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.     

Phase transitions in diluted magnets: Critical behavior,percolation, and random fields

Transition metal halides provide realizations of Ising,XY, and Heisenberg antiferromagnets in one, two, and three dimensions. The interactions, which are of short range, are generally well understood. By dilution with nonmagnetic species such as Zn⁺⁺ or Mg⁺⁺ one is able to prepare site-random alloys which correspond to random systems of particular interest in statistical mechanics. By mixing two magnetic ions such as Fe⁺⁺ and Co⁺⁺ one can produce magnetic crystals with competing interactions-either in the form of competing anisotropies or competing ferromagnetic and antiferromagnetic interactions. In this paper the results of a series of neutron scattering experiments on these systems carried out at Brookhaven over the past several years are briefly reviewed. First the critical behavior in Rb₂Mn_0.5Ni_0.5F₄ and Fe_cZn_1–cF₂ which correspond to two-dimensional and three-dimensional random Ising systems, respectively, are discussed. Percolation phenomena have been studied in Rb₂Mn_cMg_l–cF₄, Rb₂Co_cMg_l–cF₄, KMn_cZ_l-cF₃, and Mn_cZn_l–cF₂ which correspond to two-and three-dimensional Heisenberg and Ising models, respectively. In these casesc is chosen to be in the neighborhood of the nearest-neighbor percolation concentration. Application of a uniform field to the above systems generates a random staggered magnetic field; this has facilitated a systematic study of the random field problem. As we shall discuss in detail, a variety of novel, unexpected phenomena have been observed.     

Octahedral vs tetrahedral coordination of the co(II) ion in layer compounds: CoxZn1−xIn2S4(O⩽x⩽0.46) solid solution

Large crystals of Co_xZn_1−xIn₂S₄ (0.00 ⩽ x ⩽ 0.46) solid solution were grown from the vapour phase by chemical transport modified by the time variation of the temperature profile procedure. Co²⁺ ions were found, by XPS analysis, to occupy tetrahedral as well as octahedral sites of the ZnIn₂S₄-type structure. The magnetic properties of Co_0.46Zn_0.54In₂S₄, crystallizing in space group R 3m, were explained in terms of the short-range magnetic order arising from the presence of isolated clusters of magnetic ions.     

Nuclear Magnetic Resonance Relaxation Study of the Phase Transitions of Rb2CuCl4·2H2O and Cs2MnCl4·2H2O Single Crystals

The physical properties and phase transitions of Rb₂CuCl₄·2H₂O and Cs₂MnCl₄·2H₂O crystals were investigated by performing ⁸⁵Rb, ⁸⁷Rb, and ¹³³Cs nuclear magnetic resonance relaxation analyses. The temperature dependences of the spectra and the spin–lattice relaxation times T ₁ near T _C are related to changes in the symmetry of the octahedrons consisting of four Cl⁻ ions and two water molecules around Rb⁺ or Cs⁺; the forms of these octahedrons are disrupted by the loss of H₂O. The difference between the relaxation times of the two crystals is possibly due to the difference between the electron structures of the Cu and Mn ions. Cu²⁺ has nine valence electrons in its 3d orbital, whereas Mn²⁺ has five valence electrons in its 3d orbital.     

Ferroelastic crystals and their nonlinear elastic properties observed in frequency range from gigahertz to milihertz

The experiments reported in this article have been performed to unify the results of earlier and recent determinations of parameters describing the elastic properties of Rb₄LiH₃(SO₄)₄, LiCsSO₄ (LCS) and KH₂PO₄ crystals measured by different experimental methods. The above crystals undergo a second-order phase transition, incommensurate phase transition (PT) and a first-order but close to second-order phase transition, respectively. To investigate the elastic properties of the crystals in the frequency range from 10^?1 to 10¹⁰ Hz, five experimental methods were applied: dynamic mechanical analysis, piezoelectric resonance, composite oscillator bar, ultrasonic wave propagation and Brillouin light scattering. The results of the experiments allowed identification of the processes contributing to the elastic response of the crystals investigated. Moreover, for the LCS crystal a model of the incommensurate PT was presented.     

