Transport and magnetic properties of disordered LixVyO2 (x=0.8 and y=0.8)

The magnetic and electron transport properties of rhombohedral Li_xV_yO₂ (x=0.8 and y=0.8) are studied. The dc susceptibility of Li_xV_yO₂ can be well fitted to the modified Curie-Weiss law, which verified the paramagnetic ground state. The magnetic hysteresis and ac susceptibility also confirm this paramagnetism. The Li_xV_yO₂ exhibits semiconducting behavior, which is explained by thermal activated process at high temperature and variable-range hopping mechanism at low temperature. Anderson localization plays an important role in both the electron transport behavior and the magnetic behavior due to the site disorder between the Li⁺ ion and V⁴⁺ ion.     

Thermodynamic study of lithium insertion in V6O13 and Li1+xV3O8

The enthalpies of Li⁺ insertion into two V oxides of interest as cathodes for secondary Li batteries, i.e. V₆O₁₃ and Li_1+xV₃O₈ have been directly measured by solution calorimetry. By comparing the integral molar enthalpies ΔH⁰/x with the corresponding ΔG⁰/x values, ΔS⁰/x higher than expected have been found for Li_1+xV₃O₈. This has been correlated to a reorganization of its distorted structure induced by the initial Li⁺ insertion. Two other cathode materials, having the same variation of the potential with Li⁺ content, i.e. MoO₃ and (Mo_0.3V_0.7)₂O₅, show even higher ΔS⁰/x values. The entropic values stemming from structural reorganizations add to the configurational entropies of inserted ions in determining the initial profile of E as a function of Li⁺.     

Electrochemical behavior of Li intercalation processes into a Li[NixLi(1/3−2x/3)Mn(2/3−x/3)]O2 cathode

Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ (X=0.17, 0.25, 0.33, 0.5) compounds are prepared by a simple combustion method. The Rietvelt analysis shows that these compounds could be classified as having the α-NaFeO₂ structure. The initial charge-discharge and irreversible capacity increases with the decrease of x in Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂. Indeed, Li[Ni_0.50Mn_0.50]O₂ compound shows relatively low initial discharge capacity of 200 mAh/g and large capacity loss during cycling, with Li[Ni_0.17Li_0.22Mn_0.61]O₂ and Li[Ni_0.25Li_0.17Mn₀.₅₈]O₂ compounds exhibit high initial discharge capacity over 245 mAh/g and stable cycle performance in the voltage range of 4.8 -2.0 V. On the other hand, XANES analysis shows that the oxidation state of Ni ion reversibly changes between Ni²⁺ and about Ni³⁺, while the oxidation state of Mn ion sustains Mn⁴⁺ during charge-discharge process. This result does not agree with the previously reported ‘electrochemistry model’ of Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂, in which Ni ion changes between Ni²⁺ and NI⁴⁺. Based on these results, we modified oxidation-state change of Mn and Ni ion during charge-discharge process.     

Synthesis and electrochemical performances of Li4Ti4.95Al0.05O12/C as anode material for lithium-ion batteries

Spinel compounds Li₄Ti_5−xAl_xO₁₂/C (x=0, 0.05) were synthesized via solid state reaction in an Ar atmosphere, and the electrochemical properties were investigated by means of electronic conductivity, cyclic voltammetry, and charge-discharge tests at different discharge voltage ranges (0-2.5 V and 1-2.5 V). The results indicated that Al³⁺ doping of the compound did not affect the spinel structure but considerably improved the initial capacity and cycling performance, implying the spinel structure of Li₄Ti₅O₁₂ was more stable when Ti⁴⁺ was substituted by Al³⁺, and Al³⁺ doping was beneficial to the reversible intercalation and deintercalation of Li⁺. Al³⁺ doping improved the reversible capacity and cycling performance effectively especially when it was discharged to 0 V.     

Preparation and optical properties of Ce activated (Ca1 − x,Srx)Al2Si2O8 phosphors

(Ca_1 − x, Sr_x)Al₂Si₂O₈:0.06Ce³⁺, M⁺ (M⁺ = Li⁺, Na⁺, K⁺) phosphors have been prepared by conventional solid-state reaction method. The structural and optical properties of the phosphors were characterized by X-ray diffraction (XRD) technique and spectrophotometer, respectively. A regular variation was found among the XRD patterns of (Ca_1 − x, Sr_x)Al₂Si₂O₈:0.06Ce³⁺ phosphors based on the changing of Sr content. With the increase of Sr content, the maximum of emission band presented slight blue shifts (~ 15 nm). The luminescence intensity of CaAl₂Si₂O₈:0.06Ce³⁺ and SrAl₂Si₂O₈:0.06Ce³⁺ were significantly enhanced when K⁺ and Li⁺ were incorporated, respectively.     

