Modified carbothermal synthesis and electrochemical performance of LiFePO4/C composite as cathode materials for lithium-ion batteries

LiFePO₄/C active materials were synthesized via a modified carbothermal method, with a low raw material cost and comparatively simple synthesis process. Rheological phase technology was introduced to synthesize the precursor, which effectively decreased the calcination temperature and time. The LiFePO₄/C composite synthesized at 700 °C for 12 h exhibited an optimal performance, with a specific capacity about 130 mAh g^?1 at 0.2C, and 70 mAh g^?1 at 20C, respectively. It also showed an excellent capacity retention ratio of 96 % after 30 times charge–discharge cycles at 20C. EIS was applied to further analyze the effect of the synthesis process parameters. The as-synthesized LiFePO₄/C composite exhibited better high-rate performance as compared to the commercial LiFePO₄ product, which implied that the as-synthesized LiFePO₄/C composite was a promising candidate used in the batteries for applications in EVs and HEVs.     

Capacity fading reason of LiNi0.5Mn1.5O4 with commercial electrolyte

The cycling performances of LiNi_0.5Mn_1.5O₄ (LNMO) were investigated and the reasons of capacity fading were discussed. The results show that LNMO can deliver about 115 mAh?g^?1 at 1C at different temperatures; however, it retains only 61.57 % of its initial capacity after 130th cycles at 60 °C, which is much lower than 94.46 % of LNMO at 25 °C, and the cycling performance at 1C is better than that at 0.5C. The reason of capacity fading of LNMO at 60 °C is mainly due to the lower decomposition voltage of 4.3 V with commercial electrolyte and the larger decomposition current, of which the electrolyte decomposes and interacts with active materials to lead to the larger irreversible capacity loss. While the worse cycling performance at low rate is attributed to the longer interaction time between the electrolyte with the decomposition voltage of 4.5 V and the active materials.     

Robust doped BaCeO<Subscript>3-δ</Subscript> electrolyte for IT-SOFCs

Single phase polycrystalline BaZr_0.3Ce_0.5Y_0.1Yb_0.1O_{3 - δ} electrolyte material was prepared by solid state reaction route. Rietveld analysis of the XRD data confirms the tetragonal symmetry in the I4/mcm space group with unit cell parameters of a = b = 6.0567(3) Å and c = 8.5831(5) Å. The addition of ZnO as a sintering additive was found to reduce the sintering temperature and enhance both overall sinterability and grain growth. Sintering temperature was reduced by 200–300 °C, and a very high relative density of about 98% was achieved at 1400 °C. Impedance spectroscopy in humidified 5% H₂/Ar atmosphere shows that the protonic conductivity at 600 °C was 8.60 × 10^?3 S cm^?1. Thermal analysis performed in pure CO₂ atmosphere shows very good chemical stability up to 1200 °C. Good biaxial flexure strength of 100–200 MPa was reported which makes this material a promising electrolyte material for intermediate temperature solid oxide fuel cells (IT-SOFCs).     

Linear and nonlinear optical properties of MgO:LiTaO3

We derive new temperature dependent Sellmeier equations for the extra-ordinary and ordinary refractive indices of 0.5% MgO-doped stoichiometric LiTaO₃ crystal. The equations are based on quasi phase-matched frequency conversion measurements, as well as on interferometric measurements of the thermal expansion and thermal dispersion. These equations fit experimental data over wide spectral ranges: 0.35–6 μm for the extra-ordinary wave and 0.375–3.75 μm for the ordinary wave, from room temperature up to 200°C. The nonlinear optical measurements set lower-limit values for the d ₃₃, d ₂₂, and d ₂₄ elements of the second-order susceptibility tensor χ ⁽²⁾ of 12.9, 1.54, and 0.46 pm/V, respectively. The interferometric measurements enable one to determine the linear and quadratic expansion coefficients of 1.45762e?5 1/°C, and 2.68608e?8 (1/°C)², respectively. The Sellmeier equations are in good agreement with previously published data.     

