Elevated electrochemical property of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> originated from nano-sized Mn<Subscript>3</Subscript>O<Subscript>4</Subscript>

By employment of nano-sized pre-prepared Mn₃O₄ as precursor, LiMn₂O₄ particles have been successfully prepared by facile solid state method and sol-gel route, respectively. And the reaction mechanism of the used precursors of Mn₃O₄ is studied. The structure, morphology, and element distribution of the as-synthesized LiMn₂O₄ samples are characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). Compared with LiMn₂O₄ synthesized by facile solid state method (SS-LMO), LiMn₂O₄ synthesized by modified sol-gel route (SG-LMO) possesses higher crystallinity, smaller average particle size (~175 nm), higher lithium chemical diffusion coefficient (1.17 × 10^?11 cm² s^?1), as well as superior electrochemical performance. For example, the cell based on SG-LMO can deliver a capacity of 85.5 mAh g^?1 at a high rate of 5 °C, and manifests 88.3% capacity retention after 100 cycles at 0.5 °C when cycling at 45 °C. The good electrochemical performance of the cell based on SG-LMO is ascribed mainly to its small particle size, high degree of dispersion, and uniform element distribution in bulk material. In addition, the lower polarization potential accelerates Li⁺ ion migration, and the lower atom location confused degree maintains integrity of crystal structure, both of which can effectively improve the rate capability and cyclability of SG-LMO.     

Synthesis,sintering, and conductivity of Mn<Subscript>2</Subscript>V<Subscript>2</Subscript>O<Subscript>7</Subscript>

Studies on the sintering of manganese pyrovanadate depending on the temperature and the crystallite size show that we are prevented from obtaining a bulk ceramic sample by the anisotropic growth of grains. Investigation of the electrical properties of Mn₂V₂O₇ in the temperature range of 250–800°C reveals the activation energy at which bulk conductivity is 0.62 eV.     

Magnetic properties of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> surface

The magnetic properties of the magnetite Fe₃O₄(110) surface have been studied by spin resolved Auger electron spectroscopy (SRAES). Experimental spin resolved Auger spectra are presented. The results of calculation of Auger lines polarization carried out on the basis of electronic state density are presented. Problems related to magnetic moments of bivalent (Fe²⁺) and trivalent (Fe³⁺) ions on the Fe₃O₄(110) surface are discussed. It is established that the deposition of a thin bismuth film on the surface results in significant growth of polarization of iron Auger peaks, which is due to additional spin-orbit scattering of electrons by bismuth atoms.     

Electronic structure of α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> in the bulk and on the surface

Using a full-potential method of attaching plane waves, the electronic structure of Al ₂ O ₃ is calculated in a corundum structure in the bulk and on the surface (0001). It is shown that the calculations consistently reproduce the properties with respect to the experiment. The effect of surface relaxation on the structure of subsurface states is discussed. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 20–25, November, 2005.     

One-step synthesis of colloidal Mn<Subscript>3</Subscript>O<Subscript>4</Subscript> and γ-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles at room temperature

A facile room-temperature synthesis has been developed to prepare colloidal Mn₃O₄ and γ-Fe₂O₃ nanoparticles (5 to 25 nm) by an ultrasonic-assisted method in the absence of any additional nucleation and surfactant. The morphology of the as-prepared samples was observed by transmission electron microscopy. High-resolution transmission electron microscopy observations revealed that the as-synthesized nanoparticles were single crystals. The magnetic properties of the samples were investigated with a superconducting quantum interference device magnetometer. The possible formation process has been proposed.     

Structural and magnetic properties of size-controlled Mn<Subscript>0.5</Subscript>Zn<Subscript>0.5</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles and magnetic fluids

Mn_0.5Zn_0.5Fe₂O₄ ferrite nanoparticles with tunable Curie temperature and saturation magnetization are synthesized using hydrothermal co-precipitation method. Particle size is controlled in the range of 54 to 135 Å by pH and incubation time of the reaction. All the particles exhibit super-paramagnetic behaviour at room temperature. Langevin’s theory incorporating the interparticle interaction was used to fit the virgin curve of particle magnetization. The low-temperature magnetization follows Bloch spin wave theory. Curie temperature derived from magnetic thermogravimetric analysis shows that Curie temperature increases with increasing particle size. Using these particles magnetic fluid is synthesized and magnetic characterization is reported. The monolayer coating of surfactant on particle surface is confirmed using thermogravimetric measurement. The same technique can be extended to study the magnetic phase transition. The Curie temperature derived using this measurement complies with the low-temperature magnetic measurement. The room-temperature and high-temperature magnetization measurements are also studied for magnetic fluid systems. The magnetic parameters derived for fluid are in good agreement with those obtained for the particle system.     