Transport and equilibrium characteristics of γ-lithium vanadium bronze

The diffusion coefficient of Li⁺ in the γ-lithium vanadium bronze (Li_1+xV₃O₈) has been measured with the long-pulse galvanostatic technique. Values ranging from 1.7×10⁻⁷ cm²s⁻¹, at x=0.3, to 2.2×10⁻⁸ cm²s⁻¹, at x= 1.4, have been measured. The thermodynamic factors, d ln a/d ln c, determined from the OCV/x curve and from voltage relaxation after the current pulse, have a mean value of ∼15. The pseudo two-phase region observed in the OCV/x curve at high Li⁺ concentrations seems attributable to ordering of Li⁺ in specific sites and to alteration of the unit cell. This process is reversible as shown by X-ray diffractometry. Finally, from OCV/t plots at different x, the partial molar entropy of Li⁺ was determined. The values, on account of the large dE(x)/dt measured, are higher than those found for V₆O₁₃ or TiS₂.     

NMR study of Li+-ion diffusion in the solid solution Li3+x(P1−x,Six)O4> with the γII-Li3PO4 structure

Diffusive motion of a Li⁺ ion in the solid solution of Li₃+x(P₁?x, Si_x)O₄ (0?x?0.4) with the γ_II-Li₃PO₄ structure was studied by the measurement of the ⁷Li spin-lattice relaxation time. The observed motion was a local motion instead of a long-range one. In comparison with the previous study on the solid solution of Li₄?x(P_x, Si₁?x)O₄ with the Li₄SiO₄ structure, it is noticeable that the activation energy is low and almost independent of the composition and that the attempt frequency is smaller in this phase. These characteristics were attributed to the availability of a large interstitial void in the γ_II-Li₃PO₄ structure. The low values of activation energy for the Li⁺ ionic conduction may be explained on the same basis.     

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.     

Molten salt synthesis of Li1 + x (Ni0.5Mn0.5)1 − xO2 as cathode material for Li-ion batteries

Li_1 + x(Ni_0.5Mn_0.5)_1 − xO₂ cathode material for Li-ion batteries has been prepared by a molten salt method using Li₂CO₃ salt. The influences of synthetic temperature and time have been intensively investigated. It is easy to obtain materials with a hexagonal α-NaFeO₂ structure except broad peaks between 20° and 25°. Nickel in Li_1 + x(Ni_0.5Mn_0.5)_1 − xO₂ is oxidized to a trivalent state while manganese maintained a tetravalent state. It is found that the discharge capacities of all samples increase with cycling. The sample prepared at 850 °C for 5 h has a discharge capacity of 130 mAh g^− 1 between 2.5 and 4.5 V versus V_Li+/Li at a specific current of 0.13 mA cm^− 2 after 50 cycles at 25 °C.     

Enhanced luminescence from spontaneously ordered Gd2O3:Eu based nanostructures

Nanostructured Gd₂O₃:Eu³⁺ and Li⁺ doped Gd₂O₃:Eu³⁺ thin films were prepared by pulsed laser ablation technique. The effects of annealing and Li⁺ doping on the structural, morphological, optical and luminescent properties are discussed. X-ray diffraction and Micro-Raman investigations indicate a phase transformation from amorphous to nanocrystalline phase and an early crystallization was observed in Li⁺ doped Gd₂O₃:Eu³⁺ thin films on annealing. AFM images of Li⁺ doped Gd₂O₃:Eu³⁺ films annealed at different temperatures especially at 973 K show a spontaneous ordering of the nanocrystals distributed uniformly all over the surface, with a hillocks (or tips) like self-assembly of nanoparticles driven by thermodynamic and kinetic considerations. Enhanced photoemission from locations corresponding to the tips suggest their use in high resolution display devices. An investigation on the photoluminescence of Gd_2−xEu_xO₃ (x=0.10) and Gd_2−x−yEu_xLi_yO₃ (x=0.10, y=0.08) thin films annealed at 973 K reveals that the enhancement in luminescence intensity of about 3.04 times on Li⁺ doping is solely due to the increase in oxygen vacancies and the flux effect of Li⁺ ions. The observed decrease in the values of asymmetric ratio from the luminescence spectra of Li⁺ doped Gd₂O₃:Eu³⁺ films at high temperature region is discussed in terms of increased EuO bond length as a result of Li⁺ doping.     

