钙钛矿型混合离子电子导体在能源转化中应用的研究进展

钙钛矿型离子电子导体具有良好的传导氧离子和电子性能,使其在能源转化过程中具有较好的应用前景,已成为人们研究的热点。本文综述了钙钛矿型离子电子导体的主要制备方法,并着重介绍了其在化学循环燃烧、氧气的分离、制氢、太阳能电池方面的应用。钙钛矿型混合离子电子导体可作为一种复合催化剂,应用于甲烷选择性氧化工艺,为钙钛矿离子电子导体应用新途径,同时为甲烷高效催化转化利用提供了理论支持。     

Crystal structures and chemistry of double perovskites Ba2M(II)M′(VI)O6 (M=Ca, Sr, M′=Te, W, U)

Structures of the double perovskites Ba₂M(II)M ′(VI)O₆ (M=Ca, Sr, M′=Te, W, U) at room temperature have been investigated by the Rietveld method using X-ray and neutron powder diffraction data. For double perovskites with M=Sr, the observed space groups are I2/m (M′ =W) and (M′=Te), respectively. In the case of M=Ca, the space groups are either monoclinic P2₁/n (M′=U) or cubic (M′=W and Te). The tetragonal and orthorhombic symmetry reported earlier for Ba₂SrTeO₆ and Ba₂CaUO₆, respectively, were not observed. In addition, non-ambient X-ray diffraction data were collected and analyzed for Ba₂SrWO₆ and Ba₂CaWO₆ in the temperature range between 80 and 723 K. It was found that the rhombohedral structure exists in Ba₂SrWO₆ above room temperature between the monoclinic and the cubic structure, whereas the cubic Ba₂CaWO₆ undergoes a structural phase transition at low temperature to the tetragonal I4/m structure.     

阳极界面修饰对钙钛矿太阳能电池性能的影响

采用在聚(3,4-乙撑二氧噻吩)∶聚苯乙烯磺酸(Poly(3,4-ethylenedioxythiophene)∶Poly(styrenesulfonate),PEDOT∶PSS)阳极界面层上直接旋涂二甲基亚砜(Dimethyl Sulfoxide,DMSO)的方法,对PEDOT∶PSS薄膜进行修饰,以提高所制得的钙钛矿太阳能电池器件性能.在5000rpm转速条件下旋涂DMSO后,器件的能量转换效率达到11.43%,与PEDOT∶PSS阳极界面层未做任何修饰的器件相比,效率提高了29.15%.测试表征了修饰前后PEDOT∶PSS薄膜的透光性、表面形貌、电导率、器件的外量子效率曲线以及器件在光照和暗态下的J-V特性曲线,分析了器件性能提高的原因.结果表明:经过修饰的PEDOT∶PSS薄膜导电性显著增强,从而更加有利于器件阳极对空穴的抽取和收集;较未修饰时,器件的短路电流密度得到了大幅度提升,进而使得器件获得更高的能量转换效率.     

稀土掺杂锰氧化物庞磁电阻效应

过去十多年来，具有庞磁电阻效应的稀土掺杂锰氧化物成为了凝聚态物理研究的重要领域。锰氧化物的载流子自旋极化率高，且在居里温度附近表现出很大的磁电阻效应，因此在自旋电子学中有潜在的应用前景。另一方面，锰氧化物是典型的强关联电子体系，它对目前有关强关联体系的认识提出了很大挑战。本文综述了锰氧化物的各种性质及其物理原因。全文首先概述了锰氧化物的庞磁电阻效应及其晶格和电子结构，简单介绍了其他一些庞磁电阻材料；随后综述了锰氧化物的电荷／轨道有序相及其输运性质；在第四部分简单介绍了锰氧化物中庞磁电阻效应的机制；最后讨论了锰氧化物的一些可能的应用，如低场磁电阻效应、磁隧道结、磁p-n结以及全钙钛矿的场效应管和自旋极化电子注入装置等。     

Sonochemical synthesis of CH3NH3PbI3 perovskite ultrafine nanocrystal sensitizers for solar energy applications

The organic–inorganic hybrid perovskite CH₃NH₃PbI₃ is becoming an interesting material in the field of energy harvesting. This material is one of the cleanest and cheapest components in solar cells which is available in ample amounts. However, most of the previous research work was done on thin film of this material. In the present work we describe the preparation of a powder containing nanoparticles of CH₃NH₃PbI₃ using a sonochemical method. Characterization of the product was done by various methods, such as HRTEM, FTIR, PL, DLS and XRD. The particles were found to be highly crystalline (tetragonal crystal structure), polygonal in shape and having diameters of 10–40 nm.     