Effect of molybdenum on Li<Subscript>2</Subscript>Mn<Subscript>4</Subscript>O<Subscript>9</Subscript> for rechargeable lithium ion batteries

Li₂Mn₄O₉ and molybdenum-doped Li₂Mn₄O₉ have been prepared by simple solid-state method. Molybdenum is used as a dopant since it is resistant to both corrosion and high-temperature creep deformation. The structural, morphological, and electrical performances of the samples have been analyzed. The material exhibits a cubic structure with the fd3m space group. Using EDAX, the chemical compositions of the samples have been identified. The dc electrical conductivity of the Mo-doped (LM2) sample is found to be increased to 7.44?×?10^?6 S cm^?1 at 393 K. The enhanced electrical property of the molybdenum-doped Li₂Mn₄O₉ reveals it as a feasible cathode material for rechargeable Li-ion batteries.     

Influence of (In,Ni, Al,Ga)-ions Substitution on the Magnetic Properties of ZnCr<Subscript>2</Subscript>Se<Subscript>4</Subscript>

Magnetic properties of Zn_1-xM_xCr₂Se₄ (M=In, Ni, Al, Ga) in high magnetic field up to 14 T and at low temperatures are presented. ZnCr₂Se₄ belongs to the group of normal spinels with Zn²⁺ located at tetrahedral (A) sites and Cr³⁺ occupying (B) sites of the cubic close-packed array of selenium anions. Magnetic order in the compounds is connected with superexchange interactions, which are positive between the nearest neighbors and negative between the next-nearest neighbors. Substitution of one of the cations of spinel with another 3d metal causes essential changes in the cation distribution and physical properties.     

Magnetic and dielectric properties of Mn<Subscript>0.2</Subscript>Ni<Subscript>0.8</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles synthesized by PEG-assisted hydrothermal method

We present a systematic investigation on the structural and magnetic properties of Mn_0.2Ni_0.8Fe₂O₄ nanoparticles synthesized by a polyethylene glycol (PEG)-assisted hydrothermal route. XRD, FT-IR, TEM and VSM were used for the structural, morphological, dielectric properties and magnetic investigation of the products, respectively. Average crystallite size of product was estimated using Line profile fitting as 6 ± 1 nm and particle size as 6.5 ± 1.0 nm from TEM micrographs. Magnetization measurements have shown that the particles have a blocking temperature of 134 K. Magnetization and the coercive field of the sample increase by decreasing the temperature. The conductivity measurements reveal the semiconducting behaviour for the sample. Temperature-dependent dielectric properties: dielectric permittivity (ε) and ac conductivity (σ_ac) for the sample were studied as a function of applied frequency in the range from 1 Hz to 3 MHz. These studies indicated that the dielectric dispersion curve for the sample showed usual dielectric dispersion which can be explained on the basis of Koop’s theory, which is based on the Maxwell–Wagner model for the interfacial polarization of homogeneous double structure.     

Enhanced electrochemical properties and thermal stability of LiNi<Subscript>1/3</Subscript>Co<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> by surface modification with Eu<Subscript>2</Subscript>O<Subscript>3</Subscript>

Layered LiNi_1/3Co_1/3Mn_1/3O₂ cathode material is synthesized via a sol-gel method and subsequently surface-modified with Eu₂O₃ layer by a wet chemical process. The effect of Eu₂O₃ coating on the electrochemical performances and thermal stability of LiNi_1/3Co_1/3Mn_1/3O₂@Eu₂O₃ cells is investigated systematically by the charge/discharge testing, cyclic voltammograms, AC impedance spectroscopy, and DSC measurements, respectively. In comparison, the Eu₂O₃-coated sample demonstrates better electrochemical performances and thermal stability than that of the pristine one. After 100 cycles at 1C, the Eu₂O₃-coated LiNi_1/3Co_1/3Mn_1/3O₂ cathode demonstrates stable cyclability with capacity retention of 92.9 %, which is higher than that (75.5 %) of the pristine one in voltage range 3.0–4.6 V. Analysis from the electrochemical measurements reveals that the remarkably improved performances of the surface-modified composites are mainly ascribed to the presence of Eu₂O₃-coating layer, which could efficiently suppress the undesirable side reaction and increasing impedance, and enhance the structural stability of active material.     

