PRECIPITATION AND GROWTH OF PEROVSKITE PHASE IN TITANIUM BEARING BLAST FURNACE SLAG

The effects of transformation of slag composition and additive agents on the morphology, the precipitation behavior, the crystal growth, and the volume fraction (VF) of perovskite (CaO·¤TiO_2) crystal in the Ti-bearing blast furnace slags were investigated. As the morphology of perovskite is dispersed in molten slags, the crystal growth mechanism of the melting of fine dendrites and the coarsening of large grains exist throughout the solidification of molten slags. With the increase of CaO and Fe_2O_3 content, VF of perovskite obviously increases. However, high basicity leads to the viscosity of slag, which results in the reduction of the average equivalent diameter (AED). The experimental results showed that the presence of the additives CaF_2 and MnO efficiently decreased the viscosity of the slags, and obviously improved the morphology of perovskite and promoted its growth.

Selective enrichment of TiO_2 and precipitation behavior of perovskite phase in titania bearing slag

The effects of additive agents and growth behavior of perovskite phase as well as temperature change of slag at semi industry scale test were studied. The results show that the increase of steel slag does good to titania enrichment, however, it isn’t useful for the growth and coarsening of the perovskite phase. The additive Si-Fe powder can promote titania enrichment and make perovskite phase grow up easily. While air is blown into the molten slag, the reduced components in slag are oxidized and the released heat raises the temperature of slag.

Isothermal precipitation and growth process of perovskite phase in oxidized titanium bearing slag

The isothermal precipitating behavior of perovskite phase in oxidized titanium bearing slag was studied by quenching method.The kinetics of precipitating process and crystal growth of perovskite phase was analyzed.The results show that the precipitating and growth of perovskite are non-equilibrium process at the beginning of isothermal treatment.There are two factors influencing the growth rate of perovskite phase on non-equilibrium condition,one is the supersaturation concentration of perovskite and the other is the coarsening arising from the growth of larger perovskite at the expense of smaller ones.The precipitation kinetics of perovskite phase can be nearly described by the JMAK equation.

Oxygen permeation and phase structure properties of partially A-site substituted BaCo_(0.7)Fe_(0.225)Ta_(0.075)O_(3-δ) perovskites

Ba0.9R0.1Co0.TFe0.225Ta0.07503-δ （BRCFT, R = Ca, La or Sr） membranes were synthesized by a solid-state reaction. Metal cation Ca2＋, La3＋ or Sr2＋ doping on A-site partially substituted Ba2＋ in BaCoo.TFe0.225Ta0.07503-δ oxides, and its subsequent effects on phase structure stability, oxygen permeability and oxygen desorption were systematically investigated by XRD, TG-DSC, Hz-TPR, O2-TPD techniques and oxygen permeation experiments. The partial substitution with Ca2＋, La3＋ or Sr2＋, whose ionic radii are smaller than that of Ba2＋, succeeded in stabilizing the cubic perovskite structure without formation of impurity phases, as revealed by XRD analysis. Oxygen-involving experi- ments showed that BRCFT with A-site fully occupied by Ba2＋ exhibited good oxygen permeation flux under He flow, reaching about 2.3 mL.min-l .cm-2 at 900 with I mm thickness. Of all the membranes, BLCFT membrane showed better chemical stability in CO2, owing to the reduction in alkalinity of the mixed conductor oxide by La doping. In addition, we also found the stability of the perovskite structure under reducing atmospheres was strengthened by increasing the size of A-site cation （Ba2＋〉La3＋〉SrZ＋〉Ca2＋）.

Detrimental phase evolution triggered by Ni in perovskite-type cathodes for CO2 electroreduction

Perovskite oxides are popular as cathode materials of solid oxide electrolysis cells, because of their good redox stability and high resistance to coke formation.Unexpectedly, a negative effect of Ni doping is found on Sr2Fe(1.5-x)NixMo(0.5)O(x = 0, 0.05, 0.1, 0.2) cathode for pure CO2 electroreduction at 800 ℃, although Ni is highly active for CO2 electroreduction.The CO2 electroreduction performance degrades with the increase of Ni doping amount.Various characterization techniques are used to disclose the negative effect.Ni doping decreases the perovskite stability under electroreduction conditions, Fe and Ni cations in the B-site are reduced to metal nanoparticles and SrCO3 forms on the surface of the perovskite.The phase instability results from the weaker Ni–O bond.Although the Fe-Ni nanoparticles are in favor of the CO2 electroreduction, too much SrCO3 and carbon deposition block the charge transfer and diffusion of oxygenous species on the cathode surface.

