lithium storage performance, delivering a high reversible capacity (998.0 mA h g-1, 50 mA g-1), high rate performance (610 mA h g-1, 2 A g-1), and excellent cycling stability. The excellent lithium storage performance of the MoS2 nanosheets might be due to the better electrical and ionic conductivity and improved lithium ion diffusion which are related to their structural characteristics and high concentration N doping. The possible mechanism of the improved performance is proposed and discussed.

Bubble flow in a static magnetic field

A lab-based electrolytic-cell is designed to analyze the effect of external magnetic field on bubble evolution underneath an anode surface. Buckingham Pi theorem is used to provide a complete list of dimensionless parameters for a typical cell configuration. There is an increase in bubble size and the number of bubbles with time. The hydrodynamic convection is apparent due to the effect of electrolyte flow caused by swarm of bubbles rising along the anode surface. The image sequence shows that swarm of bubbles exhibit a swirling flow-field in the presence of the magnetic field. The coalescence process intensifies in an area where magnetic field is higher. As a consequence, bubbles are swept away by the magneto-hydrodynamic (MHD) convection. These results suggest that a magnetic field causes remarkable improvement on the surface coverage of the anode.

Síntese e caracterização de NiO-CGO para anodo e eletrólitos sólidos e base de Céria para SOFC

The direct use of natural gas makes the Solid Oxide Fuel Cell (SOFC) potentially more competitive with the current energy conversions technologies. The Intermediate Temperature SOFC (IT-SOFC) offer several advantages over the High Temperature SOFC (HT-SOFC), which includes better thermal compatibility among components, fast start with lower energy consumption, manufacture and operation cost reduction. The CeO2 based materials are alternatives to the Yttria Stabilized Zirconia (YSZ) to application in SOFC, as they have higher ionic conductivity and less ohmic losses comparing to YSZ, and they can operate at lower temperatures (500-800°C). Ceria has been doped with a variety of cations, although, the Gd3+ has the ionic radius closest to the ideal one to form solid solution. These electrolytes based in ceria require special electrodes with a higher performance and chemical and termomechanical compatibility. In this work compounds of gadolinia-doped ceria, Ce1-xGdxO2-δ (x = 0,1; 0,2 and 0,3), used as electrolytes, were synthesized by polymeric precursors method, Pechini, as well as the composite material NiO - Ce0,9Gd0,1O1,95, used as anode, also attained by oxide mixture method, mixturing the powders of the both phases calcinated already. The materials were characterized by X ray diffraction, dilatometry and scanning electronic microscopy. The refinement of the diffraction data indicated that all the Ce1-xGdxO2-δ powders were crystallized in a unique cubic phase with fluorite structure, and the composite synthesized by Pechini method produced smaller crystallite size in comparison with the same material attained by oxide mixture method. All the produced powders had nanometric characteristics. The composite produced by Pechini method has microstructural characteristics that can increase the triple phase boundaries (TPB) in the anode, improving the cell efficiency, as well as reducing the mass transport mechanism effect that provokes anode degradation

Estudo da viabilidade do sistema LZAS para uso como selante de PaCOS

Cells the solid oxide fuel are systems capable to directly convert energy of a chemical reaction into electric energy in clean, quiet way and if its components in the solid state differentiate of excessively the techniques for having all. Its more common geometric configurations are: the tubular one and to glide. Geometry to glide beyond the usual components (anode, cathode and electrolyte) needs interconnect and sealant. E the search for materials adjusted for these components is currently the biggest challenge found for the production of the cells. The sealants need to present chemical stability in high temperatures, to provoke electric isolation, to have coefficient of compatible thermal expansion with the excessively component ones. For presenting these characteristics the glass-ceramics materials are recommended for the application. In this work the study of the partial substitution of the ZrO2 for the Al2O3 in system LZS became it aiming at the formation of system LZAS, this with the addition of natural spodumene with 10, 20 and 30% in mass. The compositions had been casting to a temperature of 1500°C and later quickly cooled with the objective to continue amorphous. Each composition was worn out for attainment of a dust with average diameter of approximately 3μm and characterized by the techniques of DRX, FRX, MEV, dilatometric analysis and particle size analysis. Later the samples had been conformed and treated thermally with temperatures in the interval between 700-1000 °C, with platform of 10 minutes and 1 hour. The analyses for the treated samples had been: dilatometric analysis, DRX, FRX, electrical conductivity and tack. The results point with respect to the viability of the use of system LZAS for use as sealant a time that had presented good results as isolating electric, they had adhered to a material with similar α of the components of a SOFC and had presented steady crystalline phases

