Reasons for the effect of the amount of electrolyte on the performance of lithium–sulfur cells

As is known, the depth of the electrochemical reduction of sulfur and lithium polysulfides, the reduction rate, and the cycle life of lithium–sulfur cells decrease with the electrolyte content. The present paper studies the reasons for the effect of the amount of electrolyte on the depth of sulfur reduction and the cycle life of lithium–sulfur cells. The main reason for the effect of the amount of electrolyte on the depth of the electrochemical reduction of sulfur was shown to be the generation of solvate complexes of lithium polysulfides. The minimum amount of electrolyte required for complete reduction of sulfur during the discharge of lithium–sulfur cells is determined by the composition of the generated solvate complexes of lithium polysulfides. The solvate numbers of the lithium ion in the solvate complexes of lithium polysulfides generted in sulfolane electrolyte systems were evaluated from the experimental data. An analysis of the results shows that the minimum solvate number of lithium ions in the solvate complexes of lithium polysulfides with sulfolane is 1.     

The effect of Nb and Ni addition on crystallization behavior of amorphous–nanocrystalline Fe–Cr–B–Si alloys

The crystallization behavior of amorphous Fe–Cr–B–Si alloys in the presence of Ni and Nb elements was the goal of this study. In this regard, four different amorphous–nanocrystalline Fe₄₀Cr₂₀Si₁₅B₁₅M₁₀ (M=Fe, Nb, Ni, Ni_0.5Nb_0.5) alloys were prepared using mechanical alloying technique up to 20 h. Based on the achieved results, in contrast to Fe₅₀Cr₂₀Si₁₅B₁₅ alloy, the amorphous phase can be successfully prepared in the presence of Ni and Nb in composition. Although the crystallization mechanism of prepared amorphous phase in different alloys was the same, the Fe₄₀Cr₂₀Si₁₅B₁₅Nb₁₀ alloy showed higher thermal stability in comparison with other samples. The crystallization activation energy of this amorphous alloy was estimated about 410 kJ mol^?1 which was much higher than Fe₄₀Cr₂₀Si₁₅B₁₅Ni₁₀ (195.5 kJ mol^?1) and Fe₄₀Cr₂₀Si₁₅B₁₅Ni₅Nb₅ (360 kJ mol^?1) samples. The calculated values of Avrami exponent (1.5 < n < 2.2) indicated that the crystallization process in different alloying systems is the same and to be governed by a three-dimensional diffusion-controlled growth.     

The effect of Sb content on glass-forming ability,the thermal stability,and crystallization of Ge–Se chalcogenide glass

The glass formation and devitrification of intermediate alloys in the Sb–Ge–Se system were studied by differential scanning calorimetry. A comparison of various simple quantitative methods to assess the level of stability of the glassy materials in the bove mentioned system is presented. All of these methods are based on characteristic temperatures, such as the glass transition temperature, T _g, the onset temperature of crystallization, T _in , the temperature corresponding to the maximum crystallization rate, T _p, or the melting temperature, T _m . In this case, k _gl may be more suitable for estimating the glass thermal stability in above composition range than ΩT. In this work the parameter K _r (T) is added to the stability criteria. The thermal stability of some ternary compounds of the Sb–Ge–Se type has been evaluated experimentally and correlated with the activation energies of crystallization by this kinetic criterion and compared with those evaluated by other criteria. All the results of criteria and kinetic parameter K _r (T) confirm that the thermal stability decrease with increasing Sb content in the glassy system. The crystallization results are analyzed and both the activation energy of crystallization process and the crystallization mechanism are characterized. Finally, identification of the crystalline phases was made by recording the X-ray diffraction pattern of the transformed material. This pattern shows the existence of microcrystallites of two phases, the first is germanium Selenide GeSe₂ and the second is Sb₂Se₃ in amorphous matrix for annealed of Sb_2.5Ge_22.5Se₇₅ and Sb₁₀Ge₁₅Se₇₅ glass.     

Investigating the effect of π-configurations and methoxy substitution on donor and π- spacers based dyes for dye-sensitized solar cell applications–computational approach

Research on Chemical Intermediates - Triphenylamine and methoxy substituted triphenylamine-based dyes are examined by density-functional theory and time-dependent density-functional theory. The...     

