Li-Ion Battery with LiFePO<Subscript>4</Subscript> Cathode and Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> Anode for Stationary Energy Storage

Li-ion batteries based on commercially available LiFePO₄ cathode and Li₄Ti₅O₁₂ anode were investigated for potential stationary energy storage applications. The full cell that operated at flat 1.85 V demonstrated stable cycling up to 200 cycles followed by a rapid fade. A Li-ion full cell with Ketjen black modified LiFePO₄ cathode and an unmodified Li₄Ti₅O₁₂ anode exhibited negligible fade after more than 1200 cycles with a capacity of ~130 mAh/g at C/2. The improved stability, along with its cost-effectiveness, environmental benignity, and safety, make the LiFePO₄/Li₄Ti₅O₁₂ combination Li-ion battery a promising option for storing renewable energy.     

Synthesis and Characterization of Microwave Absorbing SrFe<Subscript>12</Subscript>O<Subscript>19</Subscript>/ZnFe<Subscript>2</Subscript>O<Subscript>4</Subscript> Nanocomposite

Zinc ferrite and strontium hexaferrite; SrFe₁₂O₁₉/ZnFe₂O₄ (SrFe_11.6Zn_0.4O₁₉) nanoparticles having super paramagnetic nature were synthesized by simultaneous co-precipitation of iron, zinc and strontium chloride salts using 5 M sodium hydroxide solution. The resulting precursors were heat treated (HT) at 850, 950 and 1150°C for 4 h in nitrogen atmosphere. The hysteresis loops showed an increase in saturation magnetization from 1.040 to 58.938 emu/g with increasing HT temperatures. The ‘as-synthesized’ particles have size in the range of 20–25 nm with spherical and needle shapes. Further, these spherical and needle shaped nanoparticles tend to change their morphology to hexagonal plate shape with increase in HT temperatures. The effect of such a systematic morphological transformation of nanoparticles on dielectric (complex permittivity and permeability) and microwave absorption properties were estimated in X band (8.2–12.2 GHz). The maximum reflection loss of the composite reaches −26.51 dB (more than 99% power attenuation) at 10.636 GHz which suits its application in RADAR absorbing materials.     

The Thermodynamic Behavior of Copper in the CaO-B<Subscript>2</Subscript>O<Subscript>3</Subscript> and BaO-B<Subscript>2</Subscript>O<Subscript>3</Subscript> Slag System

The Cu solubility was measured in the CaO-B₂O₃ and BaO-B₂O₃ slag systems to understand the dissolution mechanism of Cu in the slags. The Cu solubility had a linear relationship with oxygen partial pressure in the CaO-B₂O₃ slag system, which corresponds with previous studies. Also, the Cu solubilities in slag decreased with increasing the slag basicity, which value of slope was close to –0.5 in logarithmic form. From the results of experiment, the Cu dissolution mechanism established as follows:

Reaction kinetic,magnetic and microwave absorption studies of SrFe<Subscript>12</Subscript>O<Subscript>19</Subscript>/CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> ferrite nanocrystals

Mixture of cobalt ferrite and strontium hexaferrite nanocrystals i.e. SrFe₁₂O₁₉/CoFe₂O₄ exhibiting super paramagnetic nature were synthesized by modified flux method. The resulting precursors were heat treated (HT) at 900 and 1200°C for 4 h in nitrogen atmosphere. During heat treatment, transformation proceeds as instantaneous rate of nucleation and three dimensional growth with activation energy of 135.835 kJ/mole. The hysteresis loops showed a hike in saturation magnetization from 1.045 to 84.362 emu/g with an increase in HT temperature. The ‘as synthesized’ particles have size in the range of 10–20 nm with spherical shape. Further, these spherical shape particles tend to change their morphology to hexagonal plates with increase in HT temperatures. The relative complex permittivity and permeability of the composite powder are investigated. The minimum reflection loss of the composite powder reaches to −27.6 dB at 10.8 GHz which suits its application in RADAR absorbing materials.     

Thermodynamics on the Bi-Fe-Ti System and the Gibbs Energy of Bi<Subscript>9</Subscript>Ti<Subscript>8</Subscript>

Partial isothermal sections of the Bi-Fe-Ti system at 700 °C and 900 °C were constructed to investigate the reactivity of Fe with Bi-Ti liquid alloy. In the ternary system, three-phase equilibria such as liquid-Fe-Fe₂Ti, liquid-Fe₂Ti-Bi₂FeTi₄, and liquid-Bi₉Ti₈-Bi₂FeTi₄ were confirmed at both temperatures. The solubility of Fe in liquid Bi at these temperatures is negligibly small. On the other hand, it is notable that the solubility of Fe in liquid Bi containing Ti at 900 °C is much larger and reaches 2.3 mol pct. Then, we measured the electromotive force (emf) between Bi-20 mol pct Ti alloy and pure Ti at 700 °C in equimolar NaCl-KCl where 1 mol pct TiCl₂ was added. From the result, the interaction parameter of the liquid phase in the Bi-Ti system and the standard molar Gibbs energies of formation of Bi₉Ti₈ and Bi₂FeTi₄ at 700 °C were estimated.     