Effects of lithium excess amount on the microstructure and electrochemical properties of LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> cathode material

Spinel LiNi_0.5Mn_1.5O₄ cathode materials with different lithium excess amount (0, 2%, 6%, 10%) were synthesized by a facile solid-state method. The effect of lithium excess amount on the microstructure, morphology, and electrochemical properties of LiNi_0.5Mn_1.5O₄ materials was systematically investigated. The results show that the lithium excess amount does not change the particle morphology and size obviously; thus, the electrochemical properties of LiNi_0.5Mn_1.5O₄ are mainly determined by structural characteristics. With the increase of lithium excess amount, the cation disordering degree (Mn³⁺ content) and phase purity first increase and then decrease, while the cation mixing extent has the opposite trend. Among them, the LiNi_0.5Mn_1.5O₄ material with 6% lithium excess amount exhibits higher disordering degree and lower impurity content and cation mixing extent, thus leading to the optimum electrochemical properties, with discharge capacities of 125.0, 126.1, 124.2, and 118.9 mAh/g at 0.2-, 1-, 5-, and 10-C rates and capacity retention rate of 96.49% after 100 cycles at 1-C rate.     

Spin-wave resonances in Eu<Subscript>0.8</Subscript>Ce<Subscript>0.2</Subscript>Mn<Subscript>2</Subscript>O<Subscript>5</Subscript> and EuMn<Subscript>2</Subscript>O<Subscript>5</Subscript> multiferroics

Spin-wave resonances have been observed in superlattices arising due to the phase separation and self-organization of charge carriers in Eu_0.8Ce_0.2Mn₂O₅ single crystals. The resonances are found within the 5–80 K temperature range at frequencies close to 30 GHz. Similar resonances with intensities about an order of magnitude lower are also observed in EuMn₂O₅. The latter suggests the existence of charge transfer processes between the manganese ions of different valences in EuMn₂O₅.     

Study of the formation and stability of the NdSr<Subscript>2</Subscript>Mn<Subscript>2</Subscript>O<Subscript>7</Subscript> phase

The sequence of phase equilibria during synthesis of the NdSr₂Mn₂O₇ phase is determined. The stability of this phase with changes in temperature and partial oxygen pressure is investigated.     

Synthesis and electrochemical properties of P2-Na<Subscript>2/3</Subscript>Ni<Subscript>1/3</Subscript>Mn<Subscript>2/3</Subscript>O<Subscript>2</Subscript>

The pure phase P2-Na_2/3Ni_1/3Mn_2/3O₂ was synthesized by a solid reaction process. The optimum calcination temperature was 850 °C. The as-prepared product delivered a capacity of 158 mAh g^?1 in the voltage range of 2–4.5 V, and there was a phase transition from P2 to O2 at about 4.2 V in the charge process. The P2 phase exhibited excellent intercalation behavior of Na ions. The reversible capacity is about 88.5 mAh g^?1 at 0.1 C in the voltage range of 2–4 V at room temperature. At an elevated temperature of 55 °C, it could remain as an excellent capacity retention at low current rates. The P2-Na_2/3Ni_1/3Mn_2/3O₂ is a potential cathode material for sodium-ion batteries.     

Magnetoresistive effect in RCu<Subscript>3</Subscript>Mn<Subscript>4</Subscript>O<Subscript>12</Subscript> perovskite-like oxides

The electrical properties of and the magnetoresistive effect in RCu₃Mn₄O₁₂ (R=rare-earth ion or Th) are studied. In all compounds of this series, the magnetoresistive effect amounts to 20% at liquid nitrogen temperature in the presence of a field of 0.9 T. An increase in the magnetoresistance with decreasing temperature and a high sensitivity to weak magnetic fields at low temperatures point to the intergranular nature of the effect. The magnetoresistance shows a peak in the vicinity of the Curie temperature T_C. Based on the dependences of the magnetoresistance on an external magnetic field, it is assumed that the magnetoresistance peak near T_C is related to the charge carrier scattering by magnetic inhomogeneities as in substituted orthomanganites. We believe that the magnetoresistance value near the magnetic ordering temperature depends on the synthesis conditions and the effect of the intergranular spacer on the transport properties of these compounds.     