Fast ion conduction in the defect pyrochlore system KBxW2−xO6(B = Al,Ti and Ta)

K⁺ ionic conductivity has been measured by the complex impedence method for the defect pyrochlore type compounds of the general formula K(B^y+_xW⁶⁺_2?x)O₆, (x=1/(6?y)) where B=Al³⁺, Ti⁴⁺ and Ta⁵⁺. Thermogravimetric analysis showed the compounds to be hydrated at room temperature with from ∽0.2 mole for the Al compound to ∽1 mole of water for the Ta substituted phase. There is a correlation between the lattice parameter and amount of water present in the cavities. The ionic conductivity of 5.2×10^?3ω^?1cm^-1 at 300°C for KAl_0.33W_1.67O₆ is found to be best among known KB₂O₆ type pyrochlores. High ionic conductivity has been explained on the basis of occupancy of K⁺ ions in the available sites and polarization of the B₂X₆ network.     

插层化合物Li1+xV3O8的合成及其物理性能的初步研究

本文成功地合成了插层化合物Li_1+xV₃O₈,并用X射线粉末衍射和等离子体发射光谱元素定量分析进行了鉴定。同时进行了NMR研究。在298—400K之间观察到了锂离子的运动致窄效应,并以此求得它的离子运动激活能为0.18eV。还测得该材料的室温电导率为10^-3Ω^-1·cm^-1数量级。 关键词：     

Synthesis and electrochemical performance of Li1+xV3O8 as cathode material prepared by citric acid and tartaric acid assisted sol–gel processes

Lithium-ion battery cathode material Li_1+xV₃O₈ is synthesized by a citric acid/tartaric acid assisted sol–gel method and sintered at 350 °C, 450 °C and 550 °C for 3 h for the formation of Li_1+xV₃O₈ phase. The synthesized samples were fully characterized by FTIR, TG/DTA, XRD, SEM, EIS and charge–discharge tests. Li_1+xV₃O₈ material synthesized by tartaric acid assisted route and sintered at 450 °C for 3 h shows best electro-chemical performance. It shows a high initial capacity of 249 mAh g^?1 and still reserves a discharge capacity of 260 mAh g^?1 after 50 cycles. Moreover, in the case of tartaric assisted products, no capacity decadence is observed in 50 cycles. XRD together with TG/DTA measurements reveal that compared with citric acid assisted products, the adoption of tartaric acid as chelating agent effectively lowers the crystallization temperature of amorphous Li_1+xV₃O₈. Therefore, precursors obtained by tartaric acid route calcinated at 450 °C for 3 h exhibit lower crystallinity and smaller grain size, which contributes to the better electrochemical performance of the cathode electrodes. From EIS measurements, the bulk resistance is reduced, which favors the intercalation and de-intercalation of lithium ions while cycling.     

Non-stoichiometric molybdenum oxides as cathodes for lithium cells. part v. thermodynamic,kinetic and structural aspects of the behaviour of Mo8O23 and Mo18O52

A deeper insight in the electrochemical behaviour of Li cells based on two non-stoichiometric Mo oxides, Mo₈O₂₃ and Mo₁₈O₅₂, was obtained by determining the OCV's, the diffusion coefficients and the variations of lattice parameters as a function of depth of discharge. The first material is a monoclinic framework-structured compound endowed with large channels which provide easy paths for Li⁺. Occupation of sites in the cavities of this structure produces at first a shrinkage of the unit cell, followed by a moderate re-expansion. Mo₁₈O₅₂ is a triclinic step-layered material which markedly expands upon Li⁺ intercalation. Li⁺ diffuses in it relatively slowly for x<1, i.e. before increasing the interlayer distance, and for x>0.4 due to coulombic repulsion between Li⁺ ions.     

Influence of Al2O3 additions on crystallization mechanism and conductivity of Li2O-Ge2O-P2O5 glass-ceramics

The crystallization mechanism and conductivity of lithium aluminum germanium phosphate [LAGP] glass-ceramics fabricated from Li_1+xAl_xGe_2−x(PO₄)₃ (x=0.0-0.7) glass system were investigated as a function of Al₂O₃ additions. A non-isothermal analysis was performed to study the crystallization behavior of LAGP glass-ceramics at various heating rates (5-25K min⁻¹) by the Kissinger equation and the Augis-Bennett equation, illustrating volume crystallization for the glass-ceramics. The crystal identification and microstructure in glass-ceramics containing various Al₂O₃ contents were analyzed by means of XRD and FESEM. The main phase of the glass-ceramics was found to be LiGe₂(PO₄)₃, with AlPO₄ as the impurity phase. Additionally the highest total ionic conductivity (5.8×10⁻⁴ S/cm) at room temperature was obtained when x=0.5 for Li_1+xAl_xGe_2−x(PO₄)₃ (x=0.0-0.7) glass-ceramics, suggesting that it was a promising electrolyte for practical application in all-solid-state lithium batteries.     

