Enhance cycling performance of LiMn2O4 cathode by Sr2+ and Cr3+ doping

Spinel LiSr_0·1Cr_0·1Mn_1·8O₄ was synthesised by high temperature solid state method in order to enhance the electrochemical performance. The LiSr_0·1Cr_0·1Mn_1·8O₄ (LSCMO) materials were characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical tests. The XRD and SEM studies confirm that LSCMO had spinel crystal structure with a space group of Fd3m, and the particle of LSCMO shows irregular shape. The cyclic voltammetry data illustrated that the heavy current charge–discharge performance of LMO was improved by Sr²⁺ and Cr³⁺ doping. The galvanostatic charge–discharge of LSCMO cathode materials was measured at 1, 5, 10 and 20 C. The results indicated that LSCMO improved the capacity retention.     

Separation of Indium from Acid Sulfate-Containing Solutions by Ion Exchange with Impregnated Resins

Indium separation using ion exchange resins from acidic polymetallic and very diluted solutions are investigated. Since the selectivity of commercial ion exchange resins have proven to be too low for an effective separation from solutions with high content of other metals, Lewatit® TP 208 was impregnated with common extractants to enhance its properties. By resin impregnation with D2EHPA and Cyanex 272, not only the selective indium recovery was reached but also the resin capacity was increased approx. two times. The best loading and elution performance were shown by Cyanex 272-impregnated Lewatit® TP 208, increasing the indium purity in the eluate from 0.75 % to 85 %.     

Simulation studies on a rotating ring disk electrode: Effects of ionic migration with kinetic complication-disk results

In continuation to my previous work (Guha S. AIChE J. 2013;59(4):1390-1399), in this work, effects of ionic migration are evaluated for disk region of a rotating ring disk electrode system by numerically solving complex differential equations, developed for mass transfer along with kinetic complication in presence of ionic migration under limiting current condition. The system for simulation is 0.01 M Fe₂(SO₄)₃ solution with H₂SO₄ as supporting electrolyte. Simulation cases are presence and absence of ionic migration with kinetic complication (oxidation of Fe²⁺ to Fe³⁺ under O₂ pressure). Results show that concentration boundary layer thickness of reactant Fe³⁺ reduces appreciably and steady-state disk current reduces substantially in presence of migration. Simulated steady-state disk current in absence of migration case agrees well with published data. Results indicate higher Fe²⁺ concentration in presence of migration and thereby higher rate of oxidation of Fe²⁺ to Fe³⁺ at all rate constant values.     

Application of the Microsoft Excel Solver tool in the solution of optimization problems of heat exchanger network systems

Optimization of heat exchanger networks (HEN_S) is a field of interest in Chemical Engineering. The aim is to use the residual heat of process streams to raise the temperature of other process streams which are cold, thus minimizing the use of hot and cold utilities. The usual way to deal with this task is to pose a linear programming problem according to a transshipment model in order to minimize either the general services consumptions or the number of hot and cold stream matchings required. This optimization is subjected to several restrictions given by the energy balances corresponding to each heat exchange.The high number of variables and equations obliges the use of specific software to solve these problems, e.g. GAMS (General Algebraic Modelling System). However, this software is not intuitive and requires a long time of training and a certain level of practice for the students to adequately use it.This work describes the use of Microsoft Excel-Solver for the sequential solving of HEN_S optimization problems according to the transshipment model. Solver is a much simpler, intuitive and easily available tool for the students who, besides, usually learn how to use it in the first years of their degree, in Informatics or similar subjects. Thus, it is not necessary to spend extra time in the teaching of the software, time that may be devoted to other contents.This paper presents an example of HEN_S problem proposed in the subject Simulation and Optimization of Chemical Processes corresponding to the Joint Master in Chemical Engineering of the Rey Juan Carlos University and the Autónoma University of Madrid and solved by the students using Excel-Solver.     

Performance of surface ionic conduction single chamber fuel cell prepared by the sol gel method

The performance of surface ionic conduction single chamber fuel cell (SIC‐SCFC) prepared by the sol gel method was studied on electric characteristics due to the differences of the operating temperature and humidity, the electrode distance and electrolyte film depth, and multiple cells with the series and parallel connections. The SIC–SCFC was arranged the both anode of Pt and cathode of Au on the boehmite electrolyte. The open circuit voltage (OCV) of single cell achieved a maximum of 530mV in the dry gas mixtures of O₂/H₂=50% in room temperature operation, and but it became decrease as over 60%. The OCV was maintained the constant value between operating temperatures of 30°C to 80°C, and but it was decreased sharply at over 90°C because a humidity on the cell became lower as increasing operating temperature. Then, the cell property was improved to 120°C by adding to the humidity of 70% using a humidifier. The electrode distance and the electrolyte film depth of SIC‐SCFC found to be contributed to the reductions of the cell resistance and the surface roughness on the electrode, respectively. Moreover, the power property of SIC‐SCFC was significantly improved by cell stacks comprised of the series or parallel connection of a cell.     

Evolution of Local Structural Ordering and Chemical Distribution upon Delithiation of a Rock Salt–Structured Li1.3Ta0.3Mn0.4O2 Cathode

Lithium‐rich disordered rock‐salt oxides have attracted great interest owing to their promising performance as Li‐ion battery cathodes. While experimental and theoretical efforts are critical in advancing this class of materials, a fundamental understanding of key property changes upon Li extraction is largely missing. In the present study, single‐crystal synthesis of a new disordered rock‐salt cathode material, Li_1.3Ta_0.3Mn_0.4O₂ (LTMO), and its use as a model compound to investigate Li concentration–driven evolution of local cationic ordering, charge compensation, and chemical distribution are reported. Through the combined use of 2D and 3D X‐ray nanotomography, it is shown that Li removal accompanied by oxygen oxidation is correlated with the development of morphological defects such as particle cracking. Chemical heterogeneity, quantified by subparticle level distribution of Mn valence state, is minimal during Mn redox, which drastically increases upon the formation of cracks during oxygen redox. Density functional theory and bond valence sum mismatch calculations reveal the presence of local short‐range ordering in the pristine oxide, which gradually disappears along with the extraction of Li. The study suggests that with cycling the transformation into true cation–disordered state can be expected, which likely impacts the voltage profile and obtainable energy density of the oxide cathodes.     

