A novel approach to employ Li<Subscript>2</Subscript>MnSiO<Subscript>4</Subscript> as anode active material for lithium batteries

In the present paper, we describe utilization of cathode active material as anode active material, for example, Li₂MnSiO₄. The lithium manganese silicate has been successfully synthesized by solid-state reaction method. The X-ray diffraction pattern confirms the orthorhombic structure with Pmn2 ₁ space group. The Li/Li₂MnSiO₄ cell delivered the initial discharge capacity of 420 mA h g⁻¹, which is 110 mA h g⁻¹ higher than graphitic anodes. The electrochemical reversibility and solid electrolyte interface formation of the Li₂MnSiO₄ electrode was emphasized by cyclic voltammetry.     

Impedance spectroscopy study of Pb<Subscript>2</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript> compound

The lead pyrophosphate, Pb₂P₂O₇, compound was prepared by conventional solid-state reaction and identified by X-ray powder diffractometer. Pb₂P₂O₇ has a triclinic structure whose electrical properties were studied using impedance spectroscopy technique. Both impedance and modulus analysis exhibit the grain and grain boundary contribution to the electrical response of the sample. The temperature dependence of the bulk and grain boundary conductivity were found to obey the Arrhenius law with activation energies E _g = 0.66 eV and E _gb = 0.67 eV, respectively. The scaling behavior of the imaginary part of the complex impedance suggests that the relaxation describes the same mechanism at various temperatures.     

Influence of carbon additive on the properties of spherical Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> and LiFePO<Subscript>4</Subscript> materials for lithium-ion batteries

Preparing spherical particles with carbon additive is considered as one effective way to improve both high rate performance and tap density of Li₄Ti₅O₁₂ and LiFePO₄ materials. Spherical Li₄Ti₅O₁₂/C and LiFePO₄/C composites are prepared by spray-drying–solid-state reaction method and controlled crystallization–carbothermal reduction method, respectively. The X-ray diffraction characterization, scanning electron microscope, Brunauer–Emmett–Teller, alternating current impedance analyzing, tap density testing, and electrochemical property measurements are investigated. After hybridizing carbon with a proper quantity, the crystal grain size of active materials is remarkably decreased and the electrochemical properties are obviously improved. The Li₄Ti₅O₁₂/C and LiFePO₄/C composites prepared in this work are spherical. The tap density and the specific surface area are as high as 1.71 g cm⁻³ and 8.26 m² g⁻¹ for spherical Li₄Ti₅O₁₂/C, which are 1.35 g cm⁻³ and 18.86 m² g⁻¹ for spherical LiFePO₄/C powders. Between 1.0 and 3.0 V versus Li, the reversible specific capacity of the Li₄Ti₅O₁₂/C is more than 150 mAh g⁻¹ at 1.0-C rate. Between 2.5 and 4.2 V versus Li, the reversible capacity of the LiFePO₄/C is close to 140 mAh g⁻¹ at 1.0-C rate.     

Magnetic properties of LiNi<Subscript>0.5</Subscript>Mn<Subscript>0.47</Subscript>Al<Subscript>0.03</Subscript>O<Subscript>2</Subscript> as positive electrode for Li-ion batteries

The layered LiNi_0.5Mn_0.47Al_0.03O₂ was synthesized by wet chemical method and characterized by X-ray diffraction and analysis of magnetic measurements. The powders adopted the α-NaFeO₂ structure. This substitution of Al for Mn promotes the formation of Li(Ni_0.47²⁺Ni_0.03³⁺Mn_0.47⁴⁺Al_0.03³⁺)O₂ structures and induces an increase in the average oxidation state of Ni, thereby leading to the shrinkage of the lattice unit cell. The concentration of antisite defects in which Ni²⁺ occupies the (3a) Li lattice sites in the Wyckoff notation has been estimated from the ferromagnetic Ni²⁺(3a)–Mn⁴⁺(3b) pairing observed below 140 K. The substitution of 3% Al for Mn reduces the amount of antisite defects from 7% to 6.4–6.5%. The analysis of the magnetic properties in the paramagnetic phase in the framework of the Curie–Weiss law agrees well with the combination of Ni²⁺ (S = 1), Ni³⁺ (S = 1/2) and Mn⁴⁺ (S = 3/2) spin-only values. Delithiation has been made by the use of K₂S₂O₈. According to this process, known to be softer than the electrochemical one, the nickel ions in the (3b) sites are converted into Ni⁴⁺ in the high spin configuration, while Ni²⁺(3a)–Mn⁴⁺(3b) ferromagnetic pairs remain, as the Li⁺(3b) ions linked to the Ni²⁺(3a) ions in the antisite defects are not removed. The results show that the antisite defect is surrounded by Mn⁴⁺ ions, implying the nonuniform distribution of the cations in agreement with previous NMR and neutron experiments.     

