Spherical shape BaO-ZnO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> glass powders prepared by spray pyrolysis

Fine-sized BaO-ZnO-B₂O₃-SiO₂ (BZBS) glass powders were directly prepared by high temperature spray pyrolysis. The hollow glass powders prepared at low preparation temperature of 1000 °C had a low density of 2.65 g/cm³. However, the densities of the BZBS powders obtained at preparation temperatures of 1200 and 1400 °C were each 3.92 and 4.13 g/cm³. The mean size of the BZBS glass powders prepared by spray pyrolysis at preparation temperature of 1400 °C was 0.98 μm. The glass transition temperature (T_g) of the prepared BZBS glass powders was 518.9 °C. The dielectric layers formed from the prepared BZBS glass powders with a dense structure had a clean surface and a dense inner structure without voids at the firing temperature of 580 °C. The transparencies of the dielectric layers formed from the prepared BZBS glass powders were higher than 90% within the visible range. PACS 42.70.Ce; 85.60.Pg; 71.55.Jv     

Synthesis,structural and electrical properties of double perovskite Sr<Subscript>2</Subscript>NiMoO<Subscript>6</Subscript> ceramics

The double perovskite Sr₂NiMoO₆ powders and ceramics were prepared by two different (conventional and precursor) solid-state reaction methods. The phase structure was characterized by XRD and TEM techniques. It has been indicated that single-phase perovskite powders were obtained when calcined in air at 1300°C. However, nano-particles of the size 30–60 nm have been found in powders prepared with the precursor method, while those from the conventional route exhibit large irregular shaped particles with aggregation. The dielectric properties (ε _r and tanδ) were also examined in the sintered ceramics. The results showed the transition point at 280°C for conventional route, while no clear phase change was observed in ceramics from the precursor route. These observations clearly indicate that the different starting processes affected the phase formation behavior and the electrical properties of Sr₂NiMoO₆ ceramics.     

Structural and electrical properties of 0.7Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript>–0.3PbTiO<Subscript>3</Subscript> thin films grown on Ir/MgO buffered Si(100) substrates

Thin films of 0.7Pb(Mg_1/3Nb_2/3)O₃–0.3PbTiO₃ (PMN-PT) have been grown on Ir/MgO buffered Si(100) substrates at different substrate temperatures by pulsed laser deposition. Crystalline phases as well as preferred orientations in the PMN-PT films were investigated by X-ray diffraction analysis (XRD). The microstructure, dielectric and ferroelectric properties of PMN-PT film prepared at 650 °C were studied. The results show that the film prepared at 650 °C exhibits pure perovskite phase and single c-axis orientation. The dielectric constant and dissipation factor of the single c-axis oriented film are 1000 and 0.04 at a frequency of 1 kHz, while the remnant polarization and coercive field are about 13.0 μC/cm² and 100 kV/cm under an electric field of 480 kV/cm, respectively. PACS 81.15.Fg; 77.80.-e; 77. 22.Ej; 77.55.+f; 85.50.Gk     

Synthesis of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> by molten salt technique

Lithium manganese oxide powders have been successfully prepared by a molten salt synthesis using eutectic mixture of LiCl and MnO₂ salt at 900 °C. The synthesis was performed in open atmosphere. The crystalline powders were characterized for their phase identification using X-ray diffraction analysis. The physicochemical properties of the lithium manganese oxide powders are investigated by thermal analysis (thermo gravimetric analysis/ differential thermal analysis), Fourier transform infrared spectroscopy, Raman spectroscopy, atomic absorption spectroscopy, electron spin resonance spectroscopy, and scanning electron microscopy. This work shows the feasibility for obtaining lithium manganese oxide at low-temperature molten salt flux method.     

Genesis,structural, and transport properties of La<Subscript>2</Subscript>Mo<Subscript>2-x</Subscript>W<Subscript>x</Subscript>O<Subscript>9</Subscript> prepared via mechanochemical activation

Fast oxide-ion conductors La₂Mo_2-xW_xO₉ (x = 0–1) have been prepared using mechanochemical activation (MA) of starting oxides in a high-power planetary ball mill. Studies of La₂Mo_2-xW_xO₉ genesis and structural properties using thermal analysis, XRD, SEM, IR, and Raman spectroscopy have revealed that MA results in the formation of an amorphous precursor, while the cubic β-phase is formed after calcination at 700–900 °C. Due to a high dispersion of powders, high-density pellets of W-LAMOX ceramics have been obtained already after sintering at 950 °C. Their electrical conductivity measured by the impedance spectroscopy depends on the W concentration being sufficiently high (up to 5.6?10^?3 S/cm at 630 °C) at temperatures below 650 °C.     