Study of Mn2+ EPR spectra in the incommensurate phase of Rb2ZnCl4

An EPR study of Mn²⁺ centers in the incommensurate phase of rubidium tetrachlorozincate crystals is reported. It is shown that the temperature dependence of the high-field hyperfine line group M _S=3/2↔5/2 can be described in terms of a simple “local” model. The data obtained support the nonclassical type of critical behavior in Rb₂ZnCl₄ crystals corresponding to the three-dimensional Heisenberg model for a two-component order parameter. Fiz. Tverd. Tela (St. Petersburg) 41, 691–694 (April 1999)     

Facile Construction of 3D Reduced Graphene Oxide Wrapped Ni3S2 Nanoparticles on Ni Foam for High‐Performance Asymmetric Supercapacitor Electrodes

3D reduced graphene oxide (rGO)‐wrapped Ni₃S₂ nanoparticles on Ni foam with porous structure is successfully synthesized via a facile one‐step solvothermal method. This unique structure and the positive synergistic effect between Ni₃S₂ nanoparticles and graphene can greatly improve the electrochemical performance of the NF@rGO/Ni₃S₂ composite. Detailed electrochemical measurements show that the NF@rGO/Ni₃S₂ composite exhibits excellent supercapacitor performance with a high specific capacitance of 4048 mF cm^?2 (816.8 F g^?1) at a current density of 5 mA cm^?2 (0.98 A g^?1), as well as long cycling ability (93.8% capacitance retention after 6000 cycles at a current density of 25 mA cm^?2). A novel aqueous asymmetric supercapacitor is designed using the NF@rGO/Ni₃S₂ composite as positive electrode and nitrogen‐doped graphene as negative electrode. The assembled device displays an energy density of 32.6 W h kg^?1 at a power density of 399.8 W kg^?1, and maintains 16.7 W h kg^?1 at 8000.2 W kg^?1. This outstanding performance promotes the as‐prepared NF@rGO/Ni₃S₂ composite to be ideal electrode materials for supercapacitors.     

Stoichiometry of LiNiO2 Studied by Mössbauer Spectroscopy

From the ⁶¹Ni and ⁵⁷Fe Mössbauer spectroscopy data follows the cationic site assignment in Li_1–x Ni_1+x O₂. Our data explain the ferromagnetic properties of this material because of the appearance of Ni²⁺ (S=1) among Ni³⁺ (S=1/2) in Ni³⁺O₂ hexagonal planes. We have no evidence for the ferromagnetic interaction between the NiO₂ layers through the excess Ni²⁺ ions substituting the Li⁺ ions. The presence of Ni²⁺ found in the Ni³⁺O₂ planes explains the absence of the Jahn–Teller distortions probably because of the electronic transfer between the Ni³⁺ and Ni²⁺ ions.     

Characterization of the 2D antiferromagnets Rb2MnCl4 and Rb3Mn2Cl7 : Optical,Raman and magnetic circular dichroism studies

Below T_N, the site symmetry at the Mn²⁺ ion is centrosymmetric (Rb₂MnCl₄) and non-centrosymmetric (Rb₃Mn₂Cl₇) respectively. As a result, one expects the appearance of magnetic dipole or electric dipole exciton origins in the optical spectra. These were clearly seen via polarized absorption and magnetic circular dichroism measurements through the 4T₂(D) band. The zone edge magnon frequencies are found to be 80 cm^?1 (Rb₂MnCl₄) and 90 cm^?1 (Rb₃MnCl₂in7). The two compounds are also easily distinguished through their room temperature axial absorption (⁴T₂ (G) band) and Raman spectra. Low temperature data indicate that the tetragonal field plays an important role.     

Resin‐Derived Ni3S2/Carbon Nanocomposite for Advanced Rechargeable Aqueous Zn‐Based Batteries

The exploration of high‐energy and stable cathode materials is highly desirable and challenging for the development of advanced Zn‐based batteries. In this work, a facile pyrolysis method is reported to synthetize Ni₃S₂/carbon nanocomposite as high‐performance cathode by employing ion exchange resin as a precursor. Attributing to the abundant active sites and enhanced conductivity from well binding between Ni₃S₂ and carbon, a markedly high capacity of 234.3 mA h g^?1 is obtained for this Ni₃S₂/carbon at a high current density of 6.9 A g^?1. Moreover, a Zn‐based battery is demonstrated by using the Ni₃S₂/carbon as a cathode and Zn plate as an anode, which delivers a maximum power density of 58.6 kW kg^?1, together with a peak energy density of 356 W h kg^?1 and 93.7% capacity retention after 5000 charging–discharging cycles. This simple synthetic strategy to achieve robust Ni‐based composite electrodes may open up new opportunities to design other transition metal–based electrodes for energy storage applications.     

Structure and magnetotransport properties of the new quasi-two-dimensional molecular metal β″-(BEDT-TTF)4H3O[Fe(C2O4)3] · C6H4Cl2