Charge carrier dynamics in different crystal phases of CH_(3)NH_(3)PbI_(3)perovskite

Despite that organic-inorganic lead halide perovskites have attracted enormous scientific attention for energy conversion applications over the recent years,the influence of temperature and the type of the employed hole transport layer(HTL)on the charge carrier dynamics and recombination processes in perovskite photovoltaic devices is still largely unexplored.In particular,significant knowledge is missing on how these crucial parameters for radiative and non-radiative recombinations,as well as for efficient charge extraction vary among different perovskite crystalline phases that are induced by temperature variation.Herein,we perform micro photoluminescence(pPL)and ultrafast time resolved transient absorption spectroscopy(TAS)in Glass/Perovskite and two dierent Glass/ITO/HTL/Perovskite configurations at temperatures below room temperature,in order to probe the charge carrier dynamics of different perovskite crystalline phases,while considering also the effect of the employed HTL polymer.Namely,CH_(3)NH_(3)Pbb films were deposited on Glass,PEDOT:PSS and PTAA polymers,and the developed Glass/CH_(3)NH_(3)PbI_(3)and Glass/ITO/HTL/CH_(3)NH_(3)PbI_(3)architectures were studied from 85 K up to 215 K in order to explore the charge extraction dynamics of the CH_(3)NH_(3)PbI_(3)orthorhombic and tetragonal crystalline phases.It is observed an unusual blueshift of the bandgap with temperature and the dual emission at temperature below of 100 K and also,that the charge carrier dynamics,as expressed by hole injection times and free carrier recombination rates,are strongly depended on the actual pervoskite crystal phase,as well as,from the selected hole transport material.

The Evidence of Phase Separation in Perovskite Manganites Above T_c

A series of bulk ceramic samples of La_(1-x)Ca_xMnO_3 and Y_(1-x)Ca_xMnO_3 was prepared by the conventional solid state reaction method,and the samples of x=1/3 were investigated particularly.The colossal magnetoresistance phenomenon and the properties of magnetic and transport were studied in detail by the experiments of magnetic susceptibility and low temperature resistance.Small angle X-ray scattering (SAXS) was used to investigate the charge inhomogeneities in our samples at room temperature for the first time,and phase separation and colossal magnetoresistance phenomena induced by charge inhomogeneities above T_c were discovered.

B位掺杂提升CsSnI_(3)钙钛矿结构和电荷稳定性的第一性原理研究

全无机CsSnI_(3)钙钛矿拥有理想的带隙宽度(1.3 eV),光电转化效率理论峰值达到33%.目前CsSnI_(3)太阳能电池的发展受制于的CsSnI_(3)的结构不稳定性和Sn^(2+)易被氧化为Sn^(4+)的问题.研究基于第一性原理,详细探讨了一系列金属元素对CsSnI_(3)进行B位掺杂改性的方案,旨在提升CsSnI_(3)结构稳定性,并抑制CsSnI_(3)中Sn^(2+)被氧化为Sn^(4+)的问题.计算结果表明,在CsSnI_(3)钙钛矿B位掺杂三价金属Sb、Bi能够阻碍CsSnI_(3)相变生成Cs_(2)SnI_6,并且抑制Sn^(2+)的氧化;尤其在晶格中存在锡空位缺陷时,Sb、Bi掺杂对于Sn^(4+)形成的抑制效果更为显著.同时,低浓度的Sb、Bi掺杂不会改变CsSnI_(3)的直接带隙特性,且带隙宽度变化较小,因此能够在维持CsSnI_(3)优良光电活性的基础上进一步提高结构和电荷的稳定性.研究结果为实现高效且稳定的CsSnI_(3)钙钛矿太阳能电池提供了重要的理论指导.

Fe-doping induced Griffiths-like phase in La_(0.7)Ba_(0.3)CoO_3

The effect of Fe-doping on the magnetic properties of the ABO3-type perovskite cobaltites La0.7Ba0.3CoO3（0≤ y≤0.80） is reported. With no apparent structural change in any doped sample, the Curie temperature （Tc） and the magnetization （M） are greatly suppressed for y ≤0.30 samples, while a distinct increase in Tc for the y=0.40 sample is observed. With the further increase of Fe concentration, Tc increases monotonically. Griffiths-like phases in 0.40≤y ≤0.60 samples are confirmed. The formation of the Griffiths-like phase is ascribed to B-site disordering induced isolation of ferromagnetic （FM） clusters above Tc.

