Evaluation of fuels for the synthesis of Li2CoMn3O8

Li₂CoMn₃O₈, a 5 V cathode material used in rechargeable lithium batteries, has been synthesized by adopting a novel technique of using fuels along with the nitrate reactants. The effect of the fuel on the synthesis of Li₂CoMn₃O₈ has been analyzed in terms of the physical and electrochemical properties of the final product formed by various methods such as solid-state carbonate fusion and the solution route using acetate and nitrate precursors. Powder X-ray diffraction FT IR spectrum, particle size, surface area and SEM analysis were carried out. The combustion method, also known as selfpropagating high temperature (SPHT) method, has been employed in the present study by using nitrate mixtures of the respective salts and a nitrogeneous fuel (urea or glycine) at a temperature of 300 °C for 3 hrs. The nitrate reactants without the addition of fuel gave only a deliquescent product even at elevated temperature (600 °C) thus indicating the necessity of fuels. Similar attempts using acetate reactants with and without the addition of nitrogeneous fuels were made separately in order to find out the necessity of fuel also in this case. The characterization of the product in terms of purity, single-phase formation and surface morphology suggested that the fuel played no role in the case of the acetate precursors. A comparative study was made on the products obtained by the acetate precursor, combustion method and the conventional carbonate method. Among the three methods, the combustion method with glycine as fuel yielded the spinel phase with high purity Li₂CoMn₃O₈ with superior electrochemical behavior both in terms of high cell voltage and good cycle life behavior.     

Synthesis and characterization of lithium ferrite by oxalate precursor route

Nanocrystalline lithium ferrite (LiFe₅O₈) powders have been synthesized by oxalate precursor route. The effects of Fe³⁺/Li⁺ mole ratio, and annealing temperature on the formation, crystalline size, morphology and magnetic properties were systematically studied. The Fe³⁺/Li⁺ mole ratio was controlled from 5 to 3.33 while the annealing temperature was controlled from 600 to 1100 °C. The resultant powders were investigated by differential thermal analyzer (DTA), X-ray diffractometer (XRD), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM). DTA results showed that LiFe₅O₈ phase started to form at around 520 °C. XRD indicated that LiFe₅O₈ phase always contained α-Fe₂O₃ impurity and the hematite phase formation increased by increasing the annealing temperature ?850 °C for different Fe³⁺/Li⁺ mole ratios 5, 4.55 and 3.85. Moreover, lithium ferrite phase was formed with high conversion percentage at critical annealing temperature 750–800 °C. Single well crystalline LiFe₅O₈ phase was obtained at Fe³⁺/Li⁺ mole ratio 3.33 and annealing temperatures from 800 to 1000 °C. Maximum saturation magnetization (68.7 emu/g) was achieved for the formed lithium ferrite phase at Fe³⁺/Li⁺ mole ratio 3.33 and annealing temperature 1000 °C.     

Investigation on the electrochemical performances of Li<Subscript>4</Subscript>Mn<Subscript>5</Subscript>O<Subscript>12</Subscript> for battery applications

In this study, well-crystallized Li₄Mn₅O₁₂ powder was synthesized by a self-propagating combustion method using citric acid as a reducing agent. Various conditions were studied in order to find the optimal conditions for the synthesis of pure Li₄Mn₅O₁₂. The precursor obtained was then annealed at different temperatures for 24 h in a furnace. X-ray diffraction results showed that Li₄Mn₅O₁₂ crystallite is stable at relatively low temperature of 400 °C but decompose to spinel LiMn₂O₄ and monoclinic Li₂MnO₃ at temperatures higher than 500 °C. The prepared samples were also characterized by FESEM and charge-discharge tests. The result showed that the specific capacity of 70.7 mAh/g was obtained within potential range of 4.2 to 2.5 V at constant current of 1.0 mA. The electrochemical performances of Li₄Mn₅O₁₂ material was further discussed in this paper.     

