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1.
Local structure and thermal durability of semiconducting xBaO·(90?? x)V2O5 · 10Fe2O3 glasses (x = 20, 30 and 40), NTA glass TM, before and after isothermal annealing were investigated by 57Fe-Mössbauer spectroscopy and differential thermal analysis (DTA). An identical isomer shift ( $\mathit{\delta}$ ) of 0.39 ± 0.01 mm s???1 and a systematic increase in the quadrupole splitting (Δ) were observed from 0.70 ± 0.02 to 0.80 ± 0.02 mm s???1 with an increasing BaO content, showing an increase in the local distortion of FeIIIO4 tetrahedra. From the slope of the straight line in the T gΔ plot of NTA glass TM, it proved that FeIII plays a role of network former. Large Debye temperature (Θ D) values of 1000 and 486 K were respectively obtained for 20BaO · 70V2O5 · 10Fe2O3 glass before and after isothermal annealing at 400°C for 60 min, respectively. This result also suggests that FeIII atoms constitute the glass network composed of tetrahedral FeO4, tetrahedral VO4 and pyramidal VO5 units. The electric conductivity of 20BaO · 70V2O5 · 10Fe2O3 glass increased from 1.6 × 10???5 to 5.8 × 10???2 S cm???1 after isothermal annealing at 450°C for 2,000 min. These results suggest that the drastic increase in the electric conductivity caused by heat treatment is closely related to the structural relaxation of the glass network structure.  相似文献   

2.
The enthalpies of formation of a series of high and low temperature phases in the ternary oxide system LixV2O5 have been determined by solution calorimetry. Samples of the former, α-Li0.04V2O5, β-Li0.30V2O5, β'-Li0.48V2O5 and γ-LiV2O5, were prepared by solid state reaction at 650°C. The ambient temperature materials Li0.1V2O5(I), Li0.45V2O5(II) and Li1.03V2O5(III) were prepared by n-butyl lithiation in hexane. The thermochemistries of the two classes of material were examined and related to structural features and to the observed behaviour of V2O5 as a battery cathode material in lithium cells.  相似文献   

3.
《Solid State Ionics》2006,177(26-32):2285-2289
Oxygen-ionic and electronic transport in dense (SrFe)1−x(SrAl2)xOz composites, consisting of strontium-deficient Sr(Fe,Al)O3-δ and SrAl2O4 phases, is determined by the properties of perovskite-like solid solution. Increasing the content of SrAl2O4, with a total conductivity as low as 5 × 10 7   10 S × cm 1 at 973–1273 K in air, results in the gradual decrease of the partial conductivities, but also enables the suppression of thermal expansion. Compared to single-phase SrFe1−xAlxO3-δ, (SrFe)1−x(SrAl2)xOz composites exhibit enhanced thermomechanical properties, while the oxygen permeability of these materials has similar values. The composite membranes exhibit stable performance under air/(H2–H2O–N2) and air/(CH4–He) gradients at 973–1173 K. The oxidation of dry methane by oxygen permeating through (SrFe)0.7(SrAl2)0.3Oz results in dominant total oxidation, suggesting the necessity to incorporate a reforming catalyst into the ceramic reactors for natural gas conversion.  相似文献   

4.
《Solid State Ionics》1987,23(3):173-178
Conduction properties of bismuth-lead oxyfluorides (Bi,Pb)2(O,F)3 have been investigated by complex impedance analysis. A special attention has been drawn to a hexagonal solid solution Bi(1−x)PbxO(1.5−x)Fx (0.45⩽x⩽0.741 at 770 K), which is isostructural with ALa2O3. Conductivity values range from 3 × 10−5 to 3 × 10−2 (ω cm)−1 at 585 K. A minimum associated with a maximum in activation energy is observed for the composition x = 0.5 i.e. BiPbO2F.  相似文献   