The β″-(BEDT-TTF)₄A^I[M^III(C₂O₄)₃] · G(A^I=NH ₄ ⁺ , H₃O⁺, K⁺, Rb⁺; M^III=Fe, Cr; G = “guest” solvent molecule) family of layered molecular conductors with magnetic metal oxalate anions exhibits a pronounced dependence of the conducting properties on the type of neutral solvent molecules introduced into the complex anion layer. A new organic dichlorobenzene (C₆H₄Cl₂)-containing conductor of this family, namely, β″-(BEDT-TTF)₄H₃O[Fe(C₂O₄)₃] · C₆H₄Cl₂, is synthesized. The structure of the synthesized single crystals studied by X-ray diffraction is characterized by the following parameters: a = 10.421(1) Å, b= 19.991(2) Å, c= 35.441(3) Å, β = 92.87(1)°, V= 7374(1) ų, space groupC2/c, and Z = 4. In the temperature range 0.5&;2-300 K, the conductivity of the crystals is metallic without changing into a superconducting state. The magnetotransport properties of the crystals are examined in magnetic fields up to 17 T at T = 0.5 K. In fields higher than 10 T, Shubnikov-de Haas oscillations are detected, and the Fourier spectrum of these oscillations contains two frequencies with maximum amplitudes of about 80 and 375 T. The experimental results are compared with the related data obtained for other phases of this family. The possible structural mechanisms of the effect of a guest solvent molecule on the transport properties of the β″-(BEDT-TTF)₄A^I[M^III(C₂O₄)₃] · G crystals are analyzed.     

Localized magnon gap modes in the 2-d Ising antiferromagnets K2CoF4 and Rb2CoF4

The defect (Mn²⁺,Ni²⁺,Fe²⁺) induced magnon gap modes in the layered antiferromagnets K₂CoF₄ and Rb₂CoF₄ were investigated with the methods of FIR absorption-and IR emission spectroscopy. The anisotropic exchange-parameters describing the strongly localized Mn²⁺ spin excitations far below the host lattice magnon band and the Ni²⁺ excitations in the vacinity of this band are presented. In the diluted system K₂Co_1-cMn_cF₄ localized Mn²⁺ cluster modes up to about C≈0.1 were observed. The excitation energy of these modes can only be explained by assuming an anisotropic Mn²⁺-Mn²⁺ exchange which is in contrast to the pure isomorphous system K₂MnF₄. In the spin mismatch system K₂CoF₄: Fe the magnetic moments of the isolated Fe²⁺ impurities are pulled from the plane perpendicular to the c-axis and aligned parallel to the easy axis of the magnetic crystal.     

Atomic 6p-Tl0 centers in ferroelectric Rb2ZnCl4 crystals

Abstract

Several Tl⁰ (6s²6p ¹)-type paramagnetic centers, produced by low temperature X-ray irradiation, were observed and studied by electron spin resonance (ESR) in the orthorhombic ferroelectric phase of thallium doped Rb₂ZnCl₄ crystals. The centers were formed by electron trapping at Tl⁺ ions localized substitutionally at Rb⁺ sites. The number and properties of the observed centers account for the tripling of the unit cell in the ferroelectric phase.     

Magnetic and ferroelectric properties of exchange-frustrated multiferroics (Ni1 ? xTx)3V2O8 (T = Co, Mn, Zn)

The effect of the substitution of Co²⁺, Mn²⁺, and Zn²⁺ ions for Ni²⁺ ions on the magnetic, dielectric, and ferroelectric properties of vanadate single crystals (Ni_{1 − x} T _x )₃V₂O₈ has been analyzed. It has been found that the low-level (x ≤ 0.1) substitution of both magnetic and nonmagnetic ions stabilizes the ferroelectric state with a cycloidal magnetic structure. The existence region of this state is expanded to low temperatures down to 3 K for Zn²⁺ and below 1.8 K for Co²⁺ and Mn²⁺ owing to the suppression of a low-temperature weak ferromagnetic phase. At the same time, the ferroelectric phase disappears completely at large concentrations of Co and Mn. The effect of magnetic fields on the magnetic and ferroelectric states has been analyzed. It has been shown that the magnetic field along the c axis suppresses the ferroelectric state, whereas the magnetization along the antiferromagnetism axis (a axis) induces the reentrant phase transition from a paraelectric weak ferromagnetic structure to a ferroelectric structure. The corresponding H-T phase diagrams have been drawn.     

ESR spectra of Eu centers in defect Ga2S3 single crystals

In this paper, the author presents the results of measurements of the low-temperature and angular dependences of the ESR spectra of Eu²⁺ centers in defect Ga₂S₃ single crystals in the temperature range 8–29 K and for 0–180° orientations of the static magnetic field. The electron structure of impurity ¹⁵¹Eu atoms in Ga₂S₃:Eu single crystals has been studied by using the ESR method at different doping proportions of Eu atoms. Ga₂S₃ single crystals were grown from the melt using the Bridgman method. The Eu concentration was determined by atomic absorption analysis and X–ray fluorescence analysis (XRFA). By investigation on the ESR spectra, the author has first determined the values of charge states for Eu, which have turned out to be a Eu²⁺(4f⁷) ion with spin S=7/2, g=4.18±0.02 and concentration of the states of Eu N=6.3×10¹⁴ cm⁻³.     

