Mixed valence on a pyrochlore lattice - as a geometrically frustrated magnet

Above 40 K, the magnetic susceptibility of the heavy Fermion spinel LiV₂O₄ has many features in common with those of geometrically frustrated magnetic insulators, while its room temperature resistivity comfortably exceeds the Mott-Regel limit. This suggests that local magnetic moments, and the underlying geometry of the pyrochlore lattice, play an important role in determining its magnetic properties. We extend a recently introduced tetragonal mean field theory for insulating pyrochlore antiferromagnets to the case where individual tetrahedra contain spins of different lengths, and use this as a starting point to discuss three different scenarios for magnetic and electronic transitions in LiV₂O₄. Received 12 March 2002 and Received in final form 3 May 2002 Published online 25 June 2002     

Structure and electrochemical performance of LiV x Mn2 − x O4 (0 ≤ x ≤ 0.20) cathode materials for rechargeable lithium ion batteries

LiMn₂O₄ and vanadium-substituted LiV _x Mn_2???x O₄ (x?=?0.05, 0.10 0.15 and 0.20) cathode materials were synthesized by sol–gel method using aqueous solutions of metal nitrates and tartaric acid as chelating agent at 600 °C for 10 h. The structure and electrochemical properties of the synthesized materials were characterized by using X-ray diffraction, SEM, TEM and charge–discharge studies. X-ray powder diffraction analysis was changed in lattice parameters with increasing vanadium content suggesting the occupation of the substituent within LiMn₂O₄ interlayer spacing. TEM and SEM analyses show that LiV_0.15Mn_1.85O₄ has a smaller particle size and more regular morphological structure with narrow size distribution than LiMn₂O₄. It is concluded that the structural stability and cycle life improvement were due to many factors like better crystallinity, smaller particle size and uniform distribution compared to the LiMn₂O₄ cathode material. The LiV_0.15Mn_1.85O₄ cathode material has improved the structural stability and excellent electrochemical performances of the rechargeable lithium ion batteries.     

插层化合物LiV2O4的制备与实验研究

用化学方法从层状化合物LiVO₂中引出0.5个Li后得到Li_0.5VO₂,再经过低温真空热处理制备出尖晶石结构化合物LiV₂O₄,类似地处理Li_0.465VO₂,得到缺Li的Li_0.93V₂O₄,LiV₂O₄和Li_0.93V 关键词：     

Influence of NiCl2 modification on the electrochemical performance of LiV3O8 cathode for lithium ion batteries

The 5.0, 8.0, and 10.0 wt% NiCl₂-modified LiV₃O₈ materials are successfully prepared and the effects of NiCl₂ modification on the electrochemical performance of LiV₃O₈ cathode have been investigated. The structural and surface morphologic properties of synthesized materials are characterized by X-ray diffraction and scanning electron microscopy. The electrochemical properties are investigated by charge–discharge testing and cyclic voltammetry. It is found that 8.0 wt% NiCl₂-modified LiV₃O₈ shows excellent electrochemical properties. The initial discharge capacity of 8.0 wt% NiCl₂-modified LiV₃O₈ is much higher than that of pristine LiV₃O₈, and can attain 336.7 mAh g^?1 at the current rate of 0.5 C (300 mA g^?1 is assumed to be 1 C rate). Additionally, NiCl₂ modification significantly improves the cyclability of LiV₃O₈. The NiCl₂ modification is shown to be able to suppress the capacity fade of LiV₃O₈ without specific capacity expense by suppressing the characteristic phase transitions during cycling.     

