Enhanced cyclability of triple-metal-doped LiMn2O4 spinel as the cathode material for rechargeable lithium batteries

To improve the cycle performance of spinel LiMn₂O₄ as the cathode of 4-V-class lithium secondary batteries, spinel phases LiM _x Mn_2 − x O₄ (M=Li, Fe, Co; x = 0, 0.05, 0.1, 0.15) and LiFe_0.05M _y Mn_{1.95 − y} O₄ (M=Li, Al, Ni, Co; y = 0.05, 0.1) were successfully prepared using the sol–gel method. The spinel materials were characterized by powder X-ray diffraction (XRD), elemental analysis, and scanning electron microscopy. All the samples exhibited a pure cubic spinel structure without any impurities in the XRD patterns. Electrochemical studies were carried out using the Li|LiM _x Mn_2 − x O₄ (M=Li, Fe, Co; x = 0, 0.05, 0.1, 0.15) and LiFe_0.05M _y Mn_{1.95 − y} O₄ (M=Li, Al, Ni, Co; y = 0.05, 0.1) cells. These cathodes were more tolerant to repeated lithium extraction and insertion than a standard LiMn₂O₄ spinel electrode in spite of a small reduction in the initial capacity. The improvement in cycling performance is attributed to the stabilization in the spinel structure by the doped metal cations.     

Structure, ferroelectric and piezoelectric properties of?(Bi0.98?xLa0.02Na1?x)0.5BaxTiO3 lead-free ceramics

Lead-free (Bi_0.98−x La_0.02Na_1−x )_0.5Ba _x TiO₃ ceramics have been prepared by an ordinary sintering technique and their structure, ferroelectric and piezoelectric properties have been studied. The results of X-ray diffraction show that La²⁺ and Ba²⁺ diffuse into the Bi_0.5Na_0.5TiO₃ lattices to form a new solid solution with a pure perovskite structure, and a morphotropic phase boundary (MPB) exists at 0.04<x<0.10. Compared with pure Bi_0.5Na_0.5TiO₃ ceramics, the (Bi_0.98−x La_0.02Na_1−x )_0.5Ba _x TiO₃ ceramics possess much smaller coercive field E _c and larger remanent polarization P _r. Because of the low E _c (3.38 kV/mm), large P _r (46.2 μC/cm²) and the formation of the MPB of rhombohedral and tetragonal phases, the piezoelectric properties of the ceramics are significantly enhanced at x=0.06: d ₃₃=181 pC/N and k _p=36.3%. The depolarization temperature T _d reaches a minimum value near the MPB. The ceramics exhibit relaxor characteristic, which is probably a result from the cation disordering in the 12-fold coordination sites. The temperature dependences of the ferroelectric and dielectric properties suggest that the ceramics may contain both polar and non-polar regions at the temperatures above T _d.     

Quantitative analysis of charge-carrier trapping in organic thin-film transistors from transfer characteristics

A dynamic method for quantifying the amount and mechanism of trapping in organic field effect transistors (OFETs) is proposed. It exploits transfer characteristics acquired upon application of a triangular waveform gate sweep V _G. The analysis of the transfer characteristics at the turning point V _G=−V _max between forward and backward gate sweeps, viz. around the maximum gate voltage V _max applied, provides a differential slope Δm which depends exclusively on trapping. Upon a systematic change of V _max it is possible to extract the initial threshold voltage, equivalent to one of the observables of conventional stress measurements, and assess the mechanism of trapping via the functional dependence on the current. The analysis of the differential logarithmic derivative at the turning point yields the parameters of trapping, as the exponent β and the time scale of trapping τ. In the case of an ultra-thin pentacene OFET we extract β=1 and τ=10²–10³ s, in agreement with an exponential distribution of traps. The analysis of the hysteresis parameter Δm is completely general and explores time scales much shorter than those involved in bias stress measurements, thus avoiding irreversible damage to the device.     

