Magnetic phase transition of Li0.75CoO2 compared with LiCoO2 and Li0.5CoO2

Magnetic and thermodynamic properties of the LiCoO₂ positive-electrode material used in lithium-ion battery were first examined. Partially deintercalated LiCoO₂ that is Li_0.75CoO₂, showed definite anomaly in the magnetic susceptibility at T=ca. 175 K probably related to magnetic phase transition which was supported by observation of a weak anomaly in heat capacity. On the other hand, LiCoO₂ did not show such magnetic phase transition as expected, whereas Li_0.5CoO₂ a weak one in the similar temperature range. These behaviors are discussed in association with the mixing of Co³⁺ and Co⁴⁺ electronic structures.     

Properties of the perovskites, SrMn1−xFexO3−δ (x=1/3, 1/2, 2/3)

The SrMn_1−xFe_xO_3−δ (x=1/3, 1/2, 2/3) phases have been prepared and are shown by powder X-ray and neutron (for x=1/2) diffraction to adopt an ideal cubic perovskite structure with a disordered distribution of transition-metal cations over the six-coordinate B-site. Due to synthesis in air, the phases are oxygen deficient and formally contain both Fe³⁺ and Fe⁴⁺. Magnetic susceptibility data show an antiferromagnetic transition at 180 and 140 K for x=1/3 and 1/2, respectively and a spin-glass transition at 5, 25, 45 K for x=1/3, 1/2 and 2/3, respectively. The magnetic properties are explained in terms of super-exchange interactions between Mn⁴⁺, Fe^(4+δ)+ and Fe⁽³⁺⁾⁺. The XAS results for the Mn-sites in these compounds indicate small Mn-valence changes, however, the Mn-pre-edge spectra indicate increased localization of the Mn-e_g orbitals with Fe substitution. The Mössbauer results show the distinct two-site Fe⁽³⁺⁾+/Fe^(4+δ)+ disproportionation in the Mn- substituted materials with strong covalency effects at both sites. This disproportionation is a very concrete reflection of a localization of the Fe-d states due to the Mn-substitution.     

Low temperature thermodynamic properties of Gd<Subscript>2</Subscript>SrCo<Subscript>2</Subscript>O<Subscript>7</Subscript>

Summary Thermodynamic properties of a layered perovskite oxide Gd₂SrCo₂O₇ have been studied. Powder X-ray diffraction, electric resistivity, magnetic susceptibility and heat capacity measurements were carried out. The crystal structure was determined as I4/mmm. The temperature dependence of the magnetic susceptibility was fitted to the Curie-Weiss behavior with antiferromagnetic interaction. Spin state of Co³⁺ ion was derived to be intermediate spin state configuration (t_2g⁵e_g¹). The spin ordering was observed as a broad anomaly in the heat capacity curve with a peak at 2 K. The measured entropy was 35.47 J K^-1mol^-1, which was 65% of expected value. Thus the spin ordering should not be completed at the lowest temperature 0.2 K covered in the present experiments and/or some short range ordering remains at higher temperatures.     

Structural and magnetic properties of the quaternary oxides Ba6Ln2Fe4O15 (Ln=Pr and Nd)

The crystal structures and magnetic properties of the quaternary lanthanide oxides Ba₆Ln₂Fe₄O₁₅ (Ln=Pr and Nd) are reported. They crystallize in a hexagonal structure with space group P6₃mc and have the “Fe₄O₁₅ cluster” consisting of one FeO₆ octahedron and three FeO₄ tetrahedra. Measurements of the magnetic susceptibility, specific heat, and powder neutron diffraction reveal that this cluster behaves as a spin tetramer with a ferrimagnetic ground state of S_T=5 even at room temperature. The cluster moments show a long-range antiferromagnetic ordering at 23.2 K (Ln=Pr) and 17.8 K (Nd), and the magnetic moments of the Ln³⁺ ions also order cooperatively. By applying the magnetic field (∼2 T), this antiferromagnetic ordering of the clusters changes to a ferromagnetic one. This result indicates that there exists a competition in the magnetic interaction between the clusters.     