Synthesis hexagonal ZrW2O8 and its thermal properties

ZrW₂O₈ as the typical negative thermal expansion (NTE) material has attracted much attention for the potential applications in various fields such as tailored coefficient of thermal expansion (CTE) composites. The hexagonal ZrW₂O₈ (h-ZrW₂O₈), with the combination of ZrO₂ and WO₃ in a composite, was synthesized at a pressure of 2 GPa and the temperature between 600°C and 700°C. We found h-ZrW₂O₈ decomposes to ZrO₂+WO₃ oxides that start from 500°C and end at 800°C, and determined the CTE of h-ZrW₂O₈ is?16.3×10^?6°C^?1 in the temperature range from 150°C to 450°C. The results show that ZrW₂O₈ with a hexagonal structure is metastable and exhibits high NTE property like its cubic structure.     

Preparation of LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> cathode materials by electrospinning

LiNi_0.5Mn_1.5O₄ cathode material was prepared by electrospinning using lithium hydroxide, manganese acetate, nickel acetate, acetic acid, ethanol, and poly(vinyl pyrrolidone) as raw materials. The effect of calcination temperature on the structure, morphology, and electrochemical properties was investigated. XRD results indicate that the LiNi_0.5Mn_1.5O₄ composite is well crystallized as a spinel structure at calcination temperature of 650 °C for 3 h. SEM results reveal that this composite has a nanofiber shape with average size of about 300–500 nm. Electrochemical performance tests reveal that this composite shows the initial discharge capacity of 127.8 and 105 mAhg^?1 at 0.1 and 3 C rates, respectively, and exhibits good cycling performance.     

Electrochemical properties of LiFe0.9Mg0.1PO4 / carbon cathode materials prepared by ultrasonic spray pyrolysis

The LiFe_0.9Mg_0.1PO₄/C powder of pure olivine phase can be prepared with the duplex process of spray pyrolysis synthesis (at 450 ^°C) and subsequent heat treatment (at 700 ^°C for 2, 4 and 8 h). From scanning electron microscopy observation with corresponding elemental mapping images of iron, phosphorous and magnesium, it could be found that the LiFe_0.9Mg_0.1PO₄ powders are covered with fine pyrolyzed carbon. Raman spectra indicate that the phase of carbon with higher electronic conductive phase is predominant when prolonged subsequent heat treatment is carried out. The carbon coatings on the LiFe_0.9Mg_0.1PO₄ surface can improve the conductivity of the LiFe_0.9Mg_0.1PO₄ powder (3.8×10⁻⁵ S cm⁻¹) to about a factor of ∼10⁴ higher than the conductivity of LiFePO₄. The stability and cycle life of a charge/discharge cycle test of lithium ion secondary batteries are also enhanced. The results indicate that the LiFe_0.9Mg_0.1PO₄ powder, prepared at a pyrolysis temperature of 450 ^°C and with post-heat-treatment at 700 ^°C for 8 h, exhibits a specific initial discharge capacity of about 132 mA h g⁻¹ at C/10 rate, 105 mA h g⁻¹ at 1C, and 87 mA h g⁻¹ at 5C.     

Micro‐Raman and photoluminescence analysis of composite vanadium oxide/poly‐vinyl acetate fibres synthesised by electro‐spinning

Composite vanadium oxide (VO_x)‐based fibres were synthesised by the electro‐spinning method combined with conventional sol–gel processing using polyvinyl acetate (PVAc) as a polymeric binder and vanadium oxytriisopropoxide as a vanadium oxide precursor. The microstructure and composition of as‐spun and calcined (300–500 °C) VO_x–PVAc fibres were systematically investigated by scanning electron microscopy, thermogravimetry, reflectance infrared Fourier transform, micro‐Raman spectroscopy and photoluminescence in view of their possible use in gas sensor fabrication. The comparative discussion of the characterization results indicates that V₂O₅–PVAc fibres are obtained. Calcination gradually removes PVAc and promotes structural rearrangement with consequent fibre‐morphology changes. With increasing calcination temperature, the crystallinity degree of V₂O₅ improves and a more oxygen‐deficient substoichiometric surface layer forms. Calcination at 400 °C preserves the fibre integrity. Indeed, fibres calcined at this temperature appear as the most suitable ones for use as the active layer in gas‐sensing devices. Copyright © 2011 John Wiley & Sons, Ltd.     