The position effect of nitro group on the anion sensing performance of benzimidazole–naphthalimide derivatives

Six benzimidazole–naphthalimide naked-eye probes containing nitrobenzoquinone have been designed and synthesized to study the positional effect of –NO₂ group on their anion recognition abilities in DMSO. The push–pull character of –NO₂ rendered the anion-binding site hydrazinium –NH more acidic and thus easier for hydrogen bonds or deprotonation. So disubstituted isomer responded to F^?, CN^?, AcO^? and H₂PO₄^?; para-substituted isomer responded toward F^? and CN^?; and ortho-substituted isomer responded to F^? due to the forming of intramolecular hydrogen bond between oxygen in nitro and hydrogen in hydrazine. The ortho-substituted isomer demonstrated highly sensitive and selective detection toward F^? with a distinct color change from orange to blue-green accompanied by UV–Vis absorption redshift and fluorescence turn-on; the detection limits were in the range of 7?×?10^?8 mol/L. Theoretical calculations and TBAOH titration confirmed the recognition mechanism was deprotonation process.

     

Cooperative effect of Fe and Ti species over Fe–Ti–Ox catalysts on the catalytic hydrolysis performance of hydrogen cyanide

FeO_x, TiO₂, and Fe–Ti–O_x catalysts were synthesized and used in the catalytic hydrolysis of hydrogen cyanide (HCN). Nearly 100% HCN conversion was achieved at 250 °C over the Fe–Ti–O_x catalyst. TiO₂ rutile was detected over TiO₂, but not over Fe–Ti–O_x, which suggested that the interaction between Fe and Ti species could inhibit the TiO₂ phase transition. Furthermore, the interaction between Fe and Ti species over Fe–Ti–O_x could promote the selectivity of NH₃ and CO. The mechanism of hydrolysis of HCN over FeO_x, TiO₂, and Fe–Ti–O_x can be given as follows: HCN + H₂O → methanamide → ammonium formate → formic acid → H₂O + CO.     

Li–S batteries: effect of uniaxial compression on the electrical conductivity and electrochemical performance of graphene aerogel cathodes

Journal of Solid State Electrochemistry - Porous cathodes are preferred to be used in lithium-sulfur (Li–S) batteries for better impregnation of the active material. On the other hand, the...     

Synergistic effect of electrode defect regulation and Bi catalyst deposition on the performance of iron–chromium redox flow battery

Iron-chromium redox flow batteries (ICRFBs) possess advantages of high safety, long cycle time, and low-cost. Increasing Cr³⁺/Cr²⁺ reaction activity is suggested as one of the most promising strategies to improve the performance and prolong the lifetime of ICRFBs. To improve the slow reaction kinetics of the negative electrode, a type of defected carbon cloth with Bismuth (Bi) catalyst introduction is prepared by defect engineering method and electrochemical deposition, which provided defect sites and active sites to catalyze the redox couple's reaction of ICRFBs. Furthermore, this modified carbon cloth adsorbs Cr(III) hydrate more easily, which has a more stable structure and can significantly improve the performance of ICRFBs. Both experimental analysis and theoretical calculation indicated that the modified electrode has excellent electrocatalytic ability, which can enhance the reaction rate of Cr³⁺/Cr²⁺, improve capacity retention and stabilize cycling performance. The capacity degradation rate of an ICRFB single cell with the modified electrodes is just 0.23% per cycle at a current density of 140 mA/cm². Additionally, the energy efficiency (EE) remains around 83%, which is 8.45% higher than that of the pristine electrode assembled battery under 60 cycles. This work supplies a simple method to obtain a high-performance electrode material for ICRFBs and makes it a practical solution to promote ICFRBs large-scale commercialization process.     

Effect of Re addition on the crystallization,heat treatment and structure of the Cu–Ni–Si-Cr alloy

Differential scanning calorimetry (DSC) was used to investigate the thermal behavior and non-isothermal crystallization kinetics of the Fe₆₇Nb₅B₂₈ metallic glasses prepared by melt-spinning method. DSC traces exhibit that the crystallization takes place through a single exothermic reaction, and it processes a good thermal stability in thermodynamics. The activation energies for nucleation and grain growth processes were calculated to be 536 ± 22 and 559 ± 20 kJ mol^?1 by Kissinger equation, respectively, and 551 ± 24 and 574 ± 20 kJ mol^?1 by Ozawa equation, respectively. It means that the grain growth process is more difficult than the nucleation process. The variation of local Avrami exponent n(x) with crystallized fraction x demonstrates that the crystallization mechanism varies at different stages. The n(x) is larger than 2.5 at the initial stage of 0 < x < 0.3, implying a mechanism of diffusion-controlled three-dimensional growth with increasing nucleation rate. The n(x) decreases from 2.5 to 1.5 in the range of 0.3 < x < 0.65, suggesting that the crystallization belongs to three-dimensional nucleation and grain growth with decreasing nucleation rate. And n(x) lies between 1.0 and 1.5 in the range of 0.65 < x < 0.95, indicating that the crystallization corresponds to the growth of particles with an appreciable initial volume. Low-temperature annealing corresponds to the precipitation of α-Fe, Fe₂B, and Fe₂₃B₆ phases, and further annealing leads to the formation of α-Fe, Fe₂B, and FeNbB phases. The magnetic properties in relation to microstructure change of the Fe₆₇Nb₅B₂₈ metallic glasses are discussed.     