5.
《Solid State Ionics》2004,166(1-2):167-173
LiCoO2, LiNiO2 and their solid solution, LiNi1−xCoxO2, are important cathode materials for lithium ion batteries. Samples in this system were synthesized by solid state reaction of Co3O4, NiO and Li2CO3 or LiOH·H2O. Their lattice parameters were determined by Rietveld refinement. High temperature drop solution calorimetry in molten 3Na2O·4MoO3 and 2PbO·B2O3 solvents at 974 K was performed to determine the enthalpy of formation from the constituent oxides plus oxygen and the enthalpy of mixing in the solid solution series. There are approximately linear correlations between the lattice parameters, the enthalpy of formation from oxides (Li2O, NiO and CoO) plus O2 and the Co content in the compounds. The solid solution of LiCoO2 and LiNiO2 is almost ideal, showing a small positive enthalpy of mixing. The enthalpy of formation of LiCoO2 from oxides (Li2O, NiO and CoO) and oxygen at 298 K is −142.5±1.7 kJ/mol (from sodium molybdate calorimetry) or −140.2±2.3 kJ/mol (from lead borate calorimetry). That of LiNiO2 is −56.2±1.5 kJ/mol (from sodium molybdate calorimetry) or −53.4±1.7 kJ/mol (from lead borate calorimetry). The cobalt compound is thus significantly more stable than its nickel analogue. The phase assemblage LiCoO2, Li2O and CoO is seen at a lower oxygen pressure at constant temperature than the assemblage Co3O4/CoO, reflecting the stabilization of Co(III) in the ternary Li–Co–O system.  相似文献   

6.
The X-ray Absorption Near-Edge Structure (XANES) of V in vanadium-iron glasses (50P2O5 + (50?x)FeO + xV2O5) have been measured. The effective charge of V ions in glasses has been determined. At low V2O5 concentration (x ~ 5) only V4+ with 6-fold coordination is present on the contrary a static mixed valence state (V4+, V5+) has been found at high concentrations 20?x?50. The results explain the electron hopping conductivity effects at high V2O5 concentration (x ~ 50) involving V4+ ? V5+ pairs and at low V2O5 concentration (x?10) involving V4+ ? Fe3+ pairs.  相似文献   

7.
《Solid State Ionics》2006,177(26-32):2339-2345
High temperature protonic conductors of SrCe1−xYxO3−δ and Sr3Ca1+xNb2−xO9−δ were fabricated by directional solidification to produce model microstructures. Elongated cells exhibited 〈100〉 direction parallel to the growth axis; low degree of disorientation was observed between the cells. In the simple perovskite SrCe1−xYxO3−δ aluminum contamination caused the formation of intergranular second phase. Nuclear microprobe revealed that the second phase was enriched with hydrogen. Impedance spectroscopy revealed that the protons at grain boundaries have a lower mobility than within the cells. The cation distribution was not uniform in the complex perovskite. Inverse gradients in Ca2+ and Nb5+ were observed from the core to the shell of the cells. The Nb5+ substitution decreased from x = 0.12 at the core to 0.07 at the shell. Higher Nb5+/Ca2+ ratio at the shell decreased the protonic conductivity. Nanodomain were observed in both perovskite compositions; they differentiate by a 90° rotation of the direction of oxygen cage tilting. In the complex perovskite, stoichiometric domains with an ordered distribution of Nb5+ and Ca2+ were surrounded by nonstoichiometric domains with a random distribution of these cations. Further work and analyses are required to understand the mechanism of proton transfer within domains and across domain interfaces.  相似文献   