Anomalies in Heat Capacity Measurements of RuO2-TiO2 System

DSC was used for heat capacity measurements of pure RuO₂ in the temperature range from 300 to 1170 K of solid solutions corresponding to the compositions of (Ti_1−x Ru_x )O₂ (x ≤0.15 and x ≥0.85) and in the temperature range from 300 to 1550 K of pure TiO2. The analysis of experimental data obtained within ±2% of accuracy has shown that the characteristic temperatures representing the harmonic lattice vibrations do not strongly depend on the chemical composition x . It was demonstrated that non-harmonic heat capacity is strongly correlated to x. The existence of additional excess heat capacity was observed with the mixed oxide solid solution samples of low Ru content and explained by the defect formation model. This revised version was published online in August 2006 with corrections to the Cover Date.     

正极材料Li_(0.99)Nb_(0.01)Fe_(1-x)Mg_xPO_4/C的制备及电化学性能的研究

采用两步固相反应合成了锂、铁双位掺杂的锂离子电池正极材料Li0.99Nb0.01Fe1-xMgxPO4/C(x=0,0.01,0.02,0.03,0.04)。通过X射线衍射(XRD)、扫描电镜(SEM)以及恒电流充放电测试,研究了复合材料的晶体结构、形貌以及电化学性能。实验结果表明,制备的Li0.99Nb0.01Fe1-xMgxPO4/C(x=0,0.01,0.02,0.03,0.04)为纯相,掺杂适量的Nb5+、Mg2+离子可减小材料的晶粒尺寸,当Nb离子掺杂量为1mol%、Mg离子掺杂量为3mol%时,Li0.99Nb0.01Fe0.97Mg0.03PO4/C的电化学性能最佳。室温下,0.2C、1C、2C、4C(1C=170mA·g-1)倍率充放电其首次放电比容量分别为153.7、149.7、144.6、126.4mAh·g-1,即使在8C倍率下放电其放电比容量也有92.2mAh·g-1,并表现出良好的循环性能。     

Heat capacity of iron-chromium spinels,Fe3−xCrxO4

The heat capacity of Fe_3?xCr_xO₄ with the composition x = 0.6, 0.8, and 1.0 was measured from 200 to 850 K. A γ-type heat capacity anomaly due to the ferri-paramagnetic transition was observed for all compositions. The transition temperatures were 652, 563, and 451 K for the compositions x = 0.6, 0.8, and 1.0, respectively. The variation of transition temperature with composition is discussed in terms of cation distribution. The magnetic contribution to the observed heat capacity was obtained by assuming that the heat capacity is expressed by the sum of the lattice heat capacity C_v(1), the dilation contribution d(d), and the magnetic contribution C(m). Entropy changes due to the transition were calculated from C(m) as 52.6, 49.7, and 46.3 J K^?1 mole^?1 for the compositions x = 0.6, 0.8, and 1.0, respectively, which are from 7 to 12 J K^?1 mole^?1 higher than the calculated values based on the assumption of randomization of unpaired spins on each ion. The difference between the observed and the calculated values is roughly explained by taking into account the orbital contribution of Fe²⁺ ions on octahedral and tetrahedral sites.     

Synthesis and Properties of The Solid Solutions Formed in The Fe2V4O13–Cr2V4O13 System

DTA and XRD studies of the Fe₂V₄O₁₃–Cr₂V₄ O₁₃ system have shown that continuous solid solutions of a Fe_2–xCr_xV₄O₁₃ type, bearing a Fe₂ V₄ O₁₃ structure, are formed in the system. With the increasing degree of the Cr3+ ion incorporation into the Fe₂ V₄ O₁₃ structure, a contraction of the solid solution crystal lattice develops. Solid solutions of a Fe_2–x Cr_x V₄ O₁₃ type melt incongruently, their melting temperature increasing from 953 to 1003 K with increase in the degree of the Cr³⁺ ion incorporation. The solid product of melting Fe_2–x Cr_x V₄ O₁₃ solid solutions for 0.2<x >1.2 is the Fe_1–x Cr_x VO₄ solution phase, and for x ≤0.2 and x ≥1.4 – the Fe_1–x Cr_x VO₄ phase as well as FeVO₄ or CrVO₄ , respectively. This revised version was published online in July 2006 with corrections to the Cover Date.     