Structure and impedance spectroscopy of Pr1? x Sr x Fe0.8Co0.2O3? δ ( x =0.1, 0.2, 0.3) thin films grown by laser ablation

Polycrystalline samples of Pr_1−x Sr _x Fe_0.8Co_0.2 O_3−δ (x=0.1, 0.2, 0.3) (PSFC) were prepared by the combustion synthesis route at 1200°C. The structure of the polycrystalline powders was analysed with X-ray powder diffraction data. The X-ray diffraction (XRD) patterns were indexed as the orthoferrite similar to that of PrFeO₃ having a single-phase orthorhombic perovskite structure (Pbnm). Pr_1−x Sr _x Fe_0.8Co_0.2O_3−δ (x=0.1, 0.2, 0.3) films have been deposited on yttria-stabilized zirconia (YSZ) single-crystal substrates at 700°C by pulsed laser deposition (PLD) for application to thin film solid oxide fuel cell cathodes. The structure of the films was analysed by XRD, scanning electron microscopy (SEM) and atomic force microscopy (AFM). All films are polycrystalline with a marked texture and present pyramidal grains in the surface with different size distributions. Electrochemical impedance spectroscopy (EIS) measurements of PSFC/YSZ single crystal/PSFC test cells were conducted. The Pr_0.7Sr_0.3Fe_0.8Co_0.2O_3−δ film at 850°C presents a lower area specific resistance (ASR) value, 1.65 Ω cm², followed by the Pr_0.8Sr_0.2Fe_0.8Co_0.2O_3−δ (2.29 Ω cm² at 850°C) and the Pr_0.9Sr_0.1Fe_0.8Co_0.2O_3−δ films (5.45 Ω cm² at 850°C).     

Lithium ion conductivity of Li5+xBaxLa3?xTa2O12 (x?=?0–2) with garnet-related structure in dependence of the barium content

The stoichiometry range and lithium ion conductivity of Li_5+x Ba _x La_3−x Ta₂O₁₂ (x = 0, 0.25, 0.50, 1.00, 1.25, 1.50, 1.75, 2.00) with garnet-like structure were studied. The powder X-ray diffraction data of Li_5+x Ba _x La_3−x Ta₂O₁₂ indicated that single phase oxides with garnet-like structure exist over the compositional range 0 ≤ x ≤ 1.25; while for x = 1.5, 1.75 and 2.00, the presence of second phase in addition to the major garnet like phase was observed. The cubic lattice parameter increases with increasing x and reaches a maximum at x = 1.25 then decreases slightly with further increase in x in Li_5+x Ba _x La_3−x Ta₂O₁₂. The impedance plots of Li_5+x Ba _x La_3−x Ta₂O₁₂ samples obtained at 33 °C indicated a minimum grain-boundary resistance (R _gb) contribution to the total resistance (R _b + R _gb) at x = 1.0. The total (bulk + grain boundary) ionic conductivity increases with increasing lithium and barium content and reaches a maximum at x = 1.25 and then decreases with further increase in x in Li_5+x Ba _x La_3−x Ta₂O₁₂. Scanning electron microscope investigations revealed that Li_6.25Ba_1.25La_1.75Ta₂O₁₂ is much more dense, and the grains are more regular in shape. Among the investigated compounds, Li_6.25Ba_1.25La_1.75Ta₂O₁₂ exhibits the highest total (bulk + grain boundary) and bulk ionic conductivity of 5.0 × 10⁻⁵ and 7.4 × 10⁻⁵ S/cm at 33 °C, respectively.     

Polaron and ion diffusion in a poly(3-hexylthiophene) thin-film transistor gated with polymer electrolyte dielectric

Electrolytes are finding applications as dielectric materials in low-voltage organic thin-film transistors (OTFT). The presence of mobile ions in these materials (polymer electrolytes or ion gels) gives rise to very high capacitance (>10 μF/cm²) and thus low transistor turn-on voltage. In order to establish fundamental limits in switching speeds of electrolyte gated OFETs, we carry out in situ optical spectroscopy measurement of a poly(3-hexylthiophene) (P3HT) OTFT gated with a LiClO₄:poly(ethyleneoxide) (PEO) dielectric. Based on spectroscopic signatures of molecular vibrations and polaron transitions, we quantitatively determine charge carrier concentration and diffusion constants. We find two distinctively different regions: at V _G≥−1.5 V, drift-diffusion (parallel to the semiconductor/dielectric interface) of hole-polarons in P3HT controls charging of the device; at V _G<−1.5 V, electrochemical doping of the entire P3HT film occurs and charging is controlled by drift/diffusion (perpendicular to the interface) of ClO₄ ⁻ counter ions into the polymer semiconductor.     