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     

Effect of calcination conditions on lithium conductivity in Li<Subscript>1.3</Subscript>Ti<Subscript>1.7</Subscript>Al<Subscript>0.3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> prepared by sol-gel route

In order to study the influence of powder calcination temperature on lithium ion conductivity, synthesized Li_1.3Ti_1.7Al_0.3(PO₄)₃ (LATP) was calcined at temperatures between 750 and 900 °C. The shape and size of the particles were characterized employing scanning electron microscopy (SEM), and specific surface area of the obtained powder was measured. The crystallinity grade of different heat-treated powders was calculated from XRD spectra. Posteriorly, all powders were sintered at 1100 °C employing field-assisted sintering (SPS), and the electrical properties were correlated to the calcination conditions. The highest ionic conductivity was observed for samples made out of powders calcined at 900 °C.     

Structural and dielectric characterization of Sr substituted Ba(Zr,Ti)O<Subscript>3</Subscript> based functional materials

Single phase Sr substituted BaZr_0.1Ti_0.9O₃ (also known as BZT) ceramics with a formula Ba_1-xSr_xZr_0.1Ti_0.9O₃ (x=0.10, 0.20, 0.30, 0.40 and 0.50) are prepared using a solid state reaction of mixed oxides at 1250 °C for 15 h. Analysis of XRD patterns of the ceramic powders show that Sr substitutes into Ba sites and reduces the lattice parameter. The powders are sintered at 1600 °C for 6 h to investigate the microstructure and functional properties. It is found that strontium substitution significantly modifies the microstructure and greatly influences the dielectric properties. The increase in Sr content reduces the ceramic grain size and results in spherical grains. With an increase in Sr content, the Curie temperature is lowered, and the relative permittivity maximum is increased and broadened. In Ba_1-xSr_xZr_0.1Ti_0.9O₃ with x=0.30, the relative permittivity reached a maximum of 26600 and with further increase of Sr content, the relative permittivity is lowered and the phase transition is found to be broad and diffused. The ferroelectric hysteresis characteristics are discussed in detail. PACS 77.84.-s; 77.80.Bh; 77.22.Ch; 77.84.Dy; 77.22.-d     

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.     

Effect of high-temperature crystallization on the electrochemical properties of LiNi<Subscript>0.5</Subscript>Co<Subscript>0.2</Subscript>Mn<Subscript>0.3</Subscript>O<Subscript>2</Subscript> synthesized from a lithiated transition metal oxide precursor

The lithiated transition metal oxide precursor (LNCMO) with typical α-NaFeO₂ structure and imperfect crystallinity, obtained from a hydrothermal process, was pretreated at 500 °C and then subjected to sintering at 800–920 °C to synthesize the ternary layered LiNi_0.5Co_0.2Mn_0.3O₂ (NCM523). X-ray diffraction (XRD), scanning electron microscope (SEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and charge/discharge testing were used for investigating the effect of the high-temperature crystallization on the properties of the NCM523 cathode materials. The results show that the materials heated at 880–900 °C possess superior cation ordering, perfect crystallinity, and excellent electrochemical performances, among which the material heated at 900 °C delivers better performances, with the initial discharge capacity of 152.6 mAh g^?1 at 0.5 C over 3.0 to 4.3 V and the capacity retention of 95.5% after 50 cycles. Furthermore, the effect of the high-temperature crystallization on the Li⁺ diffusion coefficient, potential polarization, and electrochemical resistance are discussed.     