8.
The local magnetic properties of the V sites in the nonstoichiometric V2O3+x (0 ? x <0.08) have been examined by nuclear magnetic resonance and inelastic spin-flip neutron scattering techniques. The samples with x = 0.01 and 0.02 show a paramagnetic metal (PM)-antiferromagnetic insulator (AFI) transition. In the AFI phase, two distinct 51V NMR signals with hyperfine fields Hn = 184.9±0.5 kOe and 71±1 kOe were observed at 1.8 K, which were assigned as due to V3+ and V3+ sites, respectively. On the other hand, the samples with x = 0.04 and 0.06 were metallic down to 1.4K, and showed a paramagnetic (PM)-antiferromagnetic (AFM) transition at about 10 K. In these samples, a 51V NMR signal with Hn = 58±2 k0e and one with 〈Hn〉 = 9kOe were observed at 1.8 K, which were assigned as due to V3+-like sites and the matrix V sites, respectively. These results are entirely consistent with those obtained from the neutron experiment. We propose that in the metallic phase (0.04 ? x < 0.08) the minority V4+-like sites are magnetically localized in the delocalized V matrix and may be responsible for the antiferromagnetic long range order below 10 K.  相似文献   

9.
A relationship between physical properties and local structure of 20Li2O·10Fe2O3·xWO3·(70–x)V2O5 glass, abbreviated as xLFWV glass (x?=?0???25 in mol%), was investigated by 57Fe-Mössbauer spectroscopy, Fourier transform infrared spectroscopy (FT-IR), differential thermal analysis (DTA), leaching test using 20 vol% HCl and DC two- or four-probe method. 57Fe-Mössbauer spectra of xLFWV glass showed an increase of quadrupole splitting (Δ) from 0.67 to 0.73±0.02 mm s???1 and a constant isomer shift (δ) of 0.39±0.01 mm s???1 with an increase of ‘x’ from 0 to 25. This suggests that FeIIIO4 tetrahedra gradually increase their local distortion along with a substitution of WO3 for V2O5. DTA of xLFWV glass showed an increase in glass transition temperature (T g) from 252 to 298 $_{\pm 5}^{\circ}$ C with an increase of ‘x’. Composition dependency of T g and Δ indicates that FeIII atoms occupy substitutional sites of WO6 octahedra as network former (NWF), since a large slope of 680 K (mm s???1)???1 was obtained in T g ? Δ plot. Comparable electrical conductivities (σ) of 2.5 × 10???6, 1.9 × 10???6, 8.4 × 10???7 and 2.9 × 10???6 S cm???1 obtained for xLFWV glasses with ‘x’ of 0, 10, 20 and 25, respectively increased to 2.4 × 10???2, 2.4 × 10???3, 3.5 × 10???4 and 8.8 × 10???5 S cm???1 after annealing at 400 °C for 100 min. Smaller Δ values of 0.58 and 0.67±0.02 mm s???1 obtained in annealed xLFWV glasses with ‘x’ of 0 and 10, respectively indicate that structural relaxation occurs in VO4 units of vanadate glass units, as had been observed in other vanadate glasses.  相似文献   

10.
A relationship between electrical conductivity (σ) and local structure of 15Li2O·10Fe2O3·xSnO2·(70–x)V2O5·5P2O5 glass (x = 0–20 mol%), abbreviated as xLFSVP glass, was investigated by 57Fe- and 119Sn-Mössbauer spectroscopies, differential thermal analysis (DTA) and dc-four probe method. A small increase in quadrupole splitting (Δ) for FeIII was observed from 0.70 to 0.74± 0.02 mm s???1 with an increase of “x”, whereas isomer shift (Δ) values of 0.40±0.01 mm s???1 were independent of “x”. This result suggests that local distortion of FeIIIO4 tetrahedra was slightly increased in SnO2-containing vanadate glasses, which was reflected as an increase in glass transition temperature (Tg) from 266 to 285±5 °C. A slope of 675 K / (mm s???1) obtained in ‘Tg vs. Δ plot’ proved that FeIII occupied the site of network former (NWF). An isothermal annealing of 10LFSVP glass at 500 °C for 100 min resulted in a marked decrease of Δ from 0.72 to 0.56±0.02 mm s???1, indicating that local distortion of FeO4 tetrahedra was reduced by the structural relaxation of 3D-network. In contrast, identical δ and Δ values of 0.07±0.01 and 0.53±0.02 mms???1, respectively, were observed in 119Sn-Mössbauer spectra of 10LFSVP glass before and after the annealing. These results indicate that SnIVO6 octahedra are loosely bound in the glass matrix as a network modifier (NWM). A marked increase in σ from 7.4 × 10???7 to 9.1 × 10???3 S cm???1 was observed in 20LFSVP glass after the isothermal annealing, indicating that structural relaxation of 3D-network evidently causes a marked increase in σ.  相似文献   