Electrical conductivity and chemical stability of perovskite-type BaCe0.8-xTixY0.2O3-δ

Here we report the synthesis, chemical stability, and electrical conductivity of Ti-doped perovskite-type BaCe_0.8-x Ti _x Y_0.2O_3-δ (x = 0.05, 0.1, 0.2, and 0.3; BCTY). Samples were synthesized by conventional solid state (ceramic) reaction from corresponding metal salts and oxides at elevated temperature of 1,300–1,500 °C in air. The powder X-ray diffraction confirmed the formation of a simple cubic perovskite-type structure with a lattice constant of a = 4.374(1), 4.377(1), and 4.332(1) ? for x = 0.05, 0.1, and 0.2 members of BCTY, respectively. Like BaCe_0.8Y_0.2O_3-δ (BCY), Ti substituted BCTY was found to be chemically not stable in 100% CO₂ and form BaCO₃ at elevated temperature. The bulk electrical conductivity of BCTY decreased with increasing Ti content and the x = 0.05 member exhibited the highest conductivity of 2.3 × 10⁻³ S cm⁻¹ at 650 °C in air, while a slight increase in the conductivity, especially at low temperatures (below 600 °C), was observed in humidified atmospheres.     

<Superscript>29</Superscript>Si MAS-NMR study of oxide conductors derived from the apatite-type La<Subscript>9.33</Subscript>Si<Subscript>6</Subscript>O<Subscript>26</Subscript> compound

The preparation of (La_9.33−2x/3Sr _x □_0.67−x/3)Si₆O₂₄O₂ (0 ≤ x ≤ 2) samples with different amounts of cation vacancies is reported. Structure and unit-cell parameters were deduced by Rietveld analysis of XRD patterns. Structural features that enhance oxygen conductivity in Sr-doped apatites are discussed. Up to three components were detected in ²⁹Si MAS-NMR spectra which change with the amount and distribution of cation vacancies. In general, oxygen conductivity increases with the amount of vacancies at La1 (6h) sites, passing through a maximum for x = 0.4. In the case of activation energy, a minimum is detected near x = 1.2, indicating that entropic and enthalpic change in different ways. The presence of cation vacancies should enhance oxygen hopping along c-axis; however, the analysis of the frequency dependence of conductivity suggests that oxygen motions are produced along three axes.     

Improved electrical properties of HfTiO/GeO x N y gate dielectric Ge MOS capacitors by using wet–NO Ge-surface pretreatment

Reactive cosputtering is employed to prepare high-permittivity HfTiO gate dielectric on n-Ge substrate. Effects of Ge-surface pretreatment on the interface and gate leakage properties of the dielectric are investigated. Excellent performances of Al/HfTiO/GeO _x N _y /n-Ge MOS capacitor with wet–NO surface pretreatment have been achieved with a interface-state density of 2.1×10¹¹ eV⁻¹ cm⁻², equivalent oxide charge of −7.67×10¹¹ cm⁻² and gate leakage current density of 4.97×10⁻⁵ A/cm² at V _g =1 V.     

Characterisation of Ba2In2 − x Sn x O5 + x/2 oxide ion conductors

The Ba₂In_2 − x Sn _x O_5 + x/2 solid solution was confirmed up to x = 1 by solid-state reaction. X-ray diffraction at room and at elevated temperatures, Raman scattering and impedance spectroscopy were used to characterise the samples. The structure refinement of the composition x = 0.1 from neutron diffraction data reveals that tin is preferentially located in the tetrahedral layers of the brownmillerite. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007     

Effects of La–Zn substitution on microstructure and magnetic properties of strontium ferrite nanofibers