Synthesis and characterization of electron beam evaporated LiCoO<Subscript>2</Subscript> thin films

LiCoO₂ thin films were prepared by electron beam evaporation technique using LiCoO₂ target with Li/Co ratio 1.1 in an oxygen partial pressure of 5 × 10⁻⁴ mbar. The films prepared at substrate temperature T _s < 573 K were amorphous in nature, and the films prepared at T _s > 573 K exhibited well defined (104), (101), and (003) peaks among which the (104) orientation predominates. The X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma (ICP) data revealed that the films prepared in the substrate temperature range 673–773 K are nearly stoichiometric. The grain size increases with an increase of substrate temperature. The Co–e_g absorption bands, are empty and their peak position lies at around 1.7 eV above the top to the Co–t_2g bands. The fundamental absorption edge was observed at 2.32 eV. The films annealed at 1,023 K in a controlled oxygen environment exhibit (104) out plane texture with large grains. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006     

High-frequency tunable EPR spectroscopy of non-Kramers ions in AgGaSe<Subscript>2</Subscript>: Cr,AgGaS<Subscript>2</Subscript>: Cr,and CdGa<Subscript>2</Subscript>S<Subscript>4</Subscript>: Cr crystals

Crystals of the chalcopyrite family, AgGaSe₂, AgGaS₂, and CdGa₂S₄, doped with chromium ions have been investigated using high-frequency broad-band EPR spectroscopy in the range 65–530 GHz at T = 4.2 K. It has been revealed that, in the AgGaSe₂ and AgGaS₂ crystals, the Cr²⁺ ions occupy positions with orthorhombic and tetragonal symmetry, whereas the previously investigated CdGaS₄ crystals contain only tetragonal centers. The observed spectra have been described in the framework of the spin-Hamiltonian formalism. Apart from the divalent chromium centers, the EPR lines attributed to non-Kramers ions are observed in the frequency range 300–450 GHz for all the crystals under investigation. The nature of these lines has been discussed.     

Optical investigation of LaMnO<Subscript>3</Subscript> thin films: a study of the 2-eV band

We measure the transmittance of LaMnO₃ (LMO) thin films in the spectral range from 10 000 to 38 000 cm^-1 as a function of temperature. The optical conductivity obtained from the transmittance data is decomposed into five Drude-Lorentz contributions: three of them show evident changes below the Néel temperature T _N @\simeq 140 K. We discuss the band assignment in the framework of the tight-binding and of the orbitally degenerate Hubbard models. Our results ascribe the overall low-frequency spectrum of LMO to charge-transfer mechanisms involving the t _2g and e _g electrons of the Mn ions, without invoking the presence of excitonic contributions. This finding definitely promotes a Mott-Hubbard scenario for LMO and provides an estimate of the Hamiltonian parameters.     

Photopyroelectric spectroscopy of Sb<Subscript>2</Subscript>O<Subscript>3</Subscript> - ZnO ceramics

Photopyroelectric spectroscopy is used to study the band-gap energy of the ceramic (ZnO + xSb₂O₃), x = 0.1 - 1.5 mol% and the ceramic (ZnO + 0.4 mol%  Bi₂O₃ + xSb₂O₃), x = 0 - 1.5 mol% sintered at isothermal temperature, 1280 °C, for 1 and 2 hours. The wavelength of incident light, modulated at 9 Hz, is kept in the visible range and the photopyroelectric spectrum with reference to doping level is discussed. The band-gap energy is reduced from 3.2 eV, for pure ZnO, to 2.86, 2.83 eV for the samples without Bi₂O₃at 0.1 mol% of Sb₂O₃ for 1 and 2 hours of sintering time, respectively. It is reduced to 2.83, 2.80 eV for the samples with Bi₂O₃ at 0 mol% of Sb₂O₃ for 1 and 2 hours of sintering time, respectively. The steepness factor σ_A which characterizes the slop of exponential optical absorption is discussed with reference to the doping level. The phase constitution is determined by XRD analysis; microstructure and compositional analysis of the selected areas are analyzed using SEM and EDX.     