Research of the Spin-Hamiltonian Parameters and Defect Structure for the Trigonal Mn<Superscript>4+</Superscript> Centers in Y<Subscript>2</Subscript>Ti<Subscript>2</Subscript>O<Subscript>7</Subscript>:Mn<Superscript>4+</Superscript> Crystal

The high-order perturbation formulas founded on the two-mechanism model are applied in this paper to compute the spin-Hamiltonian parameters (g factors g _//, g _⊥ and zero-field splitting D) of the trigonal Mn⁴⁺ centers in Y₂Ti₂O₇:Mn⁴⁺ crystal. In this model, besides the contributions from the traditional crystal-field (CF) mechanism (in the CF theory) related to CF excited states, those from the charge-transfer (CT) mechanism connected with CT excited states are contained. The calculated results are reasonably coincident with the observed values. The calculations show that the contributions of CT mechanism to spin-Hamiltonian parameters (in particular, the g factors) for (MnO₆)^8? clusters are large and cannot be neglected. The defect structure of trigonal (MnO₆)^8? clusters in Y₂Ti₂O₇:Mn⁴⁺ crystals is also evaluated. The results are discussed.     

CeO<Subscript>2</Subscript> coating to improve the performance of Li[Li<Subscript>0.2</Subscript>Mn<Subscript>0.54</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>]O<Subscript>2</Subscript>

The Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ coated with CeO₂ has been fabricated by an ionic interfusion method. Both the bare and the CeO₂-coated samples have a typical layered structure with R-3m and C2/m space group. The results of XRD and TEM images display that the CeO₂ coating layer on the precursor could enhance the growth of electrochemically active surface planes ((010), (110), and (100) planes) in the following ionic interfusion process. The results of galvanostatic cycling tests demonstrate that the CeO₂-coated sample has a discharge capacity of 261.81 mAh g^?1 with an increased initial Coulombic efficiency from 62.4 to 69.1% at 0.05 °C compared with that of bare sample and delivers an improved capacity retention from 71.7 to 83.4% after 100 cycles at 1 °C (1 °C?=?250 mA g^?1). The results of electrochemical performances confirm that the surface modification sample exhibits less capacity fading, lower voltage decay, and less polarization.     

Simulation of the magnetic properties of manganese oxide Pb<Subscript>3</Subscript>Mn<Subscript>7</Subscript>O<Subscript>15</Subscript>

The magnetic susceptibility, heat capacity, and spin-spin correlation functions of manganese oxide Pb₃Mn₇O₁₅ are calculated by the Monte Carlo method. Two critical temperatures are determined: T ₁ ≈ 20 K, above which a modulated structure along the hexagonal axis is formed, and T ₂ ≈ 70 K, at which the long-range magnetic order disappears. The antiferromagnetic exchange interaction constant in a hexagonal plane is estimated to be J ₁ ～ 7 K, and the antiferromagnetic and ferromagnetic exchange interaction constants between hexagonal planes are calculated to be J ₂ ～ 3 K and K ～ 50 K, respectively.     

Dependence of electronic structure on the grain size in Mn<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocrystals

. The dependence of electron structure on the grain size in Mn₂O₃ nanocrystals has been investigated using X-ray photoelectron spectroscopy. It is found that the electron structure is sensitively dependent on the average grain size. The experimental results indicate that the O–1s core-level spectra are hardly shifted with decreasing average grain size; however, for a sample with a small grain size (e.g. a 9-nm sample), the shoulder peak evidently appears on the higher-binding-energy side. The main peak width of the Mn–2p core-level spectra becomes wide for samples with decreasing average grain size. The remarkable aspect of the Mn–3s core-level spectra is that the peak is multiply split, with a complex peak structure. The exchange interaction of the 3s and 3d electrons in the Mn³⁺ ion can be used to explain this behavior. PACS 71.23.-k; 73.22.-f     

Investigation on the electrochemical performances of Li<Subscript>4</Subscript>Mn<Subscript>5</Subscript>O<Subscript>12</Subscript> for battery applications

In this study, well-crystallized Li₄Mn₅O₁₂ powder was synthesized by a self-propagating combustion method using citric acid as a reducing agent. Various conditions were studied in order to find the optimal conditions for the synthesis of pure Li₄Mn₅O₁₂. The precursor obtained was then annealed at different temperatures for 24 h in a furnace. X-ray diffraction results showed that Li₄Mn₅O₁₂ crystallite is stable at relatively low temperature of 400 °C but decompose to spinel LiMn₂O₄ and monoclinic Li₂MnO₃ at temperatures higher than 500 °C. The prepared samples were also characterized by FESEM and charge-discharge tests. The result showed that the specific capacity of 70.7 mAh/g was obtained within potential range of 4.2 to 2.5 V at constant current of 1.0 mA. The electrochemical performances of Li₄Mn₅O₁₂ material was further discussed in this paper.