11.
The generalized exponential-integral function V(x, y) defined here includes as special cases the function E(2)1(x) = V(x, 0) introduced by van de Hulst and functions M0(x) = V(x, 1) and N0(x) = V(x, -1) introduced by Kourganoff in connection with integrals of the form ∫ En)t)Em(t±x), which play an important role in the theory of monochromatic radiative transfer. Series and asymptotic expressions are derived and, for the most important special cases, y = 0 and y = 1, Chebyshev expansions and rational approximations are obtained that permit the function to be evaluated to at least 10 sf on 0<x<∞ using 16 sf arithmetic.  相似文献   

12.
《Solid State Ionics》2006,177(13-14):1211-1217
La1−xSrxCr1−xMxO3−δ (M = Cr, Fe, V) system has been studied as anode materials for solid oxide fuel cells (SOFCs). The perovskite La0.75Sr0.25Cr0.5Mn0.5O3−δ (LSCM) is stable in both H2 and CH4 atmospheres at temperatures up to 1000°C. However, in the reducing atmospheres of H2 and CH4, its electronic conductivity is greatly reduced from its value in air. We have characterized LSCM as the anode of a SOFC having 250 μm-thick La0.8Sr0.2Ga0.83Mg0.17O2.815 (LSGM) as the electrolyte and SrCo0.8Fe0.2O3−δ (SCF) as the cathode. We report a comparison of the overpotentials at the following anodes: (1) La0.4Ce0.6O1.8 (LDC) + NiO composite in H2, (2) porous LSCM in H2 and CH4, (3) porous LSCM impregnated with CuO in H2 and CH4 and (4) porous LSCM impregnated with CuO and sputtered with Pt in H2 and CH4. An LSCM + CuO + Pt anode gave a maximum power output at 850 °C of 850 mW/cm2 and 520 mW/cm2, respectively, with H2 and CH4 as fuel whereas anode (1) gave 1.4 W/cm2 at 800 °C in H2. There was no noticeable coke formation in CH4 with anodes (2), (3) and (4), which demonstrates that the perovskite oxide is a plausible option for the anode of a SOFC operating with hydrocarbon fuels. We also report the moisture effect in the H2 and CH4 fuel-oxidation process.  相似文献   

13.
《Solid State Ionics》2006,177(19-25):2005-2008
Electronic conductivity in the potential SOFC anode material La1−xSrxCr0.5Mn0.5Oδ has been investigated in the range 0.2 < x < 0.3. log(σT) vs. 1/T plots indicate conduction via thermally activated polaron hopping. At 900 °C, conductivity in air increases with Sr2+ via an increase in [BB] holes (B—transition metal). X-ray absorption spectroscopy (XAS) studies indicate that compensation for A-site Sr substitution and oxygen vacancy formation is via the Mn cation only; Cr maintains a 3+ oxidation state and 6-fold oxygen coordination. Electronic transport occurs by percolation between Mn cations in a disordered B-site sub-lattice. Conductivity decreases with p(O2), which is indicative of p-type conduction behaviour, but the relationship cannot be explained by a simple redox equilibrium involving Mn3+, Mn4+ and oxygen, possibly due to co-existence of Mn2+, Mn3+ and Mn4+ via disproportionation as with La1−xSrxMnOδ.  相似文献   