Improvement of the intergranular pinning energy in uniaxially compacting (Bi-Pb)<Subscript>2</Subscript>Sr<Subscript>2</Subscript>Ca<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>10+δ</Subscript> ceramic samples

Measurements of the electrical resistivity as a function of temperature, ρ(T), for different values of applied magnetic field, B_a (0 ≤ B_a ≤ 50 mT), were performed in polycrystalline samples of Bi_1.65Pb_0.35Sr₂Ca₂ Cu₃O_10+δ subjected to different uniaxial compacting pressure (UCP). We have found appreciable differences in the grain orientation between samples by using X-ray diffractometry. From the X-ray diffraction patterns performed, in powder and pellet samples, we have estimated the Lotgering factor along the (00l) direction, F_(00l). The results indicate that F_(00l) increases ~23% with increasing UCP suggesting that grains of these samples are preferentially aligned along the c-axis, which is parallel to the compacting direction. The resistive transition of the samples have been interpreted in terms of the thermally activated flux-creep model. In addition, the effective intergranular pinning energy, U₀, have been determined for different applied magnetic field. The magnetic field dependence of U₀, for B_a > 8 mT, was found to follow a H^{- α} dependence with α = 0.5 for all samples. The analysis of the experimental data strongly suggested that increasing UCP results in appreciable changes in both the grain alignment and the grain connectivity of the samples. We have successfully interpreted the data by considering the existence of three different superconducting levels within the samples: the superconducting grains, the weak-links, and the superconducting clusters.     

Thermostable photocatalytically active TiO<Subscript>2</Subscript> anatase nanoparticles

Anatase is the low-temperature (300–550 °C) crystalline polymorph of TiO₂ and it transforms to rutile upon heating. For applications utilizing the photocatalytic properties of nanoscale anatase at elevated temperatures (over 600 °C) the issue of phase stabilisation is of major interest. In this study, binary TiO₂/SiO₂ particles were synthesized by a flame aerosol process with TiCl₄ and SiCl₄ as precursors. The theoretical Si/Ti ratio was varied in the range of 0.7–1.3 mol/mol. The synthesized TiO₂/SiO₂ samples were heat treated at 900 and 1,000 °C for 3 h to determine the thermostability of anatase. Pyrogenic TiO₂ P25 (from Evonik/Degussa, Germany) widely applied as photocatalyst was used as non-thermostabilized reference material for comparison of photocatalytic activity of powders. Both the non-calcinated and calcinated powders were characterized by means of XRD, TEM and BET. Photocatalytic activity was examined with dichloroacetic acid (DCA) chosen as a model compound. It was found that SiO₂ stabilized the material retarding the collapse of catalyst surface area during calcination. The weighted anatase content of 85% remains completely unchanged even after calcination at 1,000 °C. The presence of SiO₂ layer/bridge as spacer between TiO₂ particles freezes the grain growth: the average crystallite size increased negligibly from 17 to 18 nm even during the calcination at 1,000 °C. Due to the stabilizing effect of SiO₂ the titania nanoparticles calcinated at 900 and 1,000 °C show significant photocatalytic activity. Furthermore, the increase in photocatalytic activity with calcination temperature indicates that the titania surface becomes more accessible either due to intensified cracking of the SiO₂ layer or due to enhanced transport of SiO₂ into the necks thus releasing additional titania surface.     

NO<Subscript>2</Subscript>-sensing properties of La<Subscript>0.65</Subscript>Sr<Subscript>0.35</Subscript>MnO<Subscript>3</Subscript> synthesized by self-propagating combustion

Ultrafine-structure La_0.65Sr_0.35MnO₃ (LSM) powders synthesized by self-propagating combustion method have been used to fabricate sensing electrodes (SEs) for NO₂ mixed-potential sensors based on yttria-stabilized zirconia (YSZ). This type of sensor was found to provide better NO₂ sensitivity at 500 °C than sensors with LSM powders synthesized by traditional solid-state methods. The response values of the sensor have good linear relationship (sensitivity 36.6 mV/decade and linear fit 0.99) with the logarithm of NO₂ concentration varying from 30 to 500 ppm. The influence of sintering temperature (1000, 1100, 1200, and 1300 °C) on sensor response was also examined and was found to have a significant effect on the morphology of LSM-SEs. Moreover, in the presence of NO, CO₂, CO, and NO₂, the sensor exhibited good NO₂ selectivity.     