Optimization of the reflux ratio for methanol–water stage distillation column

In this paper, the enthalpy-concentration method was applied in order to model a steady-state continuous methanol–water mixture distillation column. This work includes three steps; first, to develop a code in MATLAB v.7.6 to apply to the mathematical model of the column. The second step is to simulate the column using HYSIS v.3.2. While the third is the calculation of the optimized reflux ratio to minimize the operating cost. For a distillation tower such as the methanol–water splitter in this study, there are relatively few degrees of freedom that can be manipulated in order to minimize operating costs; the reflux ratio can influence the steady-state operating point and therefore the daily costs. In this paper, we have discussed the trade-offs between reflux ratios and operating costs. A correlation is derived to define the optimum value of the reflux ratio as an exponential function of a certain economic parameter of energy prices and depreciation costs. We demonstrate that, at low energy prices or high equipment depreciation costs, the optimum reflux factor is high.     

Influence of modifiers and glass-forming ions on the crystallization of glasses of the NaCaPO4–SiO2 system

Silicate?Cphosphate glasses of the XYPO₄?CSiO₂ and XYPO₄?CSiO₂?CAlPO₄ (where X?=?Na⁺ and/or K⁺ and Y?=?Ca²⁺ and/or Mg²⁺) systems have been the subject of the presented investigations. Bioactive glasses from these systems are the base for obtaining glass-crystalline biomaterials through a direct crystallization. However, growth of crystalline phases very adversely affects the bioactivity of the glasses. Uncontrolled growth of crystalline phases can be reduced by means of a glass phase separation phenomenon in the silicate?Cphosphate glasses because boundaries of inclusion-matrix phase may be a barrier limiting the growth of crystalline phases. Microscopic and EDX investigations which have been carried out have shown that glass phase separation occurs in glasses belonging to XYPO₄?CSiO₂ and XYPO₄?CSiO₂?CAlPO₄ systems. Introduction of aluminum ions into the glass structure leads to a rapid homogenization of its texture. Based on DSC examinations it has been found out that crystallization of the glasses of XYPO₄?CSiO₂ systems is a multistep process. The presence of several (the number depends on the type of modifiers and glass-forming ions) clearly separated exothermic peaks in DSC curves of investigated glasses makes it possible to crystallize only the inclusions with the matrix remaining amorphous or vice versa. It has been shown that, crystallization of glasses of XYPO₄?CSiO₂?CAlPO₄ system is single-stage process, which is the consequence of the homogenizing effect of aluminum ions on their texture.     

Investigating the effect of coolant’s heat transfer type on thermostat placement

Journal of Thermal Analysis and Calorimetry - Nowadays, modern engines control a wide range of parameters in order to meet desired functions and standards. Measurement of mechanical systems has...     

Thermal characterization of the effect of fillers and ionic liquids on the vulcanization and properties of acrylonitrile–butadiene elastomer

Different thermal analysis techniques were used to study the effect of fillers and ionic liquids (ILs) on the vulcanization process, thermal and dynamic mechanical properties of acrylonitrile–butadiene elastomer (NBR). The products of the studies were composites of NBR filled with hydrotalcite, nanosized silica or carbon black. ILs such as 1-butyl-1-methylpyrrolidinium (BMpyrrolBF₄), 1-butyl-4-methylpyridinium (BMpyrBF₄) or 1-butyl-1-methylpiperidinium (BMpipBF₄) tetrafluoroborates were applied to improve the dispersion degree of the curatives and filler particles in the elastomer and to increase the efficiency of vulcanization. The differential scanning calorimetry results indicated that ILs reduced the vulcanization temperature of NBR compounds and increased the homogeneity of cross-link distribution in the elastomer network. NBRs filled with carbon black or silica exhibited similar thermal stabilities, whereas hydrotalcite reduced the temperature of thermal decomposition. The lowest mechanical loss factors were determined for vulcanizates filled with nanosized silica.