Investigations of EPR parameters and impurity structure for Co<Superscript>2+</Superscript> in Ca(OH)<Subscript>2</Subscript> crystal

The electron paramagnetic resonance (EPR) parameters (g _‖ andg _⊥ factors and hyperfine structure constantsA _‖,A _⊥) for Co²⁺ in Ca(OH)₂ are studied from the second-order perturbation formulas on the basis of the cluster approach. In these formulas, the contributions to EPR parameters from the state interactions and covalency effects are considered and the parameters related to both effects are obtained from the optical spectra and impurity structure of the studied system. From the study, it is found that the β angle between the metal-ligand bond and the C₃ axis changes from 61° in a pure crystal to 53.68(26)° in the impurity center of a Co²⁺-doped Ca(OH)₂ crystal because of the impurity-induced local lattice relaxation. The reduction of the angle β in the impurity center is also supported by the result obtained by analyzing the EPR zero-field splitting for Mn²⁺ in the same Ca(OH)₂ crystal. The EPR parameters of Ca(OH)₂:Co²⁺ are also reasonably explained by considering the suitable local lattice relaxation.     

Photoluminescence of fluoroacrylate polymers impregnated with Eu(bta)<Subscript>3</Subscript> using supercritical CO<Subscript>2</Subscript>

Optical properties (photoluminescence and absorption) of Eu(bta)₃(B) _n (B = H₂O or 1,10-phenanthroline) polycrystalline powders and fluoroacrylate polymers (FAPs) impregnated with these compounds using supercritical CO₂ (SC CO₂) were investigated. It was established that impregnation of Eu(bta)₃phen into the FAPs using an SC CO₂ solution was difficult to achieve. The type of B (ancillary ligand) and the polymer matrix were shown to influence the temperature quenching of photoluminescence of Eu³⁺ ions in the range 25–100°C. A comparative analysis of quantum yields (λ_ex = 300 and 380 nm) and photoluminescence decay times (λ_ex = 337.1 nm) for Eu(bta)₃B _n and for Eu(bta)₃B _n -doped FAPs was performed.     

Electron paramagnetic resonance of Ce<Superscript>3+</Superscript> and Nd<Superscript>3+</Superscript> impurity ions in YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6.13</Subscript>

The electron paramagnetic resonance (EPR) spectra of Ce³⁺ and Nd³⁺ impurity ions in unoriented powders of the YBa₂Cu₃O_6.13 compound are observed and interpreted for the first time. It is demonstrated that, upon long-term storage of the samples at room temperature, the EPR signals of these ions are masked by the spectral line (with the g factor of approximately 2) associated with the intrinsic magnetic centers due to the significant increase in its intensity.     

Charge density wave and superconductivity in 2H- and 4H-NbSe<Subscript>2</Subscript>: A revisit

Good-quality hexagonal NbSe₂ single crystals were prepared. In 2H-NbSe₂, superconducting and charge density wave (CDW) transitions were found at T _s = 7.4 K and T _c = 35 K respectively as reported previously. We have noticed that these two transitions are changed to T _c = 42 K and T _s = 6.5 K, in 4H-NbSe₂. Thermopower has shown clear anomaly at CDW transitions. The anisotropic upper critical field was calculated as ~3 and 6.3 for 2H- and 4H-single crystals around t = 0.81, where t = T/T _s, from resistivity and explained in terms of coherence length. From the relation, H_c2 (T)=H_c2 (0)[1-t²]H_{\rm c2} (T)=H_{\rm c2} (0)[1-t^2], H_c2^l (0)H_{\rm c2}^l (0) was calculated as ~8.15 T and 16.98 T at t = 0.84 in 2H-NbSe₂ and 4H-NbSe₂ respectively. However, H_c2^t (0) = 2.68H_{\rm c2}^t (0) = 2.68T for both single crystals.     