LiV2O4: electronic,magnetic structure and heavy-fermion behaviour from first principles

First principles studies based on density functional theory (DFT) calculations within the generalized gradient approximations (GGA) and GGA + U approach using the full-potential, augmented plane wave + local orbitals (APW + lo) method, as implemented in the WIEN2k code, have been used to investigate the structural, electronic and magnetic properties of spinel-structure LiV₂O₄, in particular regarding the heavy fermion (HF) behaviour. The calculations were performed for ferromagnetic, anti-ferromagnetic, and ferrimagnetic configurations using two kinds of magnetic structures (tetragonal and rhombohedral). The GGA results showed that the Fermi energy lies in the V 3d (t_2g) bands with 1.5 electrons per V atom occupying this band, and the V 3d bands are separated by a ～1.9 eV energy gap from the O 2p bands and further split into t_2g and e_g bands with a ～1.0 eV energy gap, which are in good agreement with the photoelectron spectra. The GGA + U method indicates that the ground state of LiV₂O₄ is the tetragonal anti-ferromagnetic configuration with metallic character, and ferromagnetic order character at slightly higher energy, which is consistent with experimental result. The geometric frustration and hybridization between 3d (V) and 2p (O) could induce spin fluctuation and help to explain the instability of specific heat, susceptibility and HF behaviour.     

Electrochemical behavior of nanostructured LiV3O8 in aqueous LiNO3 solution

Despite the large number of studies on the electrochemical behavior of LiV₃O₈ as a cathode material in nonaqueous lithium ion batteries, little information is available about the electrochemical behavior of LiV₃O₈ as an anode material in aqueous rechargeable lithium batteries. In this work, nanostructured LiV₃O₈ is successfully prepared using a low-temperature solid-state method. The electrochemical properties of the LiV₃O₈ electrode in 1 M, 5 M, and saturated LiNO₃ aqueous electrolytes have been characterized by cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge/discharge experiments. The results show that LiV₃O₈ electrode in saturated LiNO₃ electrolyte exhibits good electrochemical performance in terms of specific capacity and electrochemical cycling performance. LiV₃O₈ electrode can be reversibly cycled in saturated LiNO₃ aqueous electrolyte for 300 cycles at a rate of 0.5 C (300 mA g⁻¹ is assumed to be 1 C rate) with impressive specific capacities.     

Investigation of structural and magnetic properties of Ni, NiFe and NiFe2O4 thin films

Soft magnetic thin films of Ni, NiFe and NiFe₂O₄ were prepared using reactive magnetron sputtering in various deposition conditions. Experimentally observed soft magnetic property was compared and correlated with nanocrystalline structure evolution. Ni and NiFe deposited films are textured with fcc(111) phase preferred orientation. Accordingly, grain size and lattice parameter were calculated from X-ray diffraction (111) peak line width and 2θ peak position. Addition of reactive gas oxygen in deposition process has substantial effect on crystalline structure of film. There is phase transition from the ordered NiFe (111) structure to the NiFe₂O₄ nanocrystalline phase. The resulting film has shown small X-ray diffraction intensity peak corresponding to (311) and (400) orientation, indicating small amount of existing NiFe₂O₄ phase. The mechanism has been discussed to be responsible for nanocrystallization and amorphization of NiFe₂O₄ films. Magnetic measurement (M-H) loop reveal soft magnetic nature of films with magnetic anisotropy. The coercivity (H_c) of films is in accordance with random anisotropy model, where H_c reduced with grain size. The structural transformation was supported by Fourier transforms infrared spectroscopy measurement. The films are highly smooth with surface roughness in the range of ∼0.53-0.93 nm. NiFe₂O₄ films have shown lowest surface roughness with highest electrical resistivity values. The structural, surface, magnetic and infrared spectroscopy results are observed and analyzed.     