Formation and properties of the Fe<Subscript>8</Subscript>V<Subscript>10</Subscript>W<Subscript>16–x</Subscript>Mo<Subscript>x</Subscript>O<Subscript>85</Subscript> type solid solution

Solid solution phases of a formula Fe₈V₁₀W_16–xMo_xO₈₅ where 0≤x≤4, have been obtained, possessing a structure of the compound Fe₈V₁₀W₁₆O₈₅. It was found on the base of XRD and DTA investigations that these solution phases melted incongruently, with increasing the value of x, in the temperature range from 1108 (x=0) to 1083 K (x=4) depositing Fe₂WO₆ and WO₃. The increase of the Mo⁶⁺ ions content in the crystal lattice of Fe₈V₁₀W₁₆O₈₅ causes the lattice parameters a=b contraction with cbeing almost constant. IR spectra of the Fe₈V₁₀W_16–xMo_xO₈₅ solid solution phases have been recorded.     

Thermal behavior of ternary Sm2Fe17Nx magnets

The Mössbauer spectra of Sm₂Fe₁₇N_x, prepared by the nitrogenation of Sm₂Fe₁₇ powders in an ammonia and hydrogen atmosphere, were observed at elevated temperatures to shed light on the thermal behavior of nitrogen in the compounds Sm₂Fe₁₇N_x. It was found that there were large differences in thermal behavior between the starting Sm₂Fe₁₇, crystalline Sm₂Fe₁₇N_x (x≈1.7) and amorphous Sm₂Fe₁₇N_x(x～7). The thermal decomposition behavior of Sm₂Fe₁₇N_3.2, developed as one of the most promising hard magnetic materials, was found to be different under different atmospheres.     

Structure and Magnetism of Pr1−xSrxFeO3−δ

Crystal structure, redox, and magnetic properties for the Pr_1−xSr_xFeO_3−δ solid-solution phase have been studied. Oxidized samples (prepared in air at 900°C) crystallize in the GdFeO₃-type structure for 0≤x≤0.80, and probably in the Sr₈Fe₈O₂₃-type (unpublished) structure for x=0.90. Reduced samples (containing virtually only Fe³⁺) crystallize as the perovskite aristotype for x=0.50 and 0.67 with randomly distributed vacancies. The Fe⁴⁺ content increases linearly in the oxidized samples up to x≈0.70, whereupon it stabilizes at around 55%. Antiferromagnetic ordering of the G type is observed for oxidized samples (0≤x≤0.90) which show decreasing Néel temperature and ordered magnetic moment with increasing x, while the Néel temperature is nearly constant at 700 K for reduced samples. Electronic transitions for iron from an average-valence state via charge-separated to disproportionated states are proposed from anomalies in magnetic susceptibility curves in the temperature ranges 500–600 K and 150–185 K.     

Excess Heat Capacity in Yttria Stabilized Zirconia

The heat capacity of 9.70 and 11.35 mol% yttria stabilized zirconia ((ZrO₂)_1–x(Y₂O₃)_x; x=0.0970, 0.1135) was measured by adiabatic calorimetry between 13 and 300 K, and some thermodynamic functions were calculated and given in a table. A large excess heat capacity extending from the lowest temperature to room temperature with a broad maximum at about 75 K was found in comparison with the heat capacity calculated from those of pure zirconia and yttria on the basis of simple additivity rule. The shape of the excess heat capacity is very similar to the Schottky anomaly, which may be attributed to a softening of lattice vibration. The amount of the excess heat capacity decreased with increasing yttria doping, while the maximum temperature did not vary. The relationships among the excess heat capacity, defect structure and interatomic force constants, and also the role of oxygen vacancy were discussed.This revised version was published online in November 2005 with corrections to the Cover Date.     