Phase Behavior of Rare Earth Manganites

Among complex oxides containing rare earth and manganese BaLn_2Mn_2O_7 (Ln=rare earth) with the layered perovskite type and Ln_2(Mn, M)O_7 with pyrochlore-related structure were studied since these compounds show many kinds of phases and unique phase transitions. In BaLn_2Mn_2O_7 there appear many phases, depending on the synthetic conditions for each rare earth. The tetragonal phase of so-called Ruddlesden-Popper type is the fundamental structure and many kinds of deformed modification of this structure are obtained. For BaEu_2Mn_2O_7 at least five phases have been identified from the results of X-ray diffraction analysis with the space group P4_2/mnm, Fmmm, Immm and A2/m in addition to the fundamental tetragonal I4/mmm phase. In the pyrochlore-related type compounds, Ln_2Mn_(2-x)M_xO_7 (M=Ta, Nb, W etc), there also appear several phases with different crystal structures. With regard to every rare earth, Ln_2MnTaO_7 phase is stable only for excess Ta and can be obtained under high oxygen partial pressure process. This group has trigonal structure with zirkelite type (P3_121 space group). On the other hand Ln_2Mn_(2/3)Nb_(4/3)O_7 phase has monoclinic (C2/c space group) and zirconolite type structure. All of these structural models have the fundamental structure based on HTB (hexagonal tungsten bronze) layers formed by the arrangement of oxygen octahedra.

Cr doping effect in B-site of La_(0.75)Sr_(0.25)MnO_3 on its phase stability and performance as an SOFC anode

La0.75Sr0.25CryMn1-yO3 （LSCM） （y = 0.0-0.6） composite oxides were synthesized by a complexing process of combining ethylene diamine tetraacetic acid （EDTA） and citrate. X-ray diffraction （XRD）, temperature-programmed reduction, electrical conductivity, I-V polarization, and impedance spectroscopy were conducted to investigate the Cr doping effect of La0.75Sr0.25MnO3 on its phase stability and electrochemical performance as a solid-oxide fuel cell （SOFC） anode. The chemical and structural stabilities of the oxides increased steadily with increasing Cr doping concentration, while the electrical conductivity decreased on the contrary. At y 〉 0.4, the basic perovskite structure under the anode operating condition was sustained. A cell with 0.5-ram-thick scandia-stabilized zirconia electrolyte and La0.75Sr0.25CryMn1-yO3 anode delivered a Dower density of -15 mW-cm^-2 at 850℃.

Oxygen permeability and CO_2-tolerance of Ce_(0.8)Gd_(0.2)O_(2-δ)-Ln BaCo_2O_(5+δ) dual-phase membranes

A series of oxygen permeable dual-phase composite oxides 60 wt% Ce0.8Gd0.2O2-δ-40 wt% LnBaCo2O5＋δ （CGO-LBCO, Ln = La, Pr, Nd, Sin, Gd and Y） were synthesized through a sol-gel route and effects of the Ln3＋ cations on their phase structure, oxygen permeability and chemical stability against CO2 were investigated systemically by XRD, SEM, TG-DSC and oxygen permeation experiments. XRD patterns reveal that the larger Ln3＋ cations （La3＋, Pr3＋ and Nd3＋） successfully stabilized the double-layered perovskite structure of sintered LBCO, while the smaller ones （Sm3＋, Gd3＋, and Y3＋） resulted in the partial decomposition of LBCO with some impurities formed. CGO-PBCO yields the highest oxygen permeation flux, reaching 2.8× 10^-7 mol.s-1.cm-2 at 925 ℃ with 1 mm thickness under air/He gradient. The TG-DSC profiles in 20 mol% CO2/N2 and oxygen permeability experiments with CO2 as sweep gas show that CGO-YBCO demonstrates the best chemical stability against CO2, possibly due to its minimum basicity. The stable oxygen permeation flux of CGO-YBCO under CO2 atmosphere reveals its potential application in the oxy-fuel combustion route for CO2 capture.

Effects of Thermal Conditions in the Phase Formation of Undoped and Doped Pb(Zr_1-xTi_x)O₃Solid Solutions

The purpose of this research is to study the effect of thermal conditions such as temperature ramp rate and isothermal times in the phase formation of Pb(Zr1-xTix)O3 solid solutions with composition near the morphotropic phase boundary (MPB) by using the conventional ceramic method. The perovskite phase formation and morphology of undoped Pb(Zr0.52Ti0.48)O3 (abbreviated PZT) and doped new material Pb0.98Gd0.02[(Zr0.52Ti0.48)0.98(Mg1/3Nb2/3)0.01(Ni1/3Sb2/3)0.01]O3 (abbreviated PZT-PGMNNS) specimens calcined between 700°C and 900°C have been examined by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and Fourier Transform Infrared (FTIR) while the thermal evolution of the initial precursor was followed by TG-DTA. So the results of these studies have been discussed.