Sr_1−x La _x Zn _x Fe_12−x O₁₉/poly(vinylpyrrolidone) (PVP) (0.0≤x≤0.5) precursor nanofibers were prepared by the sol–gel assisted electrospinning method from starting reagents of metal salts and PVP. Subsequently, the Sr_1−x La _x Zn _x Fe_12−x O₁₉ nanofibers with diameters of around 100 nm were obtained by calcination of the precursor at 800 to 1000°C for 2 h. The precursor and resultant Sr_1−x La _x Zn _x Fe_12−x O₁₉ nanofibers were characterized by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectrometer and vibrating sample magnetometer. The grain sizes of Sr_0.8La_0.2Zn_0.2Fe_11.8O₁₉ nanofibers are in a nanoscale from 40 to 48 nm corresponding to the calcination temperature from 800 to 1000°C. With La–Zn substitution content increase from 0 to 0.5, the grain size and lattice constants for the Sr_1−x La _x Zn _x Fe_12−x O₁₉ nanofibers obtained at 900°C show a steady reduction trend. With variations of the ferrite particle size arising from the La–Zn substitution, the nanofiber morphology changes from the necklace-like structure linking by single elongated plate-like particles to the structure building of multi-particles on the nanofiber cross-section. The specific saturation magnetization of Sr_1−x La _x Zn _x Fe_12−x O₁₉ nanofibers initially increases with the La–Zn content, reaching a maximum value 72 A m² kg⁻¹ at x=0.2, and then decreases with a further La–Zn content increase up to x=0.5, while the coercivity exhibits a continuous reduction from 413 (x=0) to 219 kA m⁻¹ (x=0.5). The mechanism for the La–Zn substitution and the nanofiber magnetic property are analyzed.     

Non-steady-state photo-EMF in nanostructured GaN and polypyrrole within porous matrices

We report an experimental investigation of the non-steady-state photoelectromotive force in nanostructured GaN within porous glass and polypyrrole within chrysotile asbestos. The samples are illuminated by an oscillating interference pattern created by two coherent light beams and the alternating current is detected as a response of the material. Dependences of the signal amplitude versus temporal and spatial frequencies, light intensity, and temperature are studied for two wavelengths λ=442 and 532 nm. The conductivity of the GaN composite is measured: σ=(1.1–1.6)×10⁻¹⁰ Ω⁻¹ cm⁻¹ (λ=442 nm, I ₀=0.045–0.19 W/cm², T=293 K) and σ=(3.5–4.6)×10⁻¹⁰ Ω⁻¹ cm⁻¹ (λ=532 nm, I ₀=2.3 W/cm², T=249–388 K). The diffusion length of photocarriers in polypyrrole nanowires is also estimated: L _D=0.18 μm.     

A tunable green alkaline-earth silicon-oxynitride solid solution (Ca1? x Sr x )Si2O2N2:Eu2+ and its application in LED

A series of (Ca_1−x−y Sr _x )Si₂O₂N₂:yEu²⁺ (x=0.0–0.97, y=0.03) phosphors were synthesized by high-temperature solid-state reaction. The XRD patterns confirm the formation of a solid solution of (Ca_1−x−y Sr _x )Si₂O₂N₂:yEu²⁺. An intense tunable green light is observed with the increasing ratio of Sr/Ca. With an increase in x, the excitation and emission spectra show a redshift and blueshift, respectively, due to large centroid shift and small Stokes shift. The temperature dependent luminescence is also investigated in the temperature range of 77–450 K. The Huang–Rhys factor and the thermal-quenching temperature are determined. Intense green LEDs were successfully fabricated based on the (Ca_1−x−y Sr _x )Si₂O₂N₂:yEu²⁺ phosphor and near-ultraviolet (∼395 nm) GaN/blue (460 nm) InGaN chips. All the results indicate that the solid solution (Ca_1−x−y Sr _x )Si₂O₂N₂:yEu²⁺ is a promising phosphor applicable to near-UV and blue LEDs for solid-state lighting.     