Effect of Ce<Subscript>2</Subscript>O<Subscript>3</Subscript> on Structure,Viscosity, and Crystalline Phase of CaO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Li<Subscript>2</Subscript>O-Ce<Subscript>2</Subscript>O<Subscript>3</Subscript> Slags

Aiming at devising new mold flux for Ce-bearing stainless steel, a fundamental investigation on the effect of Ce₂O₃ on properties of the CaO-Al₂O₃-Li₂O-Ce₂O₃ slag was provided by the present work. The results show that adding Ce₂O₃ could decrease the viscosity of the slag due to its effects on decreasing the polymerization of the slag. The crystalline process was restrained by increasing the content of Ce₂O₃, and the crystalline phases also can be influenced by the slag structure. The crystalline phases were transferred from LiAlO₂ and CaO to LiAlO₂ and CaCeAlO₄ with the addition of Ce₂O₃ to the slag, which could be well confirmed by the structure of the unit cell of the crystals.     

Ferrite Formation Dynamics and Microstructure Due to Inclusion Engineering in Low-Alloy Steels by Ti<Subscript>2</Subscript>O<Subscript>3</Subscript> and TiN Addition

The dynamics of intragranular ferrite (IGF) formation in inclusion engineered steels with either Ti₂O₃ or TiN addition were investigated using in situ high temperature confocal laser scanning microscopy. Furthermore, the chemical composition of the inclusions and the final microstructure after continuous cooling transformation was investigated using electron probe microanalysis and electron backscatter diffraction, respectively. It was found that there is a significant effect of the chemical composition of the inclusions, the cooling rate, and the prior austenite grain size on the phase fractions and the starting temperatures of IGF and grain boundary ferrite (GBF). The fraction of IGF is larger in the steel with Ti₂O₃ addition compared to the steel with TiN addition after the same thermal cycle has been imposed. The reason for this difference is the higher potency of the TiO _x phase as nucleation sites for IGF formation compared to the TiN phase, which was supported by calculations using classical nucleation theory. The IGF fraction increases with increasing prior austenite grain size, while the fraction of IGF in both steels was the highest for the intermediate cooling rate of 70 °C/min, since competing phase transformations were avoided, the structure of the IGF was though refined with increasing cooling rate. Finally, regarding the starting temperatures of IGF and GBF, they decrease with increasing cooling rate and the starting temperature of GBF decreases with increasing grain size, while the starting temperature of IGF remains constant irrespective of grain size.     

Experimental Investigation and Thermodynamic Modeling of the B<Subscript>2</Subscript>O<Subscript>3</Subscript>-FeO-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-Nd<Subscript>2</Subscript>O<Subscript>3</Subscript> System for Recycling of NdFeB Magnet Scrap

NdFeB magnet scrap is an alternative source of neodymium that could have a significantly lower impact on the environment than current mining and extraction processes. Neodymium can be readily oxidized in the presence of oxygen, which makes it easy to recover neodymium in oxide form. Thermochemical data and phase diagrams for neodymium oxide containing systems is, however, very limited. Thermodynamic modeling of the B₂O₃-FeO-Fe₂O₃-Nd₂O₃ system was hence performed to obtain accurate phase diagrams and thermochemical properties of the system. Key phase diagram experiments were also carried out for the FeO-Nd₂O₃ system in saturation with iron to improve the accuracy of the present modeling. The modified quasichemical model was used to describe the Gibbs energy of the liquid oxide phase. The Gibbs energy functions of the liquid phase and the solids were optimized to reproduce all available and reliable phase diagram data, and thermochemical properties of the system. Finally the optimized database was applied to calculate conditions for selective oxidation of neodymium from NdFeB magnet waste.     