X-Ray powder diffraction study of structural phase transitions in (Ba0.5Sr0.5)PbO3 perovskite

Study of structural properties of (Ba_0.5Sr_0.5)PbO₃ has been carried out in a wide temperature range from 10 to 1223 K using the X-ray powder diffraction technique. Two temperature-induced structural phase transitions at 948 and 1198 K have been found. For polycrystallines the XPS and electrical resistivity measurements have been performed.     

Sr1−xBaxSnO3 system applied in the photocatalytic discoloration of an azo-dye

Semiconductor materials have received substantial attention as photocatalysts for controlling water pollution. Among these materials, perovskite-structured SrSnO₃ is a promising candidate for this application, whereas BaSnO₃ exhibits very low activity. In the present work, Sr_1−xBa_xSnO₃ (x = 0, 0.25, 0.50, 0.75 and 1) was synthesized by solid-state reaction and was applied in the photocatalytic discoloration of the organic dye Remazol Golden Yellow. The perovskite structure was obtained for all compositions of the solid solutions with both Sr²⁺ and Ba²⁺ present in the lattice. A remarkable change in the short-range symmetry was observed as the amount of Ba²⁺ increased, and this change led to a decrease in the band gap of the material. Although the BaSnO₃ was not active toward water photolysis, the discoloration induced by this perovskite was twice that induced by SrSnO₃. The two materials appear to feature different mechanisms of photodegradation: the direct mechanism prevails in the case of BaSnO₃, whereas the indirect mechanism appears to play a key role in the case of SrSnO₃.     

Quantized Conductance in Heteronanocontacts Between Iron Tip and Perovskite Electrode Under High-Bias Voltages

We studied the conductance of a point contact between a mechanically sharpened iron tip and a surface of the La_0.7Sr_0.3MnO₃ perovskite electrode. The tip is fixed to a piezoelectric element and the conductance is measured as a function of the piezo voltage, which controls the tip pressing on the electrode. The height of steps between conductance plateaus is a multiple of the integer quantum e ²/h, characteristic for ferromagnetic materials in which the spin degeneracy is lifted.     

Laboratory Intercomparison on the Determination of the Fe(II)/Fe(III) Ratio in Glass Using Mössbauer Spectroscopy

A Perturbed Angular Correlation (PAC) study was performed on the system that presents a rich variety of structural and magnetic phase transitions as a function of the oxygen content (δ) or as a function of temperature (T). The PAC signal at room temperature allowed the determination of the Electrical Field Gradient (EFG) parameters and to correlate them with the lattice average symmetry namely the orthorhombic (O′ or O*) Pbnm and rhombohedral (R) phases measured by X-ray diffraction.     

Synthesis, crystal structure and characterization of new 12H hexagonal perovskite-related oxides Ba6M2Na2X2O17 (M=Ru, Nb, Ta, Sb; X=V, Cr, Mn, P, As)

The new Ba₆Ru₂Na₂X₂O₁₇ (X=V, Mn) compounds have been prepared by electrosynthesis in molten NaOH and their crystal structures have been refined from single crystals X-ray diffraction, space group P6₃/mmc, Z=2, for X=V: , , R₁=4.76%, for X=Mn : , , R₁=3.48%. The crystal structure is a 12H-type perovskite with a (c′cchcc)₂ stacking sequence of [BaO₃]_c, [BaO₃]_h and [BaO₂]_c′ layers. The tridimensional edifice is formed by blocks of Ru₂O₉ dimers that share corners with NaO₆ octahedra. These blocks sandwich double sheets of X⁵⁺O₄ tetrahedra. Several isotypic Ba₆M⁵⁺₂Na₂X⁵⁺₂O₁₇ materials (X=V, Cr, Mn, P, As) and (M=Ru, Nb, Ta, Sb) have been prepared by solid state reaction and characterized by Rietveld analysis. The magnetic and electric properties have been investigated and show besides the Ru⁵⁺₂O₉ typical intradimer antiferromagnetic couplings, discrepancies of both χ and ρ versus T at 50 and 100 K for Ba₆Ru₂Na₂X₂O₁₇ (X=V, As). In this work, a review of the identified Ru-hexagonal perovskite materials is also reported in order to overview the wide variety of possibilities in the field of new compounds synthesis.