     

Effect of temperature on the performance of proton batteries based on chitosan–NH4NO3–EC membrane

Membranes of chitosan-based proton conductor polymer electrolyte were prepared by dissolving chitosan powder, ammonium nitrate (NH₄NO₃) salt and ethylene carbonate (EC) plasticizer in acetic acid solution. The temperature dependence of the chitosan-based membrane system was found to obey the Arrhenius relationship. The sample with the highest conductance, 18 wt.% CA + 12 wt.% NH₄NO₃ + 70 wt.% EC (CA40N70E), also possesses the lowest activation energy. From linear sweep voltammetry (LSV) results, the membrane is electrochemically stable at a potential of 1.6–1.8 V and a temperature of 298–353 K. The cells were fabricated using zinc powder (Zn) + zinc sulfate heptahydrate (ZnSO₄·7H₂O) + acetylene black (AB) + polytetrafluoroethylene (PTFE)|CA40N70E|manganese (IV) oxide (MnO₂) + AB + PTFE. The open circuit voltages of the cells are decreases as temperature increases, the same trend as that obtained by LSV. The cell performance is excellent at 333 K, with discharge capacity of 42.7 mAh, internal resistance of 16.8 Ω, maximum power density of 14.6 mW cm⁻² and a short-circuit current density of 31.0 mA cm⁻². However, at temperatures above 333 K, decomposition of the membrane degraded the electrochemical properties of the cells.     

Thermal analysis of cadmium addition on the glass transition and crystallization kinetics of Se–Te–Sn glassy network

Journal of Thermal Analysis and Calorimetry - Calorimetric measurements have been performed in quaternary glassy system Se78−xTe20Sn2Cdx (x&nbsp;=&nbsp;0, 2, 4, and 6) to study the...     

Growth and field crystallization of anodic films on Ta–Nb alloys

The growth behavior of amorphous anodic films on Ta–Nb solid solution alloys has been investigated over a wide composition range at a constant current density of 50 A m⁻² in 0.1 mol dm⁻³ ammonium pentaborate electrolyte. The anodic films consist of two layers, comprising a thin outer Nb₂O₅ layer and an inner layer consisting of units of Ta₂O₅ and Nb₂O₅. The outer Nb₂O₅ layer is formed as a consequence of the faster outward migration of Nb⁵⁺ ions, compared with Ta⁵⁺ ions, during film growth under the high electric field. Their relative migration rates are independent of the alloy composition. The formation ratio, density, and capacitance of the films show a linear relation to the alloy composition. The susceptibility of the anodic films to field crystallization during anodizing at constant voltage increases with increasing niobium content of the alloy.     

Pretreatment effect on the properties of the Cr–Mg catalyst for the gas-phase hydrofluorination of perchloroethylene into pentafluoroethane

The effect of the temperature of thermal pretreatment of the precursors of the Cr–Mg catalyst on its physicochemical properties (specific surface area and elemental composition) and catalytic properties has been experimentally investigated. The dehydration of the precursor takes place up to a temperature of ~500°С, making it possible to tune the catalyst composition by varying the heat-treatment temperature. The samples prepared from precursors with various compositions differ in their specific surface area and catalytic activity. The highest activity is shown by the catalyst prepared by heat treatment of the precursor at 330°С.     

Prediction and experimental verification of the salt effect on the vapour–liquid equilibrium of water–ethanol–2-propanol mixture

Experimental vapour–liquid equilibria of water–ethanol–2-propanol saturated with NaNO₃, NaCl, KCl and containing 0.05 mol CH₃COOK/mol total solvent compared well with those predicted by Tan–Wilson and Tan–non-random two liquid (NRTL) models for multicomponent solvent–solute mixture using a set of solvent–solvent interaction parameters obtained from the regression of the vapour–liquid equilibrium of the solvent mixture without the dissolved solute and a set of solute–solvent interaction parameters calculated from the bubble points of the individual solvent components saturated or containing the same molar ratio of solute/total solvents as the mixture. The results also showed that a solvent component i is salted-in or out of the liquid phase relatively more than solvent component j would depend on whether A_sj/A_si (Tan–Wilson model) or exp(τ_is−τ_js) (Tan–NRTL model) is less or greater than 1. This is consistent with earlier publications on the effect of dissolved solutes (electrolytes and non-electrolytes) on the binary solvents mixtures. These findings confirmed that Tan–Wilson and Tan–NRTL models for multicomponent solvent–solute system can provide an accurate and rapid screening of electrolytes and non-electrolytes for their suitability in facilitating solvent separation by salt distillation of ternary solvent mixtures simply by determining the relative ratios of the solute–solvent interaction parameters from the respective bubble points of the solvent components containing the dissolved solute. The results also suggest that this may also be extended to other multicomponent solvent mixtures.