钴掺杂Sr1.5La0.5MnO4的合成及高温电化学性能研究

采用EDTA-柠檬酸法合成了中温固体氧化物燃料电池阴极材料Sr_(1.5)La_(0.5)Mn_(1-x)Co_xO_4(SLMCOx),并利用粉末X射线衍射(XRD)、X射线光电子能谱(XPS)以及电化学交流阻抗谱(EIS)进行表征。结果表明,该材料与Ce0.9Gd0.1O1.95(CGO)在1 200℃烧结12 h不发生化学反应。随着Co掺入量的增加,氧化物中Mn~(3+)和Co~(2+)含量增多,晶格氧含量降低,晶格畸变率增大。交流阻抗谱(EIS)测试结果显示,钴的掺杂明显降低电极的极化电阻,其中Sr_(1.5)La_(0.5)Mn_(0.7)Co_(0.3)O_4阴极在700℃空气中的极化电阻为0.62Ω·cm~2,明显小于Sr_(1.5)La_(0.5)MnO_4阴极在750℃的极化电阻(1.5Ω·cm~2),表明钴掺杂的Sr_(1.5)La_(0.5)Mn_(1-x)CoxO_4是一种潜在的IT-SOFC阴极材料。     

Indium oxide co-doped with tin and zinc: A simple route to highly conducting high density targets for TCO thin-film fabrication

Indium oxide co-doped with tin and zinc (ITZO) ceramics have been successfully prepared by direct sintering of the powders mixture at 1300 °C. This allowed us to easily fabricate large highly dense target suitable for sputtering transparent conducting oxide (TCO) films, without using any cold or hot pressing techniques. Hence, the optimized ITZO ceramic reaches a high relative bulk density (∼ 92% of In₂O₃ theoretical density) and higher than the well-known indium oxide doped with tin (ITO) prepared under similar conditions. All X-ray diagrams obtained for ITZO ceramics confirms a bixbyte structure typical for In₂O₃ only. This indicates a higher solubility limit of Sn and Zn when they are co-doped into In₂O₃ forming a solid-solution. A very low value of electrical resistivity is obtained for [In₂O₃:Sn_0.10]:Zn_0.10 (1.7 × 10⁻³ Ω cm, lower than ITO counterpart) which could be fabricated to high dense ceramic target suing pressure-less sintering.     

The Ba2LnFeNb4O15 “tetragonal tungsten bronze”: Towards RT composite multiferroics

Several Niobium oxides of formula Ba₂LnFeNb₄O₁₅ (Ln = La, Pr, Nd, Sm, Eu, Gd) with the “tetragonal tungsten bronze” (TTB) structure have been synthesised by conventional solid state methods. The neodymium, samarium and europium compounds are ferroelectric with Curie temperature ranging from 320 to 440 K. The praseodymium and gadolinium compounds behave as relaxors below 170 and 300 K respectively. The praseodymium, neodymium, samarium, europium and gadolinium compounds exhibit magnetic hysteresis loops at room temperature originating from traces of a barium ferrite secondary phase. The presence of both ferroelectric and magnetic hysteresis loops at room temperature allows considering these materials as composites multiferroic. Based on crystal-chemical analysis we propose some relationships between the introduction of Ln³⁺ ions in the TTB framework and the chemical, structural and physical properties of these materials.     

Transport properties and in-situ Raman spectroscopy study of BaCe0.9Y0.1O3 − δ as a function of water partial pressures

The total conductivity of BaCe_0.9Y_0.1O_3 − δ material was measured under air, in a large p(H₂O) range up to 0.30 bar. The defect concentrations (OH_O^·, V_O^· · and h^·) and electrical conductivities were calculated on the basis of chemical constants (diffusion coefficients and equilibrium constants reported in the past literature) and compared to the experimental data. Protonic transport number as high as 0.8 was found at 700 °C, under air containing 0.30 bar of water, which allows a possible extension of the protonic temperature range of this material using water rich atmosphere. In-situ Raman spectroscopy under wet and dry air was performed from room temperature up to 700 °C in two wavenumber ranges. At low wavenumber, characteristic of lattice vibrations, this study clearly shows that no significant changes occur upon water insertion while at high wavenumbers, characteristic of OH vibrations, two contributions to the OH vibrations were found. This is discussed in terms of proton environment and transient hydrogen bonds. Moreover, this in situ study confirms that, at moderate p(H₂O), water insertion becomes significant at temperature below 650 °C.     