Influência do método de síntese e caracterização de pós compósitos de NiO- Ce1-xEuxO2-δ para anodos catalíticos de células a combustível

Fuel cells are electrochemical devices that convert chemical energy into electricity. Due to the development of new materials, fuel cells are emerging as generating clean energy generator. Among the types of fuel cells, categorized according to the electrode type, the solid oxide fuel cells (SOFC) stand out due to be the only device entirely made of solid particles. Beyond that, their operation temperature is relatively high (between 500 and 1000 °C), allowing them to operate with high efficiency. Another aspect that promotes the use of SOFC over other cells is their ability to operate with different fuels. The CeO2 based materials doped with rare earth (TR+3) may be used as alternatives to traditional NiO-YSZ anodes as they have higher ionic conductivity and smaller ohmic losses compared to YSZ, and can operate at lower temperatures (500-800°C). In the composition of the anode, the concentration of NiO, acting as a catalyst in YSZ provides high electrical conductivity and high electrochemical activity of reactions, providing internal reform in the cell. In this work compounds of NiO - Ce1-xEuxO2-δ (x = 0.1, 0.2 and 0.3) were synthesized from polymeric precursor, Pechini, method of combustion and also by microwave-assisted hydrothermal method. The materials were characterized by the techniques of TG, TPR, XRD and FEG-SEM. The refinement of data obtained by X-ray diffraction showed that all powders of NiO - Cex-1EuxO2-δ crystallized in a cubic phase with fluorite structure, and also the presence of Ni. Through the characterizations can be proved that all routes of preparation used were effective for producing ceramics with characteristics suitable for application as SOFC anodes, but the microwave-assisted hydrothermal method showed a significant reduction in the average grain size and improved control of the compositions of the phases

Efeito da Gália como aditivo de sinterização em eletrólitos cerâmicos à base de céria sintetizados pelo método de complexação de cátions

Fuel cells are considered one of the most promising ways of converting electrical energy due to its high yield and by using hydrogen (as fuel) which is considered one of the most important source of clean energy for the future. Rare earths doped ceria has been widely investigated as an alternative material for the electrolyte of solid oxide fuel cells (SOFCs) due to its high ionic conductivity at low operating temperatures compared with the traditional electrolytes based on stabilized zirconia. This work investigates the effect of gallium oxide (Gallia) as a sintering aid in Eu doped ceria ceramic electrolytes since this effect has already been investigated for Gd, Sm and Y doped ceria electrolytes. The desired goal with the use of a sintering aid is to reduce the sintering temperature aiming to produce dense ceramics. In this study we investigated the effects on densification, microstructure and ionic conduction caused by different molar fraction of the dopants europium (10, 15 and 20%) and gallium oxide (0.3, 0.6 and 0.9%) in samples sintered at 1300, 1350 and 1450 0 C. Samaria (10 and 20%) doped ceria samples sintered between 1350 and 1450 °C were used as reference. Samples were synthesized using the cation complexation method. The ceramics powders were characterized by XRF, XRD and SEM, while the sintered samples were investigated by its relative density, SEM and impedance spectroscopy. It was showed that gallia contents up to 0.6% act as excellent sintering aids in Eu doped ceria. Above this aid content, gallia addition does not promote significant increase in density of the ceramics. In Ga free samples the larger densification were accomplished with Eu 15% molar, effect expressed in the microstructure with higher grain growth although reduced and surrounded by many open pores. Relative densities greater than 95 % were obtained by sintering between 1300 and 1350 °C against the usual range 1500 - 1600 0 C. Samples containing 10% of Sm and 0.9% of Ga reached 96% of theoretical density by sintering at 1350 0 C for 3h, a gain compared to 97% achieved with 20% of Sm and 1% of Ga co-doped cerias sintered at 1450 0 C for 24 h as described in the literature. It is found that the addition of gallia in the Eu doped ceria has a positive effect on the grain conductivity and a negative one in the grain boundary conductivity resulting in a small decrease in the total conductivity which will not compromise its application as sintering aids in ceria based electrolytes. Typical total conductivity values at 600 and 700 °C, around 10 and 30 mS.cm -1 respectively were reached in this study. Samples with 15% of Eu and 0.9 % of Ga sintered at 1300 and 1350 °C showed relative densities greater than 96% and total conductivity (measured at 700 °C) between 20 and 33 mS.cm -1 . The simultaneous sintering of the electrolyte with the anode is one of the goals of research in materials for SOFCs. The results obtained in this study suggest that dense Eu and Ga co-doped ceria electrolytes with good ionic conductivity can be sintered simultaneously with the anode at temperatures below 1350 °C, the usual temperature for firing porous anode materials