A structural and Mössbauer study of Y3Fe5O12 nanoparticles prepared with high energy ball milling and subsequent sintering

The influence of ball milling and subsequent sintering of a 3:5 molar mixture of Y₂O₃ and α-Fe₂O₃ on the formation of nanocrystalline Y₃Fe₅O₁₂ (YIG) particles is studied. Pre-milling the mixture for 100 h lowers the onset temperature at which the material forms to 900°C which is 200°C lower than that reported when a similar mixture of reactants was premilled for shorter times. A single-phased nanocrystalline Y₃Fe₅O₁₂ phase develops as a sole product when the pre-milled mixture is heated at 1,000°C (12 h). This temperature is ~300–400°C lower than those used to prepare the material conventionally. The bulk and surface crystal structure of the nanoparticles is studied with X-ray diffraction, Mössbauer spectroscopy, Atomic Force Microscope (AFM) and X-ray photoelectron spectroscopy.     

Synthesis of corundum structure ITO nanocrystals by hydrothermal process at low pressure and low temperature

The corundum structures of In₂O₃:Sn (ITO) nanoparticles were synthesized by hydrothermal processing of InCl₃ and SnCl₄·5H₂O precursor at low temperature of 250 °C and 40 bar pressure for 3 h. The precursor was precipitated in a white gel of InOOH. After drying at 150 °C in air, it was crystallized in orthorhombic structure. InOOH powder was transformed into dark-gray rhombohedral In₂O₃ by sintering at 420 °C in forming gas for 1 h. The samples were characterized by means of XRD, SEM, and TEM. The particle size of the resulted ITO powder was about 32 nm.     

Low-temperature sintering effects on NASICON-structured LiSn<Subscript>2</Subscript>P<Subscript>3</Subscript>O<Subscript>12</Subscript> solid electrolytes prepared via citric acid-assisted sol-gel method

LiSn₂P₃O₁₂ with sodium (Na) super ionic conductor (NASICON)-type rhombohedral structure was successfully obtained at low sintering temperature, 600 °C via citric acid-assisted sol-gel method. However, when the sintering temperature increased to 650 °C, triclinic structure coexisted with the rhombohedral structure as confirmed by X-ray diffraction analysis. Conductivity–temperature dependence of all samples were studied using impedance spectroscopy in the temperature range 30 to 500 °C, and bulk, grain boundary and total conductivity increased as the temperature increased. The highest bulk conductivity found was 3.64?×?10^?5 S/cm at 500 °C for LiSn₂P₃O₁₂ sample sintered at 650 °C, and the lowest bulk activation energy at low temperature was 0.008 eV, showing that sintering temperature affect the conductivity value. The voltage stability window for LiSn₂P₃O₁₂ sample sintered at 600 °C at ambient temperature was up to 4.4 V. These results indicated the suitability of the LiSn₂P₃O₁₂ to be exploiting further for potential applications as solid electrolytes in electrochemical devices.     

Dielectric properties of Bi<Subscript>2</Subscript>PbNb<Subscript>2</Subscript>O<Subscript>9</Subscript> ceramics prepared by different techniques

Different techniques for the synthesis of Bi₂PbNb₂O₉, namely the mixed oxide technique, molten salt synthesis, hydrothermal synthesis, co-precipitation and the tartaric acid gel method were investigated and the results on the dielectric properties are reported. The heat-treatment of the precursor powders was the same for all precursor powders. Sintering at 1040 °C under ambient pressure resulted in polycrystalline specimens, while hot-forging at 1040 °C with a pressure of 20 MPa produced c-axis aligned samples. Phase composition and crystallite orientation of the sintered bodies were analyzed by X-ray diffraction. Single-phase material was obtained in all cases. Hot-forging not only yielded c-axis orientation, but also increased the relative densities above 99.4%. The relative permittivity decreased for c-axis oriented material compared to polycrystalline ceramics. Values for the relative permittivity for the hot-forged specimens at 100 °C at 100 kHz varied between 165 and 250, depending on the fabrication method. The Curie temperature for the c-axis aligned samples was 568 °C, independent of the nature of the precursor powders. PACS 77.22.-d; 77.84.-s     