A superior microwave absorption material: Ni2+-Zr4+ Co-Doped barium ferrite ceramics with large reflection loss and broad bandwidth

Large reflection loss and wide bandwidth are significant targets, determining the microwave absorption ability. However, it is still a challenge to simultaneously satisfy the two conditions. As a multifunctional material, BaFe₁₂O₁₉ possess excellent electromagnetic properties in the microwave frequency band. Due to the natural resonance phenomenon of the material, BaFe₁₂O₁₉ can produce a large magnetic loss which correlates with Fe³⁺ content, and the microwave absorption characteristics of barium ferrite can be modulated by ion doping. As a typical magnetic metal, Ni coupled with high-valence state Zr⁴⁺ doping helps to produce double resonance peaks. In this work, Ni²⁺-Zr⁴⁺ co-doping M-type barium ferrites (BaFe_12-2xNi_xZr_xO₁₉, BNZFO-x, x = 0–0.8) were prepared conveniently by solid-state reaction method. Several necessary measurements to characterize its microwave absorption property have been operated such as morphology, magnetic performance and electromagnetic parameters. The results show that reflection loss and bandwidth can be simply tuned by tailoring Ni²⁺-Zr⁴⁺ content. The reflection loss peak drifts from 18 GHz to 9.76 GHz, which involves a half of the studied frequency range. The maximum reflection loss achieves −60.6 dB and the corresponding bandwidth over −10 dB is 7.68 GHz for BNZFO-0.6 ceramic with only 2.1 mm thickness. Thus, the doping of Ni²⁺-Zr⁴⁺ ion pairs is beneficial to improve the absorbing properties of the material, and the superior microwave absorption property may originate from its inner double natural resonance in micro-scale. The excellent microwave absorption properties suggest that BNZFO-x is a promising candidate applied for designing electromagnetic shielding devices.     

Effect of Nd ion on the magnetic properties of Ni–Mn ferrite nanocrystal

The nanocrystalline Ni_0.7Mn_0.3Nd_0.1Fe_1.9O₄ ferrites were prepared by the emulsion method. X-ray diffractometer (XRD), transmission electron microscope (TEM), Mössbauer spectra and vibrating samples magnetometer (VSM) were used to study the structure, morphology and magnetic properties. The magnetic properties of Nd³⁺-doped Ni_0.7Mn_0.3Fe₂O₄ nanocrystal ferrites were investigated in detail. The Ni_0.7Mn_0.3Nd_0.1Fe_1.9O₄ nanocrystal ferrite with particle size of 10.7 nm shows superparamagnetism.     

Trimers of bivalent copper impurity ions in CaF<Subscript>2</Subscript> crystals: The structure and mechanism of formation

Crystals of CaF₂: Cu (with a copper impurity content higher than 0.1 at. %) grown by the Czochralski method from a melt in a mixed helium-fluorine atmosphere are investigated using electron paramagnetic resonance (EPR) spectroscopy. It is found that the crystals contain paramagnetic centers whose magnetic properties at low temperatures are identical to those of [CuF₄F₄]^6? (S=1/2) single centers. The magnetic properties of the centers exhibit a qualitative change in the temperature range 77–300 K. These changes are described within a model according to which the center is treated as a cluster composed of three [CuF₄F₄]^6? impurity complexes involved in exchange interactions and interactions occurring in the field of Jahn-Teller lattice distortions.     

Comparative first-principle analysis of un-doped and V3+-doped α-ZnAl2S4 spinel

The experimental and theoretical studies of the optical properties of pure α-ZnAl₂S₄ and α-ZnAl₂S₄:V³⁺ crystals were carried out. The ab initio and crystal field calculations of the structural and optical properties of α-ZnAl₂S₄:V³⁺ were compared with the corresponding experimental data. It was shown that the lowest vanadium 3d states are located at about 1.36 eV above the valence band's top. The complete energy level scheme of the α-ZnAl₂S₄:V³⁺ system, which includes the host's electronic band structure and impurity ion's energy levels, was suggested on the basis of the performed calculations.     

Electro-optic properties of LiKSO4 and LiK1-xRbxSO4 crystals

1-x Rb_xSO₄ for x varying between 0 and 0.50 were investigated by an ac modulation method based upon the Sénarmont arrangement. The electro-optic coefficient r_c, and for the first time the coefficients r₄₁ and r₅₁ were determined with good accuracy in pure LiKSO₄ around room temperature at a wavelength of 633 nm. The frequency dependence of the electro-optic coefficient r_c was measured in the frequency range from 1 kHz up to 1 MHz. The values of the factor of merit n_e ³r_c of the mixed crystals LiK_1-xRb_xSO₄ were obtained for the first time, for the concentrations x=0.05, 0.10, 0.20, and 0.50. The electro-optic properties are shown to be affected by the random presence of the rubidium ions in this disordered system. Received: 16 March 1998/Revised version: 2 June 1998