<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.     

Effects of dopant on the electrochemical properties of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> anode materials

The effects of dopant on the electrochemical properties of spinel-type Li_3.97M_0.1Ti_4.94O₁₂ (M = Mn, Ni, Co) and Li_(4-x/3)Cr_xTi_(5-2x/3)O₁₂(x = 0.1, 0.3, 0.6, 0.9, 1.5) were systematically investigated. Charge-discharge cycling were performed at a constant current density of 0.5 mA/cm² between the cut-off voltages of 3.0 and 1.0 V, the experimental results showed that Cr³⁺ dopant improved the reversible capacity and cycling stability over the pristine Li₄Ti₅O₁₂. The substitution of the Mn³⁺ and Ni³⁺ slightly decreased the capacity of the Li₄Ti₅O₁₂. Dopants such as Co³⁺ to some extent worsened the electrochemical performance of the Li₄Ti₅O₁₂.     

Structure,thermal properties,conductivity and electrochemical stability of di-urethanesil hybrids doped with LiCF<Subscript>3</Subscript>SO<Subscript>3</Subscript>

Variable chain length di-urethane cross-linked poly(oxyethylene) (POE)/siloxane hybrid networks were prepared by application of a sol-gel strategy. These materials, designated as di-urethanesils (represented as d-Ut(Y′), where Y′ indicates the average molecular weight of the polymer segment), were doped with lithium triflate (LiCF₃SO₃). The two host hybrid matrices used, d-Ut(300) and d-Ut(600), incorporate POE chains with approximately 6 and 13 (OCH₂CH₂) repeat units, respectively. All the samples studied, with compositions ∞ > n ≥ 1 (where n is the molar ratio of (OCH₂CH₂) repeat units per Li⁺), are entirely amorphous. The di-urethanesils are thermally stable up to at least 200 °C. At room temperature the conductivity maxima of the d-Ut(300)- and d-Ut(600)-based di-urethanesil families are located at n = 1 (approximately 2.0 × 10⁻⁶ and 7.4 × 10⁻⁵ Scm⁻¹, respectively). At about 100 °C, both these samples also exhibit the highest conductivity of the two electrolyte systems (approximately 1.6 × 10⁻⁴ and 1.0 × 10⁻³ Scm⁻¹, respectively). The d-Ut(600)-based xerogel with n = 1 displays excellent redox stability.     

EPR of trivalent iron centers in SrF<Subscript>2</Subscript>: Fe crystals

Paramagnetic centers of three types are found in SrF₂: Fe(0.2 at. %) crystals. Two types are observed in the untreated crystals, and the third type appears only in the crystals irradiated by x-rays. The EPR spectra of one type of centers in a nonirradiated crystal and of the centers that appear after irradiation are described by the orthorhombic Hamiltonians with an effective spin S _eff = 5/2. In both cases, the centers are observed at 4.2 and 77 K. The principal axes of the spin Hamiltonians for them are along the 〈001〉, 〈1 \(\overline 1 \) 0〉, and 〈110〉 axes. However, the fine-structure parameters of their EPR spectra differ significantly. An analysis of the superhyperfine structure (SHFS) of the EPR spectra shows that the radiation center forms through substitution of a Fe²⁺ ion for a Sr²⁺ cation. Under x-ray irradiation, the Fe²⁺ ion transforms into the Fe³⁺(⁶ A _1g ) state and is displaced to an off-center position along the C ₂ axis of its coordination cube. The absence of a SHFS in the EPR spectra of the orthorhombic centers in a nonirradiated crystal makes it impossible to determine their molecular structure unambiguously. The most probable model is proposed for this structure. The EPR spectra of centers of the third type were observed only at 4.2 K, and the structure of these centers was not studied.     