14.
We study the one-dimensional random dimer model, with Hamiltonian H ω =Δ+V ω , where for all x $\mathbb{Z}$ , V ω(2x)=V ω(2x+1) and where the V ω(2x) are i.i.d. Bernoulli random variables taking the values ±V, V>0. We show that, for all values of Vand with probability one in ω, the spectrum of His pure point. If V≤1 and V≠1/ $\sqrt 2$ , the Lyapunov exponent vanishes only at the two critical energies given by EV. For the particular value V=1/ $\sqrt 2$ , respectively, V= $\sqrt 2$ , we show the existence of new additional critical energies at E=±3/ $\sqrt 2$ , respectively, E=0. On any compact interval Inot containing the critical energies, the eigenfunctions are then shown to be semi-uniformly exponentially localized, and this implies dynamical localization: for all q>0 and for all ψ $\ell$ 2( $\mathbb{Z}$ ) with sufficiently rapid decrease $${\mathop {\sup }\limits_t} r_{\psi ,I}^{\left( q \right)} {\kern 1pt} \left( t \right): = {\mathop {\sup }\limits_t} \left\langle {P_I \left( {H\omega } \right)\psi _t ,\left| X \right|^q P_I \left( {H\omega } \right)\psi _t } \right\rangle < \infty $$ Here $\psi _t = e^{- iH_{\omega ^t}} \psi$ , and P I(H ω) is the spectral projector of H ωonto the interval I. In particular, if V>1 and V $\sqrt 2$ , these results hold on the entire spectrum [so that one can take I=σ(H ω)].  相似文献   

15.
《Solid State Ionics》1987,24(2):103-109
The diffusion coefficient of Li+ in the γ-lithium vanadium bronze (Li1+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.  相似文献   

16.
Equilibrium of 1:2:3 superconductors (CaxLa1−x)(Ba1.75−xLa0.25+x)Cu3Oy (this compound has in the past variously denoted as CLBLCO, CLBCO or CaLaBaCuO) with oxygen was studied for x=0.1 and x=0.4 in the temperature range of 150–950 °C under 1 atm. O2. The main process is the reversible reaction −Cu32+O6.625+0.25O2=−Cu22+Cu3+O7.125 which is completed with the formation of one Cu3+. The enthalpy (in kJ/mol CLBLCO) and entropy (in J(mol CLBLCO)−1K−1) of this reaction were calculated from the temperature dependence of the equilibrium constant. The values are ΔH=−33.1 and ΔS=−29.9 for x=0.1 and ΔH=−49.4 and ΔS=−42.7 for x=0.4.It was found that the equilibrium of ceramic pellet of CLBLCO with oxygen cannot be practically achieved below 300 °C while the equilibrium for powder is achieved even at 200 °C. Low rate of reaction of CLBLCO with oxygen causes the problem in low temperature equilibration. In contrast, diffusion of oxygen ions in the ceramics is observed even at 200 °C. This diffusion proceeds without the change of the oxygen content and may be applied in order to improve the homogeneity of the distribution of oxygen ions.  相似文献   

17.
Glasses of the general formula xLi2O·(20?x)CaO·30P2O5·30V2O5·20Fe2O3 with x=0, 5, 10, 15 and 20 mol% were prepared; IR, density, electrical and dielectric properties have been investigated. Lithia-containing glasses revealed more (P2O7)4?, FeO6, V–O? and PO? groups and mostly have lower densities than those of lithia-free ones. The electrical properties showed random behavior by replacing Li2O for CaO, which has been assigned to the change of the glass structure. The results of activation energy and frequency-dependent conductivity indicate that the conduction proceeds via electronic and ionic mechanisms, the former being dominant. The mechanism responsible for the electronic conduction is mostly thermally activated hopping of electrons from Fe(II) ions to neighboring Fe(III) sites and/or from V4+ to V5+. The dielectric constant (ε′) showed values that depend on the structure of glass according to its content of Li2O. The (ε′) values are ranging between 3 and 41 at room temperature for 1 kHz, yet at high temperatures, glass with 20 mol Li2O exhibits values of 110 and 3600 when measurement was carried out in the range 0.1–1 kHz, and at 5 MHz, respectively.  相似文献   