Crystallization kinetics of Li2O-PbO-V2O5 glasses

Lead vanadate glasses of the system 5Li₂O−(45−x) PbO−(50+x) V₂O₅, with x=0, 5, 10, and 15 mol% have been prepared and studied by differential scanning calorimetry (DSC). The crystallization kinetics of the glasses were investigated under non-isothermal conditions applying the formal theory of transformations for heterogeneous nucleation to the experimental data obtained by DSC using continuous-heating techniques. In addition, from dependence of the glass-transition temperature (T_g) on the heating rate, the activation energy for the glass transition was derived. Similarly the activation energy of the crystallization process was determined and the crystallization mechanism was characterized. The results reveal the increase of the activation energy for glass transition which was attributed to the increase in the rigidity, the cross-link density and the packing density of these glasses. The phases into which the glass crystallizes have been identified by X-ray diffraction. Diffractograms of the transformed material indicate the presence of microcrystallites of Li_0.30V₂O₅, Li_0.67O₅V₂, LiV₆O₁₅, Li₄O₄Pb, and O₇Pb₂V₂ in a remaining amorphous matrix.     

Characterization of Ni–Cu mixed spinel ferrite

Crystal structure, X-ray density, porosity, compressive strength of Ni_1−xCu_xFe₂O₄ have been investigated along with scanning electron microscopy (SEM) to study the effect of composition and microstructure on the magnetic and electrical properties. The formation of single-phase ferrite is confirmed by the X-ray diffraction. Tetragonal deformation is observed for the sample of composition x=1, i.e. for pure CuFe₂O₄ Crystal structure for samples of other compositions are face centered cubic (FCC). SEM micrographs exhibit increase in grain size with the increase of copper content. Compressive strength decreases with the increase of Cu. Initial magnetic permeability and saturation magnetization is maximum for the composition of x=0.2, i.e. for Ni_0.8Cu_0.2Fe₂O₄, which can be attributed to the maximum sintered density obtained for this composition. Resistivity decreases with the increase of Cu content.     

First-principles study of the electronic and magnetic properties of a Nickel-Zinc ferrite: ZnxNi1−xFe2O4

Using first-principles density functional theory within the generalized gradient approximation method, the effect of Zn doping on electronic and magnetic properties of NiFe₂O₄ ferrite spinel has been studied. The crystal structure of the compounds is assigned to a pseudocubic structure and the lattice constant increases as the Zn concentration increases. Our spin-polarized calculations give a half-metallic state for NiFe₂O₄ and a normal metal state for Zn_xNi_1−xFe₂O₄ (0<x≤0.5). Based on the magnetic properties calculations, it is found that the saturation magnetic moment enhances linearly with increase in the Zn content in NiFe₂O₄. The Zn doping in NiFe₂O₄ also induces strong ferrimagnetism since it decreases the magnetic moment of A-sites.     

Synthesis and characterization of K2NiF4-type phases Ln0.5Sr1.5Mn0.5Fe0.5O4 (Ln = La, Nd, Gd, and Dy)

A systematic investigation of layered perovskite oxides with general formula Ln_0.5Sr_1.5Mn_0.5Fe_0.5O₄ (Ln?=?La, Nd, Gd, and Dy) has been undertaken mainly to understand their structural, magnetic, as well as electrical behavior. The materials were prepared by the ceramic method. X-ray data have been analyzed by using program Checkcell and the variations of various parameters are explained. It has been concluded that not only A-site cation radius, <r _A>, but also the size variance factor (σ ²) influence electrical and magnetic properties. A systematic study of electrical resistivity of all the four materials was undertaken as a function of temperature to understand the conduction mechanism. On analyzing the electrical resistivity data, it has been concluded that variable range hopping model is found to fit well. The magnetic studies suggest that the phases are antiferromagnetic and this behavior could arise from Mn⁴⁺–O–Mn⁴⁺, and Fe³⁺–O–Fe³⁺ superexchange interaction.     

The superexchange interactions in mixed Co-Fe ludwigite

The crystal structure, cation distribution and exchange interactions in the Co_2.25Fe_0.75O₂BO₃ ludwigite have been explored through X-ray diffraction, electrical resistivity, ac-susceptibility and Mossbauer effect measurements. The crystal data have shown that iron atoms occupy the most symmetric crystallographic sites Fe4 and Fe2. The complex magnetic behavior with two magnetic transitions near 70 and 115 K at low temperatures was found. The Mossbauer data have displayed the trivalent iron states only. The values of superexchange energies have been estimated for Co₃O₂BO₃ and Co_2.25Fe_0.75O₂BO₃ yielding a significant role of frustrations in the ludwigite magnetic system. Variable range Mott hopping conductivity law was proved to be valid in the wide temperature region, pointing out a localized character of charge carriers rather than collective.     