Wear of Plasma Sprayed Conventional and Nanostructured Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>, Based Coatings

An ever increasing demand for high-performance ceramic coatings has made it inevitable for developing techniques with precise control over the process parameters to enable the fabrication of coatings with the desired microstructure and improved structural properties. The literature on plasma sprayed nanostructured ceramic coatings such as of Al₂O₃, Cr₂O₃, and their composites obtained using reconstituted nano sized ceramic powders has been reviewed in this study. Ceramic coatings due to their enhanced properties are on the verge of replacing conventional ceramic coatings used for various applications like automotive systems, boiler components, power generation equipment, chemical process equipment, aircraft engines, pulp and paper processing equipment, land-based and marine engine components, turbine blades etc. In such cases, the advantage is greater longevity and reliability for realizing the improved performance of ceramic coatings. It has been observed that the plasma sprayed nanostructured ceramic coatings show improvement in resistance to wear, erosion, corrosion, and mechanical properties as compared to their conventional counterparts. This article reviews various aspects concerning the plasma sprayed ceramic coatings such as (i) the present understanding of formation of plasma-spray coatings and factors affecting them, (ii) wear performance of nanostructured Al₂O₃, Cr₂O₃ and their composite ceramic coatings in comparison to their conventional counterparts, and (iii) mechanisms of wear observed for these coatings under various conditions of testing.     

Effect of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Concentration on Density and Structure of (CaO-SiO<Subscript>2</Subscript>)-xAl<Subscript>2</Subscript>O<Subscript>3</Subscript> Slag

The effect of Al₂O₃ concentration on the density and structure of CaO-SiO₂-Al₂O₃ slag was investigated at multiple Al₂O₃ mole percentages and at a fixed CaO/SiO₂ ratio of 1. The experiments were conducted in the temperature range of 2154 K to 2423 K (1881 °C to 2150 °C) using the aerodynamic levitation technique. In order to understand the relationship between density and structure, structural analysis of the silicate melts was carried out using Raman spectroscopy. The density of each slag sample investigated in this study decreased linearly with increasing temperature. When the Al₂O₃ content was less than 15 mole pct, density decreased with increasing Al₂O₃ content due to the coupling of Si (Al), whereas above 20 mole pct density of the slag increased due to the role of Al³⁺ ion as a network modifier.     

Thermodynamic evaluation and optimization of the MnO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and MnO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> systems and applications to inclusion engineering

All available thermodynamic and phase-diagram data have been critically evaluated and optimized for the liquid-slag phase and for all solid phases at 1 bar pressure from 298 K to above the liquidus temperatures for the systems MnO-Al₂O₃ and MnO-Al₂O₃-SiO₂, and a database of model parameters has been prepared. The modified quasichemical model was employed for the molten-slag phase. Calculations using the database were performed with applications to inclusion engineering for Mn/Si killed steel.     

Combustion Synthesized Porous Body of Fe₃O₄/Al System by Controlled Microwave Heating and Heating Behavior of the Products

Microwave-induced substitutional combustion reaction was utilized to fabricate porous ceramic composite from Fe₃O₄/Al powder mixtures.The porous composite body was obtained by controlling the combustion reaction progress in a 2.45 GHz single mode applicator.Prior to the fabrication of the porous body,heating behavior of the powder mixtures were studied in the separated electric（E）and magnetic（H）fields.In addition,heating ability of the microwave fabricated porous product was also investigated.Fe₃O₄powder can be heated up easily in both maximum H and E field,but a better heating was observed in the maximum H field.Regardless of the mixtures ratio（mixing compositions）,maximum H field shows better heating characteristics.In E-field heating,temperature of the Fe₃O₄ samples decreased sharply when Al powder was added.However,the same phenomenon was not observed in the maximum H field heating.Thus,fabrication of the porous composite body was carrying out in maximum H field.Through an adequate control of the reaction progress,products with a porous structure consisting of well-distributed metal particles in the alumina and/or hercynite matrix were obtained.Consequently,heating of the fabricated porous composite body was also been successfully carried out in the maximum H field.Product phases and microstructure were the main factors influencing the heating ability of the porous composite body.     

Mechanical behaviour of Ti<Subscript>5</Subscript>Si<Subscript>3</Subscript> based alloys and composites

The demand for materials to be used in the components operating above 1100°C in advanced aero-engines drives the development of the silicide-based intermetallic alloys and composites, including the titanium silicides. The mechanical behaviour of Ti₅Si₃ and its composites has been reviewed with emphasis on the microstructure-property relationships. It is found that the grain size is a critical parameter, and smaller grain sizes are desirable for reducing the magnitude of internal residual stress caused by the crystallographic anisotropy in coefficients of thermal expansion. The reduction in grain size leads to significant improvement in hardness, room temperature flexural strength and fracture toughness. On the other hand, the high temperature strength observed at slow strain rates and creep resistance are higher in the samples with the coarser grain sizes. Further improvements in the strength, fracture toughness and high temperature creep resistance are possible, either through the development of multiphase alloys, or by the use of ceramic reinforcements in composites.     