Dopant Spin States and Magnetic Interactions in Transition Metal (Fe3+)-Doped Semiconductor Nanoparticles: An EMR and Magnetometric Study

In this work, electron magnetic resonance (EMR) spectroscopy and magnetometry studies were employed to investigate the origin of the observed room-temperature ferromagnetism in chemically synthesized Sn_1?x Fe _x O₂ powders. EMR data clearly established the presence of two different types of signals due to the incorporated Fe ions: paramagnetic spectra due to isolated Fe³⁺ ions and broad ferromagnetic resonance (FMR) spectra due to magnetically coupled Fe³⁺ dopant ions. EMR data analysis and simulation suggested the presence of high-spin (S = 5/2) Fe³⁺ ions incorporated into the SnO₂ host lattice both at substitutional and at interstitial sites. The FMR signal intensity and the saturation magnetization M _s of the ferromagnetic component increased with increasing Fe concentration. For Sn_0.953Fe_0.047O₂ samples, well-defined EMR spectra revealing FMRs were observed only for samples prepared in the 350–600°C range, whereas for samples prepared at higher annealing temperatures up to 900°C, the FMRs and saturation magnetization were vanished due to diffusion and eventual expulsion of the Fe ions from the nanoparticles, in agreement with data obtained from Raman and X-ray photoelectron spectroscopy.     

Influence of Gd3+ and Dy3+ co-doping and sintering regime on enhancement of electrical conductivity of ceria-based solid electrolyte

In order to improve the conductivity of ceria-based solid electrolytes, effect of co-doped Gd³⁺ and Dy³⁺ was evaluated. For this purpose, nano-crystalline Gd_0.2???x Dy _x Ce_0.8O_1.9 powders with various composition ranges (x?=?0.05, 0.1, 0.15, 0.2) were initially synthesized by high-energy milling method. The effect of micro-structural evolution and co-doping on electrical properties of the dense sintered samples fabricated by two-step sintering and conventional sintering of the synthesized powders were investigated. Electrical conductivity of the samples was discussed based on the results obtained by AC impedance spectroscopy at temperatures in the range of 300–700 °C. The co-doping and sintering regime were found to significantly influence the conductivity of the electrolytes. The electrical conductivity of the co-doped samples depends on Dy³⁺ content and the maximum conductivity obtained by 0.15 mol% Dy and 0.05 mol% Gd. The conductivity of Gd_0.2???x Dy _x Ce_0.8O_1.9 (x?=?0.15) was 0.03 S/cm at 700 °C. A thorough discussion was made, based on the present experimental data.     

Fluorescent Coumarin Derivatives with Viscosity Sensitive Emission - Synthesis,Photophysical Properties and Computational Studies

New derivatives of (benzo[d]azolyl)-benzo[f]chromenone were synthesized from the intermediate 3-(1,3-benzazol-2-yl)naphthalen-2-ol, obtained from 3-hydroxynaphthalene-2-carboxylic acid and 2-amino phenol in the presence of PCl₃ in chlorobenzene at 130–135 °C. The compounds were characterized by FT-IR, ¹ H NMR, mass spectroscopy and elemental analysis. The synthesized compounds are fluorescent which absorb in the range of 296 to 332 nm while emit in the range of 368 to 404 nm. The experimental absorption and emission wavelengths for the compounds 5 and 6 are in good agreement with those predicted using the Time-Dependent Density Functional Theory (TD-DFT) [B3LYP/6-31G(d)]. The largest wavelength difference between the experimental and computed absorption maxima was 29 nm (tetrahedrofuran) for compound 5 while for emission it was 61 nm (dichloromethane) for compound 7. The emission intensities of all the compounds decrease continuously as the viscosity of the microenvironment increases. The compounds are thermally stable up to a temperature range of 300 to 350 °C.     

Electrochemical capacitance of porous NiO–CeO2 binary oxide synthesized via sol–gel technique for supercapacitor

Nanocrystalline NiO–CeO₂ binary oxide as a novel electrode material for ultracapacitor was synthesized via glycol assisted citrate sol–gel method. Unique cubic phases with aggregated crystalline microstructure of NiO–CeO₂ mixed oxides were examined by X-ray diffraction and transmission electron microscope. The observed electrochemical measurements further reveal the strong pseudocapacitance features of the mixed oxides at different current density. Binary oxide annealed at 500 °C shows an optimum specific capacitance (C _s ) of 305 Fg^?1 at the constant current density of 1 Ag^?1. The achieved C _s value undoubtedly certifies that in combination with NiO the structural stability and redox property of CeO₂ have been enhanced. Especially, increasing the calcination temperature binary oxide has shown well reversible redox features which confirm the high chemical and thermal stability of CeO₂ and it could be involve in the charge storage process effectively by their strong Ce³⁺/Ce⁴⁺ redox couples. Capacity retention and cyclic stability of the electrode was quite good, only ～5 % capacity fading was observed after 1,000 cycles. Moreover, binary oxide calcined at 700 °C exhibits a specific capacitance of 167 Fg^?1 at the constant current density of 1 Ag^?1 which states that presence of CeO₂ with NiO have controlled the grain growth and maintains their porous microstructure even at 700 °C. This facilitates to the redox process at both NiO and CeO₂ active surfaces at elevated temperature significantly.     