SiC/SiC mini-composites with multilayer ZrSiO4 interphase: Room-temperature properties and toughening mechanism

SiC/SiC mini-composites reinforced with SiC fibers coated with different numbers of ZrSiO₄ sublayers prepared via a non-hydrolytic sol-gel process were fabricated. The tensile strength and work of fracture of the prepared SiC/SiC mini-composites were determined, and the relationship between their mechanical properties and fracture morphologies was discussed. The toughening mechanism and the variation tendency of their mechanical properties were further elaborated by analyzing the interfacial debonding morphologies of the SiC/SiC mini-composites with 1 and 4 layers of ZrSiO₄ interphase as well as the results of prior studies. A relatively rare phenomenon—the delamination of the multilayer ZrSiO₄ interphase in the SiC/SiC mini-composites but not on the SiC fibers—was observed, which clearly demonstrated the weak bonding between the ZrSiO₄ sublayers in the SiC/SiC mini-composites. The ZrSiO₄ sublayer delamination mechanism was then explained based on the high-magnification morphologies found in and beside the ZrSiO₄ interphase.     

Efficient dye-sensitized solar cells based on CNTs and Zr-doped TiO2 nanoparticles

The light scattering, harvesting and adsorption effects in dye-sensitized solar cells (DSSCs) are studied by preparation of coated carbon nanotubes (CNTs) with TiO₂ and Zr-doped TiO₂ nanoparticles in the forms of mono- and double-layer cells. X-ray diffraction (XRD) analysis reveals that the phase composition of Zr-doped TiO₂ electrode is a mixture of anatase and rutile phases with major rutile content, whereas it is the same mixture with major anatase content for coated CNTs with TiO₂. Furthermore, the average crystallite size of Zr-doped TiO₂ electrode is slightly decreased with Zr introduction. Field emission scanning electron microscope (FE-SEM) images show that the porosity of Zr-doped TiO₂ electrodes is higher than that of undoped electrode, enhancing dye adsorption. UV–visible spectroscopy analysis reveals that the absorption onset of Zr-doped TiO₂ electrodes is slightly shifted to longer wavelength (the red-shift) in comparison with that of undoped TiO₂ electrode. Moreover, the band gap energy of TiO₂ nanoparticles is decreased by Zr introduction, enhancing light absorption. It is found that electron injection of monolayer TiO₂ electrode is improved by introduction of 0.025 mol% Zr, resulted in enhancement of its power conversion efficiency (PCE) up to 6.81% compared with 6.17% for pure TiO₂ electrode. Moreover, electron transport and light scattering are enhanced by incorporation of 0.025 wt% coated CNTs with TiO₂ in the over-layer of double layer electrode. Therefore, double layer solar cell composed of 0.025 mol% Zr-doped TiO₂ nanoparticles as the under-layer and mixtures of these nanoparticles and 0.025 wt% coated CNTs with TiO₂ as the over-layer shows the highest PCE of 8.19%.     

Polyimide/nano-TiO2 hybrid films having benzoxazole pendent groups: In situ sol–gel preparation and evaluation of properties

Polyimide/titania (PI/TiO₂) nanocomposite films have been successfully fabricated through the in situ formation of TiO₂ within a PI matrix via sol–gel method. Poly(amic acid) (PAA), which is the precursor of PI, was successfully synthesized by mixing pyromellitic dianhydride (PMDA), with equimolar amount of a diamine monomer having a pendent benzoxazole unit and two flexible ether linkages in N,N-dimethylformamide (DMF) solvent. Tetraethyl orthotitanate [Ti(OEt)₄] and acetylacetone were then added to the resulted PAA. After imidization at high temperature, PI/TiO₂ hybrid films were formed. The structure and morphology of the hybrid nanocomposites with different titania contents (0 wt%, 5 wt%, 10 wt%, and 15 wt%) were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, and transmission electron microscopy. The results indicate that the TiO₂ nanoparticles were homogeneously dispersed in the hybrid films. The thermogravimetric analysis of nanocomposites confirms the improvement in the thermal stability with the increase in the percentage of titania nanoparticle. Transmission electron microscopy showed that the nanoparticles with an average diameter of 25–40 nm were dispersed in the polymer matrix.     

Structures and properties of chicken myofibrillar protein gel induced by microwave heating

Structures and properties of myofibrillar protein gel prepared at different power (300–800 W) were evaluated. Amino acid analysis demonstrated that changes in microwave power did not alter primary structure of gel. However, an increase in microwave power could change higher structures of gel. As microwave power increased, α-helix content decreased and β-sheet content increased. Increased microwave power probably facilitated protein to unfold and expose the internal groups, causing surface hydrophobicity and the formation of disulphide bonds were enhanced, which indicated changes in tertiary and quaternary structures of protein. At 500 W, gel had the best ultrastructure where surface morphology, springiness and water holding capacity reached the optimum. Our findings suggested that microwave at an appropriate power (500 W) could change higher structures of myofibrillar protein gel to achieve desired processing and quality protein gel characteristics.