Magnetic and EPR studies of the EuFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> single crystal

Magnetic and electron paramagnetic resonance (EPR) properties of EuFe₃(BO₃)₄ single crystals have been studied over the temperature range of 300–4.2 K and in a magnetic field up to 5 T. The temperature, field and orientation dependences of susceptibility, magnetization and EPR spectra are presented. An antiferromagnetic ordering of the Fe subsystem occurs at about 37 K. The easy direction of magnetization perpendicular to the c axis is determined by magnetic measurements. Below 10 K, we observe an increase of susceptibility connected with the polarization of the Eu sublattice by an effective exchange field of the ordered Fe magnetic subsystem. In a magnetic field perpendicular to the c axis, we have observed an increase of magnetization at T < 10 K in the applied magnetic field, which can be attributed to the appearance of the magnetic moment induced by the magnetic field applied in the basal plane. According to EPR measurements, the distance between the maximum and minimum of derivative of absorption line of the Lorentz type is equal to 319 Gs. The anisotropy of g-factor and linewidth is due to the influence of crystalline field of trigonal symmetry. The peculiarities of temperature dependence of both intensity and linewidth are caused by the influence of excited states of europium ion (Eu³⁺). It is supposed that the difference between the g-factors from EPR and the magnetic measurements is caused by exchange interaction between rare earth and Fe subsystems via anomalous Zeeman effect.     

Superhyperfine Structure of EPR Spectra in LiLuF<Subscript>4</Subscript>:U<Superscript>3+</Superscript> and LiYF<Subscript>4</Subscript>:Yb<Superscript>3+</Superscript> Single Crystals

Electron paramagnetic resonance (EPR) spectra of doped paramagnetic crystals LiLuF₄:U³⁺ and LiYF₄:Yb³⁺ have been investigated at a frequency of about 9.42 GHz in the temperature range of 10–20 K. The U³⁺ ion spectrum is characterized by g-factors g _∥ = 1.228 and g _⊥ = 2.516, and contains the hyperfine structure due to the ²³⁵U isotope with nuclear spin I = 7/2 and natural abundance of 0.71%. The observed hyperfine interaction constants are A _∥ = 81 G and A _⊥ = 83.8 G. Moreover, the spectrum reveals the well-resolved superhyperfine structure (SHFS) due to two groups of four fluorine ions forming the nearest surrounding of the U³⁺ ion. This SHFS contains up to nine components with the spacing between components being about 12.7 G. The SHFS is observed also in the EPR spectrum of the LiYF₄:Yb³⁺ crystal; up to 17 components with spacing of about 3.7 G may be traced. Some parameters of the effective Hamiltonian of the SHF interaction are estimated, the contribution of covalent bonding of f-electrons with ligands into these parameters is discussed. Authors' address: Igor N. Kurkin, Kazan State University, Kremlevskaya ulitsa 18, Kazan 420008, Russian Federation     

Fluorescent Carbon Dots Capped with PEG<Subscript>200</Subscript> and Mercaptosuccinic Acid

The synthesis and functionalization of carbon nanoparticles with PEG₂₀₀ and mercaptosuccinic acid, rendering fluorescent carbon dots, is described. Fluorescent carbon dots (maximum excitation and emission at 320 and 430 nm, respectively) with average dimension 267 nm were obtained. The lifetime decay of the functionalized carbon dots is complex and a three component decay time model originated a good fit with the following lifetimes: τ ₁ = 2.71 ns; τ ₂ = 7.36 ns; τ ₃ = 0.38 ns. The fluorescence intensity of the carbon dots is affected by the solvent, pH (apparent pK _a of 7.4 ± 0.2) and iodide (Stern-Volmer constant of 78 ± 2 M⁻¹).     

Electronic spectra and phase transitions in thin [N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>CuCl<Subscript>4</Subscript> microcrystals

Optical absorption spectra in thin [N(CH₃)₄]₂CuCl₄ crystals in the thickness range 10 μm ≤ d < 100 μm have been studied. Strengthening of the crystal field has been found with a decrease in the [N(CH₃)₄]₂CuCl₄ crystal size. The reasons for absorption band shifts in the visible region depending on the [N(CH₃)₄]₂CuCl₄ crystal thickness and the manifestation of a size effect in crystals with an incommensurate superstructure are discussed.