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.     

Effect of sintering conditions on the magnetic and structural properties of Fe 0.6 Mn 0.1 Al 0.3 synthesized by mechanical alloying

In order to study the effect of sintering condition on the structural and magnetic behavior of prealloyed metallic powders of Fe _0.6 Mn _0.1 Al _0.3 system, two different thermal treatments were employed. All samples were previously milled and then compacted. Later, the sintering process was carried out in two cycles. For the first one, a sintering time of 2 h was followed by a cooling process governed by the inertia of the furnace. In the second treatment, a sintering time of 0.17 h with a controlled slow ramp of 1 °C/min between 500 °C and 250 °C. All samples were characterized by X-ray diffraction and Mössbauer spectroscopy. It was found that the sintering time improves the crystallinity while the magnetic behavior was modified by the changes in the cooling rate.     

Diffusion of titanium in slightly reduced rutile

The self-diffusion of ⁴⁴Ti in slightly reduced rutile. TiO_2?δ, was measured along the c axis over the temperature range of 1000–1100°C between 0.2 and 1 × 10^?18atm. oxygen pressure. These measurements enabled the determination of the defect structure of TiO_2-δ for 0.02 ?gd ? 0.001. For oxygen pressures between 1 × 10^?13 and 1 × 10^?16atm. at 1058.4°C random tetravalent titanium atoms are the predominant defects evident from self-diffusion. The enthalpy of motion was determined as ΔH_m = 57.03 ± 4.9% kcal/mole. From the activation energy at 1.69 × 10^?16atm., the enthalpy of formation for tetravalent titanium interstitials was determined as ΔH_f = 276 ± 15.6% kcal/mole.For oxygen pressures less than 1 × 10^?16atm. at 1058.4°C, the tracer diffusion coefficient shows a continuous decline as the oxygen pressure is lowered. Comparisons with thermogravimetric studies and consideration of the similarity in structure between nonstoichiometric point defect phases and the first homologous series phase indicate that the order-disorder transition retains a considerable degree of short range order below the critical concentration in the form of Wadsley defects.     

Winkelverteilung der Polarisation der Neutronen aus der Reaktion14C(d,n 0)15N bei Deuteronenenergien zwischen 1,3 und 1,9 MeV

Polarization distributions of ground state neutrons emitted from the¹⁴C(d,n ₀)¹⁵N reaction were investigated over the angular range from 15 ° (lab) to 150 ° (lab) at bombarding energies of 1.28, 1.55 and 1.88 MeV. Scattering of neutrons from helium served as polarization analyzer. The experimental results show a large variation with energy of the polarization ranging betweenP(Θ_lab=130 °)=?21% andP(Θ_lab=130 °)=+50% at 1.28 and 1.88 MeV respectively.     

Configuration and Performance of a Mobile 129Xe Polarizer

A stand-alone, self-contained and transportable system for the polarization of ¹²⁹Xe by spin exchange optical pumping with Rb is described. This mobile polarizer may be operated in batch or continuous flow modes with medium amounts of hyperpolarized ¹²⁹Xe for spectroscopic or small animal applications. A key element is an online nuclear magnetic resonance module which facilitates continuous monitoring of polarization generation in the pumping cell as well as the calculation of the absolute ¹²⁹Xe polarization. The performance of the polarizer with respect to the crucial parameters temperature, xenon and nitrogen partial pressures, and the total gas flow is discussed. In batch mode the highest ¹²⁹Xe polarization of P_Xe = 40 % was achieved using 0.1 mbar xenon partial pressure. For a xenon flow of 6.5 and 26 mln/min, P _Xe = 25 % and P _Xe = 13 % were reached, respectively. The mobile polarizer may be a practical and efficient means to make the applicability of hyperpolarized ¹²⁹Xe more widespread.     