Structural and electrical properties of KCa<Subscript>2</Subscript>Nb<Subscript>5</Subscript>O<Subscript>15</Subscript> ceramics

A polycrystalline sample of KCa₂Nb₅O₁₅ with tungsten bronze structure was prepared by a mixed oxide method at high temperature. A preliminary structural analysis of the compound showed an orthorhombic crystal structure at room temperature. Surface morphology of the compound shows a uniform grain distribution throughout the surface of the sample. Studies of temperature variation on dielectric response at various frequencies show that the compound has a transition temperature well above the room temperature (i.e., 105°C), which was confirmed by the polarization measurement. Electrical properties of the material have been studied using a complex impedance spectroscopy (CIS) technique in a wide temperature (31–500°C) and frequency (10²–10⁶ Hz) range that showed only bulk contribution and non-Debye type relaxation processes in the material. The activation energy of the compound (calculated from both the loss and modulus spectrum) is same, and hence the relaxation process may be attributed to the same type of charge carriers. A possible ‘hopping’ mechanism for electrical transport processes in the system is evident from the modulus analysis. A plot of dc conductivity (bulk) with temperature variation demonstrates that the compound exhibits Arrhenius type of electrical conductivity.      

CeO<Subscript>2</Subscript> coating to improve the performance of Li[Li<Subscript>0.2</Subscript>Mn<Subscript>0.54</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>]O<Subscript>2</Subscript>

The Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ coated with CeO₂ has been fabricated by an ionic interfusion method. Both the bare and the CeO₂-coated samples have a typical layered structure with R-3m and C2/m space group. The results of XRD and TEM images display that the CeO₂ coating layer on the precursor could enhance the growth of electrochemically active surface planes ((010), (110), and (100) planes) in the following ionic interfusion process. The results of galvanostatic cycling tests demonstrate that the CeO₂-coated sample has a discharge capacity of 261.81 mAh g^?1 with an increased initial Coulombic efficiency from 62.4 to 69.1% at 0.05 °C compared with that of bare sample and delivers an improved capacity retention from 71.7 to 83.4% after 100 cycles at 1 °C (1 °C?=?250 mA g^?1). The results of electrochemical performances confirm that the surface modification sample exhibits less capacity fading, lower voltage decay, and less polarization.     

Elevated electrochemical property of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> originated from nano-sized Mn<Subscript>3</Subscript>O<Subscript>4</Subscript>

By employment of nano-sized pre-prepared Mn₃O₄ as precursor, LiMn₂O₄ particles have been successfully prepared by facile solid state method and sol-gel route, respectively. And the reaction mechanism of the used precursors of Mn₃O₄ is studied. The structure, morphology, and element distribution of the as-synthesized LiMn₂O₄ samples are characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). Compared with LiMn₂O₄ synthesized by facile solid state method (SS-LMO), LiMn₂O₄ synthesized by modified sol-gel route (SG-LMO) possesses higher crystallinity, smaller average particle size (~175 nm), higher lithium chemical diffusion coefficient (1.17 × 10^?11 cm² s^?1), as well as superior electrochemical performance. For example, the cell based on SG-LMO can deliver a capacity of 85.5 mAh g^?1 at a high rate of 5 °C, and manifests 88.3% capacity retention after 100 cycles at 0.5 °C when cycling at 45 °C. The good electrochemical performance of the cell based on SG-LMO is ascribed mainly to its small particle size, high degree of dispersion, and uniform element distribution in bulk material. In addition, the lower polarization potential accelerates Li⁺ ion migration, and the lower atom location confused degree maintains integrity of crystal structure, both of which can effectively improve the rate capability and cyclability of SG-LMO.     

Ultra-rapid combustion synthesis of Na<Subscript>2</Subscript>FePO<Subscript>4</Subscript>F fluorophosphate host for Li-ion and Na-ion insertion

Exploring soft-chemistry synthesis of Fe-based battery cathode materials, we have optimized combustion synthesis as an ultra-rapid approach to produce Na₂FePO₄F fluorophosphate cathode. It yields nanoscale, carbon-coated target product by annealing (at 600 °C) for just 1 min. The purity of the material crystallizing in the orthorhombic structure was confirmed by powder X-ray diffraction pattern and XPS analysis, while the morphology was studied by scanning electron microscopy. The as-synthesized material exhibits good electrochemical performance delivering a first discharge capacity of more than 70 mAh/g at C/10 rate versus both Li⁺/Li and Na⁺/Na, hence acting as an efficient host for both Li-ion and Na-ion insertion. Combustion synthesis can be employed as an economic route for synthesis and rapid screening of various phosphate-based insertion materials.     