Estudo de reatores eletroquímicos para remoção de Cu2+ , Zn2+, Fenol e BTEX em água produzida

The production of water has become one of the most important wastes in the petroleum industry, specifically in the up stream segment. The treatment of this kind of effluents is complex and normally requires high costs. In this context, the electrochemical treatment emerges as an alternative methodology for treating the wastewaters. It employs electrochemical reactions to increase the capability and efficiency of the traditional chemical treatments for associated produced water. The use of electrochemical reactors can be effective with small changes in traditional treatments, generally not representing a significant additional surface area for new equipments (due to the high cost of square meter on offshore platforms) and also it can use almost the same equipments, in continuous or batch flow, without others high costs investments. Electrochemical treatment causes low environmental impact, because the process uses electrons as reagent and generates small amount of wastes. In this work, it was studied two types of electrochemical reactors: eletroflocculation and eletroflotation, with the aim of removing of Cu2+, Zn2+, phenol and BTEX mixture of produced water. In eletroflocculation, an electrical potential was applied to an aqueous solution containing NaCl. For this, it was used iron electrodes, which promote the dissolution of metal ions, generating Fe2+ and gases which, in appropriate pH, promote also clotting-flocculation reactions, removing Cu2+ and Zn2+. In eletroflotation, a carbon steel cathode and a DSA type anode (Ti/TiO2-RuO2-SnO2) were used in a NaCl solution. It was applied an electrical current, producing strong oxidant agents as Cl2 and HOCl, increasing the degradation rate of BTEX and phenol. Under different flow rates, the Zn2+ was removed by electrodeposition or by ZnOH formation, due the increasing of pH during the reaction. To better understand the electrochemical process, a statistical protocol factor (22) with central point was conducted to analyze the sensitivity of operating parameters on removing Zn2+ by eletroflotation, confirming that the current density affected the process negatively and the flow rate positively. For economical viability of these two electrochemical treatments, the energy consumption was calculated, taking in account the kWh given by ANEEL. The treatment cost obtained were quite attractive in comparison with the current treatments used in Rio Grande do Norte state. In addition, it could still be reduced for the case of using other alternative energy source such as solar, wind or gas generated directly from the Petrochemical Plant or offshore platforms

Estimulação transcraniana por corrente contínua e a flutuação de força em idosas durante exercício isométrico

The fluctuacion force has been increasingly used in studies with elderly as a good predictor of performance and functionality of the motor. However, most analyzes the fluctuation of force in one session. Thus, identifying the minimum amount of sessions needed for familiarization with the fluctuation strength in isometric exercise become relevant. Furthermore, to investigate the effects of applying transcranial direct current stimulation (tDCS) associated with regular exercise on rates fluctuation task force is extremely important. In the first experiment, volunteers were subjected to a protocol marked by a familiarization session to establish the parameters of VCM and eight sessions with intensity of 30% MVC in office. It was observed that two familiarization sessions are required so there is a fluctuation stabilizing force. In experiment II, subjects performed an isometric contraction before and after applying tDCS (cathode, anode and sham) applied to M1. ETCC anodic effectively contributed to reducing the fluctuation of force during isometric exercise in the elderly, while the cathodic caused the increased levels of strength fluctuation. It was concluded that there is a need to implement a familiarization protocol with at least two sessions to avoid possible misunderstandings of measurements in tests of fluctuacion force. Besides that tDCS interfered with the behavior of the oscillations of force, with cathodic promoting increased fluctuation strength and anodic contributed to greater stability, demonstrating the potential of this technique neuromodulation associated with exercise as rehabilitation tools

Crystallization and preliminary X-ray diffraction analysis of a glutathione S-transferase from Xylella fastidiosa