Experimental Investigation of Subcooled Vertical Upward Flow Boiling in a Narrow Rectangular Channel

Accurate models for the onset of nucleate boiling, density of active nucleation sites (N_a), bubble departure size (D_d), and departure frequency (f_d) are essential to the success of computational fluid dynamics analysis of two-phase thermal-hydraulics involving subcooled flow boiling in nuclear reactor systems. This work presents an experimental study of subcooled flow boiling in a vertical upward narrow rectangular channel that mimics the flow passage in the plate fuel assembly of boiling water reactors. The experiments are conducted over a range of mass flux (G = 122–657 kg/m²s), inlet subcooling (ΔT_sub = 4.7–33.3?C), and heat flux (q″ = 1.7–28.9 W/cm²). Based on the experimental data, empirical correlations are developed for the prediction of onset of nucleate boiling, N_a, D_d, and f_d for given flow conditions. These correlations are valid in the nucleate boiling regime when the wall superheat is less than 12°C and can be incorporated in the computational fluid dynamics codes to enable more precise simulation of subcooled flow boiling heat transfer and two-phase flow in nuclear energy applications.     

Synthesis and electric properties of perovskite Pr0.6Ca0.4Fe0.8Co0.2O3 for SOFC applications

In this study, polycrystalline powder Pr_0.6Ca_0.4Fe_0.8Co_0.2O₃ (PCFC) was synthesized by a sol–gel process. This oxide was analyzed by X-ray powder diffraction. Synthesized Pr_0.6Ca_0.4Fe_0.8Co_0.2O₃ showed up to be single phase and belongs to the orthorhombic crystalline system with a Pbnm space group. The microstructural features of the synthesized products display particles having an irregular morphology and a size in the range of 50–100 nm. X-ray diffraction (XRD) analysis shows the chemical compatibility between the PCFC cathode and the electrolyte Sm-doped ceria since no reaction products were honored when the material was mixed and co-fired at 1,000 °C for 168 h. The thermal expansion coefficient of PCFC 16.9?×?10^?6 °C^?1 is slightly higher than that of Ce_0.8Sm_0.2O_1.9 (SDC) over the studied temperature range. The greater contribution to the total resistance of the electrode is the electrochemical resistance associated with oxygen exchange in the cathode surface (0.96 Ωcm²). The dc four-probe measurement indicated that PCFC exhibits fairly high electrical conductivity, over 100 S cm^?1 at T?≥?500 °C, making this material promising as a cathode material for intermediate temperature solid oxide fuel cells.     

Shear‐Enhanced Nucleation of Isotactic Polypropylene in Limited Space

The nucleation rate was measured by directly counting the number of nuclei, which were developed while an isotactic polypropylene melt was flowing under shear in a thin film. The nucleation rate was enhanced with an increased rate of shear, e.g., by a factor of 10 larger at the rate of shear of 14 s^?1 compared with the quiescent state, at 134°C. The ratio of the shear‐enhanced nucleation rate to the nucleation rate in the quiescent state was larger at a higher temperature of crystallization, i.e., about 10 times at 134°C to 590 times at 140°C. The increase of the nucleation rate under shear flow was explained by a reduction of the lateral and end (fold) surface free energies; the product σ _s ² σ _e decreased to 3.2×10^?7 for the sheared melt, from 6.0×10^?7 (J m^?2)³ for the isotropic state. The free energy reduction was caused by transition of the nucleus formation mode from three‐dimensional folded chain nuclei to two‐dimensional bundle nuclei, in which chains lie down on the glass substrate, aligning parallel to the flow direction.     

Novel layered perovskite GdBaCuFeO5+x as a potential cathode for proton-conducting solid oxide fuel cells

A layered perovskite GdBaCuFeO_5+x (GBCuF) was developed as a cathode material for intermediate-temperature solid oxide fuel cells based on a proton-conducting electrolyte of stable BaZr_0.1Ce_0.7Y_0.2O_3?δ (BZCY). The X-ray diffraction results showed that GBCuF was chemically compatible with BZCY after co-fired at 1,000 °C for 10 h. The thermal expansion coefficient of GBCuF, which showed a reasonably reduced value (15.1?×?10^?6 K^?1), was much closer to that of BZCY than the cobalt-containing conductor. The button cells of Ni–BZCY/BZCY/GBCuF were fabricated and tested from 500 to 700 °C with humidified H₂ (～3 % H₂O) as a fuel and ambient oxygen as the oxidant. A high open-circuit potential of 1.04 V, maximum power density of 414 mW cm^?2, and a low electrode polarization resistance of 0.21 Ω cm² were achieved at 700 °C, with calculated activation energy (E _a) of 128 kJ mol^?1 for the GBCuF cathode. The experimental results indicated that the layered perovskite GBCuF is a good candidate for cathode material.     