Variations of ionic binding energies and the distribution of charge carriers in orthorhombic La2−x Sr x CuO4

The significance of heterovalent, substitutional disorder for the distribution of charge carriers in La_2−x Sr _x CuO₄ has been investigated. Disorder is shown to cause strong variations of binding energies of the ions ranging to some eV for Sr contentsx=0.1. Balancing the energy for a hole transport, Cu³⁺+O²⁻→Cu²⁺+O⁻, and taking binding energy variations into account, the process is realized to become possible without consuming energy for a subset Θ for allx Cu³⁺ in one formula unit of La_2−x Sr _x CuO₄. The functions Θ(x) are presented for hole transports to apex and in-plane oxygens, respectively. The delocalization of charge carriers is interpreted to be caused by valency disorder on metal lattice sites.     

The superconducting properties of YBa2(Cu1−xMx)3O7 for M=Zn and Ni

Transverse and zero-field μSR measurements were made on YBa₂(Cu_1−xNi_x)₃O_7−y withx=0.1 and 0.2, and YBa₂(Cu_1−x Zn _x )₃O_7−y withx=0.03, 0.06, 0.1, and 0.16, wherey≈0.1. Since doping may lead to magnetic ordering this was searched for with both zero and transverse field μSR, but no evidence was found over the temperature range studied: 10–100 K. However, depolarization rates as functions of temperature were obtained, and the low temperature values of these are σ=3.2 μs⁻¹.1.6μs⁻¹, and 1 μs⁻¹ forx=0.01, and 0.2 Ni, respectively, and σ=0.8 μs⁻¹, 0.75 μs⁻¹, 0.65 μs⁻¹, and 0.4 μs⁻¹ forx=0.03, 0.06, 0.1, and 0.16 Zn, respectively. Estimates for the effect of decreasing electron concentration for Zn are made, but these alone do not account for the drop in σ. Estimates for the effect of scattering on λ and hence σ are made. The reduction in σ for Ni dopant is in surprisingly good agreement with these estimates. For Zn the order of magnitude is correct, but the relative lack of further change in σ after the effect of the first 0.03 addition seems to imply a saturation of the effect of scattering.     

Physicochemical properties of LiAl x Mn2 − x O4 and LiAl0.05Mn1.95O4 − y F y cathode material by the citric acid-assisted sol–gel method

LiAl _x Mn_2 − x O₄ and LiAl_0.05Mn_1.95O_4 − y F _y spinel have been successfully synthesized by citric acid-assisted sol–gel method. The structure and physicochemical properties of this as-prepared powder were investigated by electronic conductivity test, powder X-ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS), and galvanostatic charge–discharge test in detail. The electronic conductivity decreases with increasing of the content of doped Al. XRD patterns show that the diffraction of LiAl_0.05Mn_1.95O_4 − y F _y samples is similar, with all the peaks indexable in the Fd3m space group, and a little impurity appears in the LiAl_0.05Mn_1.95O_3.8F_0.2 sample. SEM reveals that all LiAl_0.05Mn_1.95O_4 − y F _y powders have the uniform, nearly cubic structure morphology with narrow size distribution which is less than 500 nm. Galvanostatic charge–discharge test indicates that LiAl_0.05Mn_1.95O₄ has the highest discharge capacity and electrochemical performance among all LiAl _x Mn_2 − x O₄ samples after 50 cycles, and the initial discharge capacity of LiAl_0.05Mn_1.95O_4 − y F _y (y = 0, 0.02, 0.05, 0.1) is 123.9, 124.6, 124.9, and 125.0 mAh g⁻¹, respectively, and their capacity retention ratios are 94.2%, 94.9%, 91.7%, and 89.9% after 50 cycles, respectively. EIS indicates that LiAl_0.05Mn_1.95O_3.98F_0.02 have smaller charge transfer resistance than that of LiAl_0.05Mn_1.95O₄ corresponding to the extraction of Li⁺ ions.     