18.
A number of absorptions between 100 and 300 cm?1 in the infrared spectrum of trimethylene sulfoxide vapor have been observed and assigned to Δvp = 1 and 2 transitions in the ring puckering mode. With the aid of a computer program providing for a potential function essentially of the form V(x) = V2x2 + V3x3 + V4x4 (x the dimensioned puckering coordinate), the barrier to inversion between the stable equatorial and a possible axial conformer is established to be 1205 cm?1 with an uncertainty of ±11 cm?1 at the worst or ±1 cm?1 at best, depending upon the assignment of several very weak absorptions. The axial well depth, depending more critically upon these assignments, is no greater than 150 cm?1 and may be as low as 5 cm?1.  相似文献   

19.
Glasses with composition xBi2O3·(30−x)M2O·70B2O3 (M=Li, Na) containing 2 mol% V2O5 have been prepared over the range 0≤x≤15 (x is in mol%). The electron paramagnetic resonance spectra of VO2+ of these glasses have been recorded in the X-band (≈9.3 GHz) at room temperature (RT≈300 K). Spin Hamiltonian parameters, g, g, A, A, dipolar hyperfine coupling parameter, P, and Fermi contact interaction parameter, K, have been calculated. The molecular orbital coefficients, α2 and γ2, have been calculated by recording the optical transmission spectra. In xBi2O3·(30−x)Li2O·70B2O3 glasses there is decrease in the tetragonality of the V4+O6 complex for x up to 6 mol% whereas for x≥6 mol%, tetragonality increases. In xBi2O3·(30−x)Na2O·70B2O3 glasses there is increase in the tetragonality of the V4+O6 complex with increasing x. The 3dxy orbit expands with increase in Bi2O3:M2O ratio. Values of the theoretical optical basicity, Λth, have also been reported. The DC conductivity increases with increase in temperature. The order of conductivity is 10−5 ohm−1 m−1 at low temperature and 10−3 ohm−1 m−1 at high temperature. The DC conductivity decreases and the activation energy increases with increase in Bi2O3:M2O ratio.  相似文献   

20.
《Solid State Ionics》2006,177(3-4):237-244
Ongoing studies of the KHSeO4–KH2PO4 system aiming at developing novel proton conducting solids resulted in the new compound K2(HSeO4)1.5(H2PO4)0.5 (dipotassium hydrogenselenate dihydrogenphosphate). The crystals were prepared by a slow evaporation of an aqueous solution at room temperature. The structural properties of the crystals were characterized by single-crystal X-ray analysis: K2(HSeO4)1.5(H2PO4)0.5 (denoted KHSeP) crystallizes in the space group P 1¯ with the lattice parameters: a = 7.417(3) Å, b = 7.668(2) Å, c = 7.744(5) Å, α = 71.59(3)°, β = 87.71(4)° and γ = 86.04(6)°. This structure is characterized by HSeO4 and disordered (HxSe/P)O4 tetrahedra connected to dimers via hydrogen bridges. These dimers are linked and stabilized by additional hydrogen bonds (O–H–O) and hydrogen bridges (O–H…O) to build chains of dimers which are parallel to the [0, 1, 0] direction at the position x = 0.5.The differential scanning calorimetry diagram showed two anomalies at 493 and 563 K. These transitions were also characterized by optical birefringence, impedance and modulus spectroscopy techniques. The conductivity relaxation parameters of the proton conductors in this compound were determined in a wide temperature range. The transport properties in this material are assumed to be due to H+ protons hopping mechanism.  相似文献   

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