Effects of deposition temperature and hydrogen flow rate on the properties of the Al-doped ZnO thin films and amorphous silicon thin-film solar cells

A compound of 98 mol% ZnO and 1 mol% Al₂O₃ (AZO, Al:Zn = 98:2) was sintered at 1350 °C as a target and the AZO thin films were deposited on glass using a radio frequency magnetron sputtering system. The effects of deposition temperature (from room temperature to ～300 °C) on the optical transmission spectrum of the AZO thin films were studied. The Burstein–Moss shift was observed and used to prove that defects in the AZO thin films decreased with increasing deposition temperature. The variations in the optical band gap (E _g) values of the AZO thin films were evaluated from plots of (αhv)²=c(hν?E _g), revealing that the measured E _g values increased with increasing deposition temperature. The effects of the H₂ flow rate during deposition (0 %～11.76 %, deposition temperature of 200 °C) on the crystallization, morphology, resistivity, carrier concentration, carrier mobility, and optical transmission spectrum of the AZO thin films were measured. The chemical structures of the Ar-deposited and 2 % H₂-flow rate-deposited AZO thin films (both were deposited at 200 °C) were investigated by XPS to clarify the mechanism of improvement in resistivity. The prepared AZO thin films were also used as transparent electrodes to fabricate amorphous silicon thin-film solar cells, and their properties were also measured.     

Di-urethanesil hybrid electrolytes doped with Mg(CF3SO3)2

Two siloxane-based di-urethanesil frameworks incorporating poly(oxyethylene) (POE) chains have been synthesized by the sol–gel process and doped with magnesium triflate (Mg(CF₃SO₃)₂) with the goal of developing electrolytes for the fabrication of solid-state rechargeable magnesium batteries. In these matrices, short POE chains are covalently bonded to the siloxane network via urethane linkages. The xerogels have been represented by the notation d-Ut(Y) _n Mg(CF₃SO₃)₂, where Y?=?300 and 600 represents the average molecular weight of the POE chains and n stands for salt composition (molar ratio of OCH₂CH₂ units per Mg²⁺). Xerogels with compositions ranging from 2?≤?n?<?∞ were prepared. A crystalline POE/Mg(CF₃SO₃)₂ complex of unknown stoichiometry is formed in the d-Ut(300) _n Mg(CF₃SO₃)₂ materials with n?≤?6 and in the d-Ut(600) _n Mg(CF₃SO₃)₂ materials with n?≤?5. The organically modified silicate electrolytes with the highest conductivity of the d-Ut(300) _n Mg(CF₃SO₃)₂ and d-Ut(600) _n Mg(CF₃SO₃)₂ series are the samples with n?=?6 (3.9?×?10^?8 S cm^?1 at 26 °C and 8.7?×?10^?5 S cm^?1 at 97 °C) and n?=?100 (2.63?×?10^?7 S cm^?1 at 20 °C and 1.4?×?10^?5 S cm^?1 at 85 °C), respectively. Since the electrolytes for Mg batteries that have been proposed up to now have many intrinsic problems and although the room temperature conductivity values exhibited by the systems developed in the present study are still low in view of practical application, this work opens new directions for the development of solid-state Mg ion electrolytes.     

Thermogravimetric and electrical study of non-stoichiometric titanium dioxide TiO2−x, between 800 and 1100°C

By means of thermogravimetrie and electrical measurements, it has been possible to give accurate informations on the nature of the defects produced by reduction of TiO₂ between 800 and 1100°C. For small partial pressures of oxygen P_o2. interstitial titanium Ti⁴_i prevails at temperature higher than 900°C. When P_O2 increases, oxygen vacancies are produced at first in the doubly ionized form V″_o and a progressive transition to singly ionized vacancies V″_o can be assumed. The formation enthalpies associated with these defects as calculated from our experimental results are 10.1 eV for Ti⁴_i, 4.6 eV for V″_o and 3.6–4.0 eV for V′_o. The electronic drift mobility μ is independent both of nature and concentration of the defects. The shape of its temperature dependence leads to conclude that the conduction in spite of the low μ value (0.06 cm² V^?1 s^?1 at 1100°C) is of the classical type for wide band semiconductors and not a hopping process.