Microstructure-property relationship in magnetoelectric bulk composites

We present systematic studies that comprise phase connectivity and dielectric, multiferroic (MF) and magnetoelectric (ME) properties of (x) Ni_0.8Co_0.2Fe₂O₄+(1−x) Pb(Mg_1/3Nb_2/3)_0.67Ti_0.33O₃ [where x=0.15, 0.30 and 0.45] ME composites prepared by conventional solid-state reaction method. Scanning electron microscopic images of the composites predict different types of connectivity schemes viz 3-0, 3-1 and 3-3. The phase transition temperature of PMN-PT is independent of Ni_0.8Co_0.2Fe₂O₄ content. Room temperature P-E and M-H loops indicate the simultaneous existence of ferroelectric/magnetic ordering. In order to study the possibility of monitoring electrical ordering by means of a magnetic field, ME measurements were carried out. The composition-dependent phase connectivity was well co-related to formation of percolation path and inturn magnetoelectric output.     

The stability of K2[Pt(CN)4]Cl0·3·x.H2O in wet and dry atmosphere

The behavior of the one-dimensional electrical conductor K₂[Pt(CN)₄Cl_0·3·x.H₂O is studied at several temperatures in both wet and dry atmospheres using chemical analysis, X-ray diffraction and magnetic susceptibility data. It is concluded that the material is a series of hydrates with x between 2.5 and 3, and that a variation in x might influence its physical properties.     

Structure and the electrical and magnetic properties of perovskite-like Gd x Cu3V4O12 oxide

A new perovskite-like compound Gd _x Cu₃V₄O₁₂ (x = 0.67?0.73) is synthesized under high pressures (P = 4?9 GPa) and at high temperatures (T = 1000°C). Its structure (space group Im3, Z = 2, a = 7.2930(5) ?) is estrablished by X-ray analysis. The bond lengths and bond angles are determined. The temperature dependences of electrical resistivity (10?C300 K) and magnetic susceptibility are studied. The high-pressure Gd _x Cu₃V₄O₁₂ phase is found to have a semi-conductor type of conductivity and paramagnetic properties.     

First-principles study of the effect of iron doping on the electronic and magnetic properties of TbMn2O5

We have studied the electronic and magnetic properties of TbFe_xMn_2−xO₅ (x=0, 0.125, 0.25) samples using first-principles density functional theory within the generalized gradient approximation (GGA) schemes. The crystal structure of TbMn₂O₅ is orthorhombic containing Mn⁴⁺O₆ octahedra and Mn³⁺O₅ pyramids. The structure changes to monoclinic symmetry for the Fe-doping at the Mn sites. Our spin-polarized calculations give an insulating ground state for TbMn₂O₅ and a metallic ground state for Fe-doped TbMn₂O₅. Based on the magnetic properties calculations, it is found that the magnetic moment enhances with increase in the Fe-content in TbMn₂O₅. Most interestingly, the enhanced magnetic moment is due to a substantial reduction of the magnetic moments at the Fe sites.     