Thermoeletrochemical study on LiNi<Subscript>0.8</Subscript>Co<Subscript>0.1</Subscript>Mn<Subscript>0.1</Subscript>O<Subscript>2</Subscript> with in situ modification of Li<Subscript>2</Subscript>ZrO<Subscript>3</Subscript>

To improve the electrochemical performance of Nickel-rich cathode material LiNi_0.8Co_0.1Mn_0.1O₂, an in situ coating technique with Li₂ZrO₃ is successfully applied through wet chemical method, and the thermoelectrochemical properties of the coated material at different ambient temperatures and charge-discharge rates are investigated by electrochemical-calorimetric method. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests demonstrate that the Li₂ZrO₃ coating decreases the electrode polarizatoin and reduces the charge transfer resistance of the material during cycling. Moreover, it is found that with the ambient temperatures and charge-discharge rates increase, the specific capacity decreases, the amount of heat increases, and the enthalpy change (ΔH) increases. The specific capacity of the cells at 30 °C are 203.8, 197.4, 184.0, and 174.5 mAh g^?1 at 0.2, 0.5, 1.0, and 2.0 C, respectively. Under the same rate (2.0 C), the amounts of heat of the cells are 381.64, 645.32, and 710.34 mJ at 30, 40, and 50 °C. These results indicate that Li₂ZrO₃ coating plays an important role to enhance the electrochemical performance of LiNi_0.8Co_0.1Mn_0.1O₂ and reveal that choosing suitable temperature and current is critical for solving battery safety problem.     

Phase transition in Bi<Subscript>8</Subscript>Fe<Subscript>6</Subscript>Ti<Subscript>3</Subscript>O<Subscript>27</Subscript> multiferroic ceramics

The polycrystalline Bi₈Fe₆Ti₃O₂₇ compound was prepared by a high-temperature solid-state reaction technique. Preliminary structural analysis by X-ray diffraction (XRD) confirms the formation of a single-phase compound in an orthorhombic crystal system at room temperature. The elemental content of the compound was analyzed by EDAX microanalysis. Microstructural analysis by scanning electron microscopy (SEM) shows that the compound has well defined grains, which are distributed uniformly throughout the surface of the pellet sample. Detailed studies of temperature-dependent dielectric response at various frequencies show dielectric anomalies at 380, 389 and 403°C for 10 kHz, 100 kHz, and 1 MHz respectively. The hysteresis loop observed by applying an electric field of 12 kV/cm on the poled sample with smaller remanent polarization supports the existence of ferroelectricity in this material. The value of d₃₃ of the compound was found to be 19 pC/N.      

Modification research of LiAlO<Subscript>2</Subscript>-coated LiNi<Subscript>0.8</Subscript>Co<Subscript>0.1</Subscript>Mn<Subscript>0.1</Subscript>O<Subscript>2</Subscript> as a cathode material for lithium-ion battery

The LiNi_0.8Co_0.1Mn_0.1O₂ with LiAlO₂ coating was obtained by hydrolysis–hydrothermal method. The morphology of the composite was characterized by SEM, TEM, and EDS. The results showed that the LiAlO₂ layer was almost completely covered on the surface of particle, and the thickness of coating was about 8–12 nm. The LiAlO₂ coating suppressed side reaction between composite and electrolyte; thus, the electrochemical performance of the LiAlO₂-coated LiNi_0.8Co_0.1Mn_0.1O₂ was improved at 40 °C. The LiAlO₂-coated sample delivered a high discharge capacity of 181.2 mAh g^?1 (1 C) with 93.5% capacity retention after 100 cycles at room temperature and 87.4% capacity retention after 100 cycles at 40 °C. LiAlO₂-coated material exhibited an excellent cycling stability and thermal stability compared with the pristine material. These works will contribute to the battery structure optimization and design.