Long-range antiferromagnetic ordering in Cu2NiB2O6

Magnetic properties of peculiar structural-type borate Cu₂NiB₂O₆ are investigated by means of ac susceptibility, dc magnetization, and heat capacity measurements. This material is isostructural to Cu₂CoB₂O₆, of which the structural configuration is composed of quasi-one-dimensional six-columns ribbons. Our experimental results show that this material displays an antiferromagnetic phase transition at ∼15 K, which differs from Cu₂CoB₂O₆ showing spin-glass behavior below 5 K. The different magnetic ground states in these compounds may be attributed mainly to the subtle balance of the exchange energy in the scalene triangles.     

Magnetische Eigenschaften der ternären Phase (Fe x Ni1-x )11Se8

The partial substitution of nickel by iron in the body centered tetragonal crystal structure of the ternary compound (Fe _x Ni_1–x )₁₁Se₈ is restricted to the range of 0.04<x<0.23 at 580°C. The magnetic properties of samples with different compositions were studied by susceptibility measurements in the temperature region from 100 to 300 K. The continuous addition of Fe atoms resulted in a decreasing temperature dependence of the magnetic susceptibilities. Only for compositions withx0.14 an approximatedCurie—Weiss behaviour was observed. The Fe-rich samples (x>0.14) showed a very high constant paramagnetism which could not be interpreted asPauli paramagnetism. The evaluation of magnetic moments was based on the assumption that only the Fe atoms contribute to the temperature dependence of the magnetic susceptibilities. The actual value of the magnetic moments is supposed to be affected by magnetic interactions between neighbouring Fe atoms. The extrapolation of the magnetic moments towardsx=0 is compatible with a magnetic moment of 3.87 _B corresponding to three unpaired d-electrons per Fe atom. According to the negativeWeiss constants derived fromCurie—Weiss law antiferromagnetic interactions at low temperatures can be expected.

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Mit 3 Abbildungen     

Coexistence of 3d‐Ferromagnetism and Superconductivity in [(Li1−xFex)OH](Fe1−yLiy)Se

Superconducting [(Li_1?xFe_x)OH](Fe_1?yLi_y)Se (x≈0.2, y≈0.08) was synthesized by hydrothermal methods and characterized by single‐crystal and powder X‐ray diffraction. The structure contains alternating layers of anti‐PbO type (Fe_1?yLi_y)Se and (Li_1?xFe_x)OH. Electrical resistivity and magnetic susceptibility measurements reveal superconductivity at 43 K. An anomaly in the diamagnetic shielding indicates ferromagnetic ordering near 10 K while superconductivity is retained. The ferromagnetism is from the iron atoms in the (Li_1?xFe_x)OH layer. Isothermal magnetization measurements confirm the superposition of ferromagnetic and superconducting hysteresis. The internal ferromagnetic field is larger than the lower, but smaller than the upper critical field of the superconductor. The formation of a spontaneous vortex phase where both orders coexist is supported by ⁵⁷Fe‐Mössbauer spectra, ⁷Li‐NMR spectra, and μSR experiments.     

Low-temperature heat capacities and thermodynamic properties of rare-earth triisothiocyanate hydrates (III) —Sm(NCS)3 · 6H2O, Gd(NCS)3 · 6H20, Yb(NCS)3 · 6H20 and Y(NCS)3 · 6H20

The heat capacities of four RE isothiocyanate hydrates, Sm(NCS)₃, · 6H₂0, Gd(NCS)₃ · 6H₂0, Yb(NCS)₃, · 6H₂O and Y(NCS)₃, · 6H₂0, have been measured from 13 to 300 K with a fully-automated adiabatic calorimeter. No obvious thermal anomaly was observed for the above-mentioned compounds in the experimental temperature ranges. The polynomial equations for calculating the heat capacities of the four compounds in the range of 13–300 K were obtained by the least-squares fitting based on the experimentalC _P, data. TheC _P, values below 13 K were estimated by using the Debye-Einstein heat capacity functions. The standard molar thermodynamic functions were calculated from 0 to 300 K. Gibbs energies of formation were also calculated. Project supported by the National Natural Science Foundation of China.     