多晶Li3+xV1-xTxO4(T=Ge,Si)离子导电性能的改善

本文用阻抗谱方法研究了Li_3+xV_1-xT_xO₄(T=Si,Ge)多晶的离子导电性,发现一些工艺条件如成型压强、烧结时间和烧结程序对电导率有很大影响。注意分析了这些影响的物理起因。最佳工艺条件是:在大约8t/cm²压强下成型样品。在1000℃连续烧结5至6天,烧结过程中,应尽量避免温度波动。在此条件下制备的Li_3.5V_0.5Ge_0.5关键词：     

Enhanced photoluminescence properties of Zn2SiO4:Mn co-activated with Y/Li under VUV excitation

A series of green phosphors Zn_1.92−2xY_xLi_xSiO₄:0.08Mn²⁺ (0≤x≤0.03) were prepared by solid-state synthesis method. Phase and lattice parameters of the synthesized phosphors were characterized by powder X-ray diffractometer (XRD) and the co-doped effects of Y³⁺/Li⁺ upon emission intensity and decay time were investigated under 147 nm excitation. The results indicate that the co-doping of Y³⁺/Li⁺ has favorable influence on the photoluminescence properties of Zn₂SiO₄:Mn²⁺, and the optimal photoluminescence intensity of Zn_1.90Y_0.01Li_0.01SiO₄:0.08Mn²⁺ is 103% of that of commercial phosphor when the doping concentration of Y³⁺/Li⁺ is 0.01 mol. Additionally, the decay time of phosphor is much shortened and the decay time of Zn_1.90Y_0.01Li_0.01SiO₄:0.08Mn²⁺ is 3.39 ms, shorter by 1.83 ms than that of commercial product after Y³⁺/Li⁺ co-doping.     

NMR study on an Li+-ion diffusion in the solid solution Li4−x(PO4)x(SiO4)1−x with the Li4SiO4-type structure

Diffusive motion of an Li⁺ion in the solid solution Li_4?x(PO₄)_x(SiO₄)_1?x (0 ≦ x ≦ 0.35) was studied by ⁷Li pulsed nmr between ? 70 and 440°C. Activation energies for an Li⁺ ion diffusion decreased monotonically with increasing x in the composition. These values are smaller than those reported from the measurement of ionic conductivity. Discrepency seems to result from the local nature of an Li⁺ diffusion observed by nmr contrary to the long-range one in the ionic conduction.     

Magnetic resonance study of phases in FeVO4-Co3V2O8 system

Multicomponent vanadates Co_3+xFe_4−xV₆O₂₄ have been synthesized using the solid state reaction method from Co₃V₂O₈ and FeVO₄.oxides. The electron paramagnetic resonance/ferromagnetic resonance (EPR/FMR) spectra of 20 samples containing solid state phases formed in the FeVO₄-Co₃V₂O₈ system have been recorded at room temperature. The howardevansite structure (H-type phase) is produced, which corresponds to the Co_2.616Fe_4.256V₆O₂₄ formula while a homogeneity range of lyonsite (L-type phase) type structure could be described by the Co_3+1.5xFe_4−xV₆O₂₄ formula (0.476<x<1.667). Considering the values of g-factor and linewidth of each registered spectrum the existence of three types of magnetic centers was inferred and correlated with phases detected by XRD method.     

A novel UV-emitting phosphor: Li6CaB3O8.5:Pb

Pure Li₆CaB₃O_8.5 and Li₆Ca_1−xPb_xB₃O_8.5 (0.005≤x≤0.04) materials were prepared by a solution combustion synthesis method. The phase of synthesized materials was determined using the powder XRD and FTIR. The synthesized materials were investigated using spectrofluorometer at room temperature. The emission and excitation bands of the synthesized phosphors were observed at 307 and 268 nm, respectively. The dependence of the emission intensity on the Pb²⁺ concentration for the Li₆Ca_1−xPb_xB₃O_8.5 (0.005≤x≤0.04) was studied and observed that the optimum concentration of Pb²⁺ in phosphor is 0.01 mol. The Stokes shift of the synthesized phosphor was calculated to be 4740 cm^-1.