Kinetic analysis of the thermal decomposition of pristine and γ-irradiated zinc uranyl acetate

Thermal decomposition of pristine and γ-irradiated zinc uranyl acetate was investigated in air using isothermal and dynamic thermogravimetric techniques. The decomposition proceeded via one major process with the formation of triuranates ZnU₃O₁₀ as solid residues. Kinetic analysis of isothermal data, when compared with various solid-state reaction models, showed that the decomposition reaction is best fitted by the phase-boundary model. Kinetic analysis of the dynamic TG curves was discussed with reference to integral methods of modified Coats and Redfern equations. Kinetic and thermodynamic parameters were calculated and evaluated. IR spectroscopy and X-ray powder diffraction techniques were employed to follow the chemical composition of solid residue at different calcination temperatures. The results display that the triuranate ZnU₃O₁₀ starts forming by calcination of zinc uranyl acetate at temperatures?>?300 °C and undergoes decomposition at higher temperatures (>600 °C) with the formation of U₃O₈. The results were evaluated regarding the utilization of zinc uranyl acetate as an important source of diuranates and triuranates.     

Electrical properties of GdBaCo2O5+x for ITSOFC applications

In order to develop a cathode that can be used in intermediate temperature solid oxide fuel cells (ITSOFC), the double perovskite material GdBaCo₂O_5+x has been prepared and its electrode performance investigated at temperatures below 700 °C by AC impedance spectroscopy. Preliminary results show that the ASRs of GdBaCo₂O_5+x cathode materials are as low as 0.53 Ω cm² at 645 °C. This encouraging data identifies GdBaCo₂O_5+x as a potential cathode material for ITSOFCs.     

Promising anode material for lithium-ion cells based on cobalt oxide synthesized by microwave heating

High-performance anode material for lithium-ion cell based on cobalt oxide was synthesized through a combination of sol-gel route and subsequent microwave heating. The influence of microwave irradiation temperature of the precursor on the characteristics of the active materials formed was studied. The physicochemical, structural, and morphological properties of the materials were studied in addition to the electrochemical performance by cyclic voltammetry and charge-discharge cycling vs. Li⁺/Li. Microwave heating at 350 °C resulted in the formation of Co₃O₄, whereas at 450 and 550 °C, a mixture of Co₃O₄, CoO, and Co was formed. Co₃O₄ synthesized at 350 °C possessed porous morphology with high specific surface area and exhibited superior electrochemical performance with initial specific capacity of 982 mAh g^?1 and coulombic efficiency of ~75% along with good cycle performance retaining ~87% of initial capacity after 60 cycles.     

Nanocrystalline CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> powders prepared by egg white solution route: synthesis,characterization and its giant dielectric properties

Nanocrystalline CaCu₃Ti₄O₁₂ powders with particle sizes of 50–90 nm were synthesized by a simple method using Ca(NO₃)₂·4H₂O, Cu(NO₃)₂·4H₂O, titanium(diisoproproxide) bis(2,4-pentanedionate) and freshly extracted egg white (ovalbumin) in aqueous medium. The synthesized precursor was characterized by TG-DTA to determine the thermal decomposition and crystallization temperature which was found to be at above 400 °C. The precursor was calcined at 700 and 800 °C in air for 8 h to obtain nanocrystalline powders of CaCu₃Ti₄O₁₂. The calcined CaCu₃Ti₄O₁₂ powders were characterized by XRD, FTIR, SEM and TEM. Sintering of the powders was conducted in air at 1100 °C for 16 h. The XRD results indicated that all sintered samples have a typical perovskite CaCu₃Ti₄O₁₂ structure and a small amount of CuO, although the sintered sample of the 700 °C calcined powders contained some amount of CaTiO₃. SEM micrographs showed the average grain sizes of 12.0±7.8 and 15.5±8.9 μm for the sintered CaCu₃Ti₄O₁₂ ceramics prepared using the CaCu₃Ti₄O₁₂ powders calcined at 700 and 800 °C, respectively. The sintered samples exhibit a giant dielectric constant, ε^′ of ∼ 1.5–5×10⁴. The dielectric behavior of both samples exhibits Debye-like relaxation, and can be explained based on a Maxwell–Wagner model. PACS 77.22.Gm; 81.05.Je; 81.07.Wx; 81.20.Ev     