Magnetic properties of FexV3−xS4 (0 ≤ x ≤ 2)

The magnetic susceptibility data of Fe_xV_3?xS₄ (0 ≤ x ≤ 2) are reported in the temperature range between 4.2 and 1300 K. The behavior of the susceptibility at high temperatures changes significantly at the composition boundary x = 1.0. The magnitude of the effective magnetic moment remains unchanged at 3.2 μ_B in the composition range x < 1.0. It decreases with increasing iron content in the range > 1.0, and rapidly decreases for x close to 2.0. The c lattice parameter varies in a manner analogous to the change in magnetic moment. These phenomena suggest that metallic bonding forms between metal layers and that it becomes stronger with increasing in x. The susceptibility measurements at low temperatures show that Fe_xV_3?xS₄ is basically antiferromagnetic, although some of the Fe_xV_3?xS₄ compounds become weakly ferromagnetic after cooling in a magnetic field. The origin of the weak ferromagnetism is briefly discussed.     

Crystal structure and magnetic properties of high-oxygen pressure annealed Sr1−xLaxCo0.5Fe0.5O3−δ (0?x?0.5)

Structural and magnetic studies are presented for the perovskite type Sr_1−xLa_xCo_0.5Fe_0.5O_3−δ (0?x?0.5) materials annealed under moderately high-oxygen pressures of ∼200 atm. A detailed analysis of the room temperature neutron time-of-flight diffraction data reveals that the crystal structure of the sample SrCo_0.5Fe_0.5O_2.89(1), previously described as vacancy-disordered cubic, is similar to the formerly reported, oxygen-vacancy ordered Sr₈Fe₈O₂₃ compound, i.e. Sr₈Co₄Fe₄O₂₃ is tetragonal with the I4/mmm symmetry. With an increase of the La content the studied materials become nearly oxygen stoichiometric and a lowering of the crystal symmetry is observed from cubic (x=0.1 and 0.2) to tetragonal I4/mcm (x=0.3 and 0.4), and finally to monoclinic I12/c1 (x=0.5). Low-temperature structural and magnetic measurements show a ferromagnetic ordering with the maximum Curie temperature near 290 K at x=0.2.     

Untersuchungen an Hydriden im Bereich der Phase Ti2CO1—x Fe x (x=0–0,5)

The hydrogen absorption of the phase Ti₆₄Co_32–x Fe _x (x=0...16) and its influence on the magnetic properties have been investigated. Measurements of the vapour-pressure, wide-line NMR and magnetic susceptibility have been performed. Substitution of Co by Fe does not change the amount of absorbed hydrogen. However the reaction rate of hydriding process, the activation energy of diffusion and the magnetic quantities change upon this substitution.

     

Magnetic properties of barium uranate Ba2U2O7

Unique magnetic properties of a ternary uranate Ba₂U₂O₇ are reported. Magnetic susceptibility measurements reveal that this compound undergoes a magnetic transition at 19 K. Below this temperature, magnetic hysteresis was observed. The results of the low-temperature specific heat measurements below 30 K support the existence of the second-order magnetic transition at 19 K. Ba₂U₂O₇ undergoes a canted antiferromagnetic ordering at this temperature. The magnetic anomaly which sets in at 58 K may be due to the onset of one-dimensional magnetic correlations associated with the linear chains formed by U ions. The analysis of the experimental magnetic susceptibility data in the paramagnetic temperature region gives the effective magnetic moment μ_eff=0.73 μ_B, the Weiss constant θ=−10 K, and the temperature-independent paramagnetic susceptibility χ_TIP=0.14×10⁻³ emu/mole.The magnetic susceptibility results and the optical absorption spectrum were analyzed on the basis of an octahedral crystal field model. The energy levels of Ba₂U₂O₇ and the crystal field parameters were determined.