Glutathione S-transferases (GSTs) form a group of multifunctional isoenzymes that catalyze the glutathione-dependent conjugation and reduction reactions involved in the cellular detoxification of xenobiotic and endobiotic compounds. GST from Xylella fastidiosa (xfGST) was overexpressed in Escherichia coli and purified by conventional affinity chromatography. In this study, the crystallization and preliminary X-ray analysis of xfGST is described. The purified protein was crystallized by the vapour-diffusion method, producing crystals that belonged to the triclinic space group P1. The unit-cell parameters were a = 47.73, b = 87.73, c = 90.74 angstrom, alpha = 63.45, beta = 80.66, gamma = 94.55 degrees. xfGST crystals diffracted to 2.23 angstrom resolution on a rotating-anode X-ray source.

Synthesis and Characterization of Ordered Intermetallic Nanostructured PtSn/C and PtSb/C and Evaluation as Electrodes for Alcohol Oxidation

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Tratamento eletroquímico de água produzida sintética para remoção de hidrocarbonetos policíclicos aromáticos

The aim of this work is the treatment of produced water from oil by using electrochemical technology. Produced water is a major waste generated during the process of exploration and production in the oil industry. Several approaches are being studied aiming at the treatment of this effluent; among them can be cited the biological process and chemical treatments such as advanced oxidation process and electrochemical treatments (electrooxidation, electroflotation, electrocoagulation, electrocoagulation). This work studies the application of electrochemical technology in the treatment of the synthetic produced water effluent through the action of the electron, in order to remove or transform the toxic and harmful substances from the environment by redox reactions in less toxic substances. For this reason, we used a synthetic wastewater, containing a mixture H2SO4 0,5M and 16 HPAs, which are: naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo (a) anthracene, chrysene, benzo(b)fluoranthene, benzo(k) fluoranthene, benzo(a)pyrene, indeno(1,2,3-cd)pyrene, dibenzo(a, h)anthracene, benzo(g, h, i)perylene. Bulk electrochemical oxidation experiments were performed using a batch electrochemical reactor containing a pair of parallel electrodes, coupled with a power supply using a magnetic stirrer for favoring the transfer mass control. As anodic material was used, a Dimensionally Stable Anode (DSA) of Ti/Pt, while as cathode was used a Ti electrode. Several samples were collected at specific times and after that, the analysis of these samples were carried out by using Gas Chromatography Coupled to Mass Spectrometry (GC - MS) in order to determine the percentage of removal. The results showed that it was possible to achieve the removal of HPAs about 80% (in some cases, more than 80%). In addition, as an indicator of the economic feasibility of electrochemical treatment the energy consumption was analyzed for each hour of electrolysis, and based on the value kWh charged by ANEEL, the costs were estimated. Thus, the treatment costs of this research were quite attractive

Tecnologia eletroquímica como tratamento alternativo de efluentes têxteis sintéticos utilizando ânodos de platina e diamante

In this work, the treatment of synthetic wastewaters containing Remazol Red BR (RRB) and Novacron Blue C-D (NB) by anodic oxidation using boron doped diamond anodes (BDD) and Novacron Yellow (YN) using BDD and Platinum (Pt) anodes was investigated. Galvanostatic electrolyses of RRB and NB synthetic wastewaters have led to the complete decolorization removal at different operating conditions (current density, pH and temperature). The influence of these parameters was investigated in order to find the best conditions for dyestuff colour removal. According to the experimental results obtained, the electrochemical oxidation process is suitable for decolorizing wastewaters containing these textile dyes, due to the electrocatalytic properties of BDD and Pt anode. Energy requirements for removing colour during galvanostatic electrolyses of RRB, NB and YN synthetic solutions depends mainly on the operating conditions; for example for RRB, it passes from 3.30 kWh m-3 at 20 mA cm-2 to 4.28 kWh m-3 at 60 mA cm-2 (pH = 1); 15.23 kWh m-3 at 20 mA cm-2 to 24.75 kWh m-3 at 60 mA cm-2 (pH = 4.5); 10.80 kWh m-3 at 20 mA cm-2 to 31.5 kWh m-3 at 60 mA cm-2 (pH = 8) (data estimated per volume of treated effluent). In order to verify the Brazilian law regulations of NB and RRB synthetic solutions after electrochemical decolourisation treatment, Hazen Units values were determined and the total colour removal was achieved; remaining into the regulations. Finally, electrical energy cost for removing colour was estimated