On the ternary UCu6.68Al4.32 phase

Uranium copper aluminide, UCu_6.68Al_4.32, has been synthesized by arc-melting, followed by annealing at 600 °C. The phase belongs to the tetragonal BaCd₁₁-type (space group I4₁/amd, Pearson symbol tI48, Z = 4, a = 10.2471(4) and c = 6.5883(3) Å, V = 691.78(4) Å³). Electrical resistivity, specific heat and magnetic susceptibility data, measured from room temperature down to ∼3 K do not show any magnetic phase transition. The compound stays in its paramagnetic state, and at high temperatures can be adjusted according to the modified Curie–Weiss model (μ_eff ∼ 2.7 μ_B/U-atom). The Sommerfeld value of the specific heat, γ ∼ 98 mJ/molK², is well above the values derived for simple metallic systems. In this context, with the overall shape of the temperature dependent electrical resistivity, spin fluctuations can be concluded, dominating the ground state behaviour in UCu_6.68Al_4.32.     

Infrared absorptive properties of Al-doped ZnO divided powder

Al-doped ZnO powders were synthesised by a Pechini process in order to obtain visible non-absorbent and near-Infrared absorbent particles. Firstly, it has been shown that synthesis under argon combined with the lowest synthesis temperatures (700 °C) allows getting the optimal properties for pure ZnO compounds due to creation of n-type defects segregated on oxide grain surface (Zn/O ratio superior to 1). Nevertheless, the near-Infrared absorption properties of the pure ZnO compounds remain low. The Al³⁺ doping of ZnO compounds was then investigated. The Al solubility limit inside ZnO doped compounds decreases drastically with the grain size, i.e. with the synthesis temperature. Then, the Al cations distribution varies inside ZnO grains, Al³⁺ segregation at the grain surfaces taking place for high synthesis temperatures. The optimal optical properties (high near-Infrared absorption) are reached combining Al-doping and adequate synthesis conditions: annealing under argon at low temperatures. In these conditions, the highest extrinsic (via Al doping) and intrinsic n-types defects rates are indeed reached.     

Emission-photoactivity cross-processing of mesoporous interfacial charge transfer in Eu3+ doped titania

Periodic mesoporous Eu(3+) doped titania materials were obtained through the EISA (Evaporation Induced Self Assembly) process. Eu(3+) ions, entrapped within the semi-crystalline walls of the highly porous framework, appear to be advantageous during the probing of surface photochemical reactions. Its emission intensity is very sensitive to the presence of physisorbed molecules, in gas or liquid phase, that reside within the pores. In particular, strong fluctuations in intensity of the (5)D(0)→(7)F(2) transition were observed under UV light exposure on the time scale of tens of seconds. The emission modulation dynamics show a strong correlation with the crystallinity of the titania matrix. Correlation of the emission with the photocatalytic activity of the semiconductor for photodegradation of an organic molecule is observed. A model is proposed to describe the involved mechanisms.     

Structure of Li2MnO3 with different degrees of defects

The synthesis and structural properties of the layered oxide Li₂MnO₃ have been studied in details. It represents a key for a better understanding of the complex structural evolutions pointed out in the materials like Li(Li,Ni,Mn,Co)O₂ when they are used as positive electrode materials in lithium-ion batteries. Li₂MnO₃ samples were prepared either via coprecipitation or via a two step solid state reaction followed by different annealing treatments. Using X-ray and electron diffraction in combination with diffraction data simulations, we show that in function of the synthesis conditions, Li₂MnO₃ is obtained with various degrees of disorder, along the c monoclinic direction, in the stacking of the ordered Li_1/3Mn_2/3 sheets within the cfc oxygen packing. We show that this disorder decreases when the synthesis temperature increases but the synthesis of a material free of stacking faults is not possible with these synthesis routes. Finally, the similarities between the evolutions pointed out in Li₂MnO₃ due to the synthesis conditions and those previously observed in the materials like Li(Li,Ni,Mn,Co)O₂ related to the evolution of the cations distribution in the slabs are underlined.     

Modulation of the crystallinity of hydrogenated nitrogen-rich graphitic carbon nitrides

An hydrogenated nitrogen-rich graphitic carbon nitride, structurally related to the theoretical graphitic phase of C₃N₄, has been synthesized in a bulk well-crystallized form. This new material was prepared by thermal decomposition of thiosemicarbazide up to 600 °C at ambient pressure under nitrogen flow. Its composition was determined by elemental combustion analysis. Powder X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy and C¹³ MAS NMR characterizations were performed. This material can be schematically described with a two-dimensional framework and a composition close to C₃N_4.17H_1.12. In this nitrogen-rich material, C₃N₃ voids are fully occupied by water molecules which are strongly trapped into the material. A loss of crystallinity associated with a modification of the thermal behavior is observed when the amount of trapped molecules decreases in the graphitic material, order being damaged both between and in the graphitic planes.