The Viscous Behavior of FeO<Subscript>t</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> Copper Smelting Slags

Understanding the viscous behavior of copper smelting slags is essential in increasing the process efficiency and obtaining the discrete separation between the matte and the slag. The viscosity of the FeO_t-SiO₂-Al₂O₃ copper smelting slags was measured in the current study using the rotating spindle method. The viscosity at a fixed Al₂O₃ concentration decreased with increasing Fe/SiO₂ ratio because of the depolymerization of the molten slag by the network-modifying free oxygen ions (O²⁻) supplied by FeO. The Fourier transform infrared (FTIR) analyses of the slag samples with increasing Fe/SiO₂ ratio revealed that the amount of large silicate sheets decreased, whereas the amount of simpler silicate structures increased. Al₂O₃ additions to the ternary FeO_t-SiO₂-Al₂O₃ slag system at a fixed Fe/SiO₂ ratio showed a characteristic V-shaped pattern, where initial additions decreased the viscosity, reached a minimum, and increased subsequently with higher Al₂O₃ content. The effect of Al₂O₃ was considered to be related to the amphoteric behavior of Al₂O₃, where Al₂O₃ initially behaves as a basic oxide and changes to an acidic oxide with variation in slag composition. Furthermore, Al₂O₃ additions also resulted in the high temperature phase change between fayalite/hercynite and the modification of the liquidus temperature with Al₂O₃ additions affecting the viscosity of the copper smelting slag.     

Effect of CaO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-MgO slags on the formation of MgO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> inclusions in ferritic stainless steel

A thermodynamic equilibrium between the Fe-16Cr melts and the CaO-Al₂O₃-MgO slags at 1823 K as well as the morphology of inclusions was investigated to understand the formation behavior of the MgO-Al₂O₃ spinel-type inclusions in ferritic stainless steel. The calculated and observed activities of magnesium in Fe-16Cr melts are qualitatively in good agreement with each other, while those of aluminum in steel melts exhibit some discrepancies with scatters. In the composition of molten steel investigated in this study, the log (X _MgO/X _{Al 2}O₃) of the inclusions linearly increases by increasing the log [a _Mg/a _Al ² ·a _O ² ] with the slope close to unity. In addition, the relationship between the log (X _MgO/X _{Al 2}O₃) of the inclusions and the log (a _MgO/a _{Al 2}O₃) of the slags exhibits the linear correlation with the slope close to unity. The compositions of the inclusions are relatively close to those of the slags, viz. the MgO-rich magnesia-spinel solid solutions were formed in the steel melts equilibrated with the highly basic slags saturated by CaO or MgO. The spinel inclusions nearly saturated by MgO were observed in the steel melts equilibrated with the slags doubly saturated by MgO and MgAl₂O₄. The spinel and the Al₂O₃-rich alumina-spinel solid solutions were formed in the steel melts equilibrated with the slags saturated by MgAl₂O₄ and MgAl₂O₄-CaAl₂O₄ phases, respectively. The apparent modification reaction of MgO to the magnesium aluminate inclusions in steel melts equilibrated with the highly basic slags would be constituted by the following reaction steps: (1) diffusion of aluminum from bulk to the metal/MgO interface, (2) oxidation of the aluminum to the Al³⁺ ions at the metal/intermediate layer interface, (3) diffusion of Al³⁺ ions and electrons through the intermediate layer, and (4) magnesium aluminate (MgAl₂O₄ spinel, for example) formation by the ionic reaction.     

Electrical conductivity of NaF-AlF<Subscript>3</Subscript>-CaF<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> melts

The electrical conductivity of NaF-AlF₃-Al₂O₃ melts with a CaF₂ concentration of 5 wt % is measured at a continuously varying cell constant when the molar cryolitic ratio CR = [NaF]/[AlF₃] changes from 1.2 to 2.0 [1, 2]. The experimental data are used to obtain a regression equation to describe the dependence of the electrical conductivity of the melts under study on CR, the alumina content, and temperature {χ] = f(CR, [Al₂O₃], T)}.     

Phase-equilibrium data and liquidus for the system “MnO”-CaO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> at Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/SiO<Subscript>2</Subscript> of 0.55 and 0.65

Phase-equilibrium data and liquidus isotherms for the system “MnO”-CaO-(Al₂O₃+SiO₂) at silicomanganese alloy saturation have been determined in the temperature range of 1373 to 1723 K. The results are presented in the form of the pseudoternary sections “MnO”-CaO-(Al₂O₃+SiO₂) with Al₂O₃/SiO₂ weight ratios of 0.55 and 0.65. The primary-phase fields have been identified in this range of conditions.