Systematic study on synthesis and structural, electrical transport and magnetic properties of Pb-substituted Bi-Ca-Co-O misfit-layer cobaltites

Single-phases of Pb-substituted Bi-Ca-Co-O misfit-layer cobaltites with various Pb concentrations have been synthesized and the Pb-substitution effects on the structural, electrical and magnetic properties have been systematically investigated. Powder X-ray diffraction analysis showed that the single-phases of Bi_1.8−x/2Pb_xCa₂Co₂O_z were obtained up to x=0.6-0.7 under the optimized synthesis conditions. The lattice parameters of Bi_1.8−x/2Pb_xCa₂Co₂O_z continuously changed with increasing Pb concentration. The electron diffraction analysis suggested that the structure consisted of two different sublattices with a rock salt structure (RS) and a hexagonal CdI₂ structure (H), respectively, without modulation. In combined with the chemical composition analysis, the chemical formulas of the x=0 and x=0.6 samples were determined approximately as [Bi_1.74Co_0.31Ca_2.01O₄]^RS[CoO₂]_1.69 and [Bi_1.47Pb_0.38Co_0.29Ca_1.98O₄]^RS[CoO₂]_1.71, respectively. The electrical resistivity became more metallic with increasing the Pb concentration up to x=0.6. Moreover, the Pb-substitution simultaneously increased the antiferromagnetic Weiss temperatures and decreased the effective magnetic moments of the Co ions.     

Sr doping effects on the transport and magnetic properties of GdBaCo2O5+δ

Studies on some new members of the cobalt perovskite Gd_1−xSr_xBaCo₂O_5+δ with low strontium concentrations (0<x<0.1) have been carried out with the aim of investigating possible metallization of the GdBaCo₂O_5+δ system by hole doping. Low temperature electrical resistivity, magnetic susceptibility and thermopower of the above system have been studied. The pristine compound with x=0 and δ∼0.5 exhibits a semiconductor-like behavior and two magnetic transitions below room temperature. Upon Sr²⁺ substitution, there is a fall in resistivity by 2-3 orders of magnitude at low temperature and also a dramatic reduction in the ferromagnetic to antiferromagnetic transition temperature. These changes can be explained on the basis of hole doping (and increase in the Co⁴⁺content). Evidence for an increase in Co⁴⁺ with Sr²⁺ substitution is provided by iodometric analysis.     

NiZnCu ferrite applied for LTCC microinductor

This paper describes the fabrication of thin magnetic layers for an LTCC planar-type inductor with a 0.11 mm thickness. The thin ferrite layers were fabricated by tape casting method. Synthesis conditions and X-ray analysis (300 K) of the Ni_0.3Zn_0.62Cu_0.08Fe₂O₄ ferrite are presented. A pure cubic, Fd 3m crystal structure was observed for the Ni_0.3Zn_0.62Cu_0.08Fe₂O₄ ferrite. The complex impedance and dielectric permittivity of Ni_0.3Zn_0.62Cu_0.08Fe₂O₄ ferrite were determined as a function of temperature (from −55 to 170 °C) and frequency (from 10 Hz to 2 MHz). Dc resistivity was measured in a temperature range from −55 to 170 °C. Magnetization and magnetic hysteresis were measured by a vibrating sample magnetometer (VSM) in an applied magnetic field up to 60 kOe. The inductance and quality factor were measured in a frequency range 0.1-120 MHz. With the help of finite elements method (FEM) simulation it is possible to calculate the elements electrical parameters and optimize the design. This paper presents a magnetic field modelling of an inductor structure.     

Magnetic properties and electronic structure of the LaGaO3 perovskite doped with nickel

Solid solutions of the composition LaGa_{1 ? x} Ni _x O₃ (0.01 ≤ x ≤ 0.10) are synthesized, and their magnetic and electrical properties are investigated. It is established that the ground state of the Ni(III) atoms is the low-spin state ² E _g ; however, in the temperature range under investigation, there occurs the ² E _g ? ⁴ T _1g spin equilibrium. An increase in the nickel concentration leads to an increase in the electron conduction of the solid solutions. The band structure of the LaGa_0.5Ni_0.5O₃ model compound is calculated using the ab initio full-potential linearized augmented-plane-wave method within the generalized gradient approximation (FLAPWGGA). It is shown that the dominant role in the variations observed in the magnetic and electrical properties of the nonmagnetic semiconductor LaGaO₃ upon doping with nickel is played by the Ni 3d(e _g ↑, ↓) states.