A correlation between structural and optical properties of cobalt oxide nanoparticles for various annealing conditions

Two stable phases of cobalt oxide nanoparticles of controlled sizes have been synthesized using environmentally friendly inorganic precursor. Structural characterization using X-ray diffraction (XRD) shows a single-phase spinal Co₃O₄ structure up to annealing temperature of 800 °C and a mixed phase of Co₃O₄ and CoO particles for T>900 °C. Single-phase CoO nanoparticles are also obtained by annealing the particles at a temperature >900 °C and cooling in inert atmosphere. Average macro- and micro-strain were estimated using XRD data. Macrostrain was found to be the minimum for particles annealed at 600 °C, whereas microstrain was found to decrease with increasing annealing temperature up to 900 °C. A correlation between the density of localized states (DOS) in the band gap and strain is expected because the origin of both strain and DOS are defects and bond length distortions. Sub-gap absorption measurement and model calculations have been used for the determination of DOS. For cobalt oxide nanoparticle samples we find a correlation between estimated strain and density of states in the band gap.     

Soft acoustic mode in ferroelastic lanthanum pentaphosphate

The temperature dependence of the C₅₅ elastic constant of LaP₅O₁₄ has been investigated, using Brillouin scattering, between room-temperature and 225°C, across the 126°C ferroelastic phase transition of this material. C₅₅ is found to vanish at the transitión. Physical implications of this result are discussed.     

Influence of heat treatment on structure and some physical properties of lithium boro-niobate glass

The glass composition (90?mol% Li₂B₄O₇–10?mol% Nb₂O₅) was prepared by the melt quenching technique. The quenched sample was heat treated at 480°C, 545°C and 630°C for 5?h and heat treated at 780°C with different time. The times were 5, 10, 15, 20, 28, and 36?h. The glass and glass ceramics were studied by differential thermal analysis (DTA), X-ray diffraction (XRD), and dc conductivity as a function of temperature. Lithium niobate (LiNbO₃) and lithium diborate (Li₂B₄O₇) were the main phases in glass ceramic addition to traces from LiNb₃O₈. Crystallite size of the main phases determined from the X-ray diffraction peaks are in the range <100?nm. The fraction of crystalline (LiNbO₃) phase increases with increase the heat treatment temperature and time. The relation between physical properties and structure were studied.     

Structural and electrochemical properties of LiNi0.4Co0.4−xAl0.2+xO2 cathode materials for lithium-ion batteries

Three Al doped lithium nickel cobalt oxide (LiNi_0.4Co_0.4−xAl_0.2+xO₂) cathode materials for lithium ion batteries were synthesized by solid state reaction method at a temperature of 800 °C for 18 hours. The samples were crystalline as revealed by powder X-Ray diffraction (XRD). The ratios of the elements were determined by Energy Dispersive Analysis of X-rays (EDAX). The electrochemical properties obtained by charge/discharge cycling showed that the average discharge capacity for LiNi_0.4Co_0.4Al_0.2O₂ was 117 mAh/g. A good capacity retention was also shown by the material upon cycling. Paper presented at the International Conference on Functional Materials and Devices 2005, Kuala Lumpur, Malaysia, June 6 – 8, 2005.     

A nearly zero temperature gradient furnace system for high pressure multi-anvil experiments

A new furnace system with an almost zero temperature gradient throughout the sample area was designed for multi-anvil high pressure experiments. Test experiments of the new design were performed using 18/11 and 25/15 cell assemblies at 4?GPa, 1400°C and 1500°C, respectively. The temperature field within the sample capsules appeared to be very homogenous as indicated by Mg₂Si₂O₆–MgCaSi₂O₆ two-pyroxene thermometry, by direct temperature measurements using two thermocouples within the same assembly, and by distribution of solid and liquid phases in the sample capsule. The temperature gradient is estimated to be <2.4°C/mm over an area of 4?×?5?mm² within the furnace. It is significantly lower than standard multi-anvil experiments with straight or stepped furnace systems, which are at the levels of 20–200°C/mm.