Steady State and Time-Resolved Fluorescence Studies of a Hemagglutinin from Moringa oleifera

The saccharide binding and conformational characterization of a hemagglutinin, a low molecular weight protein from the seeds of Moringa oleifera was studied using steady state and time resolved fluorescence. The lectin binds sugars LacNAc (K _a = 1380 M⁻¹) and fructose (K _a = 975 M⁻¹), as determined by the fluorescence spectroscopy. It has a single tryptophan per monomer which is exposed on the surface and is in a strong electropositive environment as revealed by quenching with iodide. Quenching of the fluorescence by acrylamide involved both static (K _s = 0.216 M⁻¹) and collisional (K _sv = 8.19 M⁻¹) components. The native protein showed two different lifetimes, τ ₁ (1.6 ns) and τ ₂ (4.36 ns) which decrease and get converted into a single one, (2.21 ns) after quenching with 0.15 M acrylamide. The bimolecular quenching constant, k _q was 7.55 × 10¹¹ M⁻¹ s⁻¹. ANS binding studies showed that the native protein has exposed hydrophobic patches which get further exposed at extreme acidic or alkaline pH. However, they get buried in the interior of the protein in presence of 1 M GdnHCl or urea.     

Hyperfine Interactions of 181Ta in Zr2Ni Observed Using PAC Spectroscopy

We have measured nuclear electric–quadrupole interactions (EQI) at ¹⁸¹Ta impurities substituted as Hf atoms into the Zr site in Zr₂Ni. Using perturbed-angular-correlation (PAC) spectroscopy, we measured the EQI over temperatures ranging from 10 to 1200 K. Over the entire range of temperature, the Zr₂Ni crystal has a bct Al₂Cu structure that includes a single Zr site. The crystal field symmetry surrounding this site is rather low, giving rise to a highly asymmetric electric-field gradient tensor. At 10 K, the EQI is characterized by an angular frequency ω₀=601(3) Mrad s⁻¹, and an asymmetry parameter η=0.835(2). At 1200 K, ω₀ decreases to 516(3) Mrad s⁻¹, and η also decreases to 0.790(4). Although weak, the temperature dependence of ω₀ is consistent with a (1−BT ^3/2) power law, in which B=6×10⁻⁶ K^−3/2. The EQI also manifests a very narrow linewidth. We observed no evidence either for magnetic ordering or for structural phase transitions in the temperature range covered by this experiment. Moreover, the sharpness of the EQI indicates that the samples as prepared are remarkably free of strain and defects. These results indicate that the Zr₂Ni structure does not promote the formation of defects and that the power-law dependence of ω₀ on T is insensitive to the asymmetric nature of the crystal. This revised version was published online in September 2006 with corrections to the Cover Date.     

Cuspons and Smooth Solitons of the Degasperis–Procesi Equation Under Inhomogeneous Boundary Condition

This paper is contributed to explore all possible single peakon solutions for the Degasperis–Procesi (DP) equation m _t  + m _x u + 3mu _x  = 0, m = u − u _xx . Our procedure shows that the DP equation either has cusp soliton and smooth soliton solutions only under the inhomogeneous boundary condition lim_|x|→ ∞ u =A ≠0, or possesses the regular peakon solutions ce ^{− |x − ct|} ∈ H ¹ (c is the wave speed) only when lim_|x|→ ∞ u = 0 (see Theorem 4.1). In particular, we first time obtain the stationary cuspon solution of the DP equation. Moreover we present new cusp solitons (in the space of ) and smooth soliton solutions in an explicit form. Asymptotic analysis and numerical simulations are provided for smooth solitons and cusp solitons of the DP equation.      

Ionic conductivity and structural properties of MnO-doped Bi4V2O11 system

Bi₄V₂O₁₁ exists in three phases viz. α, β, and γ. High temperature γ-phase can be stabilized to room temperature owing to its higher conductivity by the partial substitution of metallic cations for vanadium in Bi₄V₂O₁₁. Phase transitions from α → β and β → γ are composition and temperature-dependent. Mn²⁺-doped compounds Bi₄V_2−x Mn _x O_{11− δ} (0 ≤ x ≤ 0.4) have been synthesized by solid state reaction technique and investigated by X-ray diffraction and ionic conductivity measurement. High ionic conducting γ-phase is stabilized for x ≥ 0.2. The ionic conductivity of the series of Bi₄V_2−x Mn _x O_{11− δ} samples has been measured by using ac impedance spectroscopy technique. The conductivity data do show departure from its simple Arrhenius behavior for all of the compositions. The highest conductivity observed for x = 0.2 sample can be attributed to lower activation energy.