Nanostructured Ceramics of Potassium Sodium Bismuth Titanate: Hydrothermal Synthesis and Piezoelectric Response at Morphotropic Phase Boundary

Potassium Sodium Bismuth Titanate (KNBT) ceramics, with the general formula (1 - x)K0.5Bi0.5TiO3 -xNa0.5Bi0.5TiO3, have been synthesized following hydrothermal route, starting with solid solutions of pure perovskite nanoceramics of KBT and NBT in desired stoichiometric weight ratios, followed by sintering between 850°C and 1000°C for few hours. Pure KNBT nanoceramics with perovskite structure, having mean particle size around 30 nm, could be obtained. Morphology of the samples is found to depend strongly on composition. A change of composition results in a phase change, as evident from X-ray structure analysis. This phase change is a result of rhombohedral to tetragonal morphotropic phase boundary (MPB) in the sample with x around 0.80. Composition dependent occurrence of MPB leads to formation of needle like structures with micrometer length scales. These are typical of tetragonal lamellar structures, suggesting partial induction of tetragonal polar order from rhombohedral structure at MPB. Dielectric and piezoelectric properties, such as dielectric constant and loss, piezoelectric coefficients and figures of merit, exhibit threshold maxima in their values at the composition corresponding to MPB. These values reported for a lead-free piezoceramic, synthesized by a comparatively simple hydrothermal route, are highly promising, and comparable to well-known PZT.

Review of magnetocaloric effect in perovskite-type oxides

We survey the magnetocaloric effect in perovskite-type oxides （including doped ABO3-type manganese oxides, A3B2OT-type two-layered perovskite oxides, and A2B＇B＇＇O6-type ordered double-perovskite oxides）. Magnetic entropy changes larger than those of gadolinium can be observed in polycrystalline La1-xCaxMnO3 and alkali-metal （Na or K） doped La0.8Ca0.2MnO3 perovskite-type manganese oxides. The large magnetic entropy change produced by an abrupt reduction of magnetization is attributed to the anomalous thermal expansion at the Curie temperature. Considerable mag- netic entropy changes can also be observed in two-layered perovskites Lal.6Cal.4Mn207 and La2.5-xK0.5＋xMn2O7＋6 （0 〈 x 〈 0.5）, and double-perovskite Ba2Fe1＋xMol-xO6 （0 〈 x 〈 0.3） near their respective Curie temperatures. Com- pared with rare earth metals and their alloys, the perovskite-type oxides are lower in cost, and they exhibit higher chemical stability and higher electrical resistivity, which together favor lower eddy-current heating. They are potential magnetic refrigerants at high temperatures, especially near room temperature.

Cation engineering on lead iodide perovskites for stable and high-performance photovoltaic applications

Perovskite solar cells （PSCs） based on methylammonium lead iodide （CH3NH3PbI3） have shown unprecedentedly outstanding performance in the recent years. Nevertheless, due to the weak interaction between polar CH3NH3＋ （MA＋） and inorganic PbI3 sublattices, CH3NH3PbI3 dramatically suffers from poor moisture stability, thermal decomposition and device hysteresis. As such, strong electrostatic interactions between cations and anionic frameworks are desired for synergistic improvements of the abovementioned issues. While replacements of I with Br and/or CI evidently widen optical bandgaps of perovskite materials, compositional modifications can solely be applied on cation components in order to preserve the broad absorption of solar spectrum. Herein, we review the current successful practices in achieving efficient, stable and minimally hysteretic PSCs with lead iodide perovskite systems that employ photoactive cesium lead iodide （CsPbI3）, formamidinium lead iodide （HC（NH2）2PbI3, or FAPbI3）, MA1-x y-zFAxCsyRbzPbI3 mixed-cation settings as well as two-dimensional butylammonium （C4H9NH3＋, or BA＋）/MA＋, polymeric ammonium （PEI＋）/MA＋ co-cation layered structures. Fundamental aspects behind the stabilization of perovskite phases α-CsPbi3, α-FAPbI3, mixed-cation MA1-x-y-zFAxCsyRb2PbI3 and crystallographic alignment of （BA）2（MA）3Pb4I13 for effective light absorption and charge transport will be discussed. This review will contribute to the continuous development of photovoltaic technology based on PSCs.

准二维钙钛矿发光二极管中的相调控研究

金属卤化物钙钛矿凭借其优异的光电性能和易于制备的特点,近年来在光电子学领域引起了广泛关注,被认为是具有广阔应用前景的革命性新型光电半导体材料。准二维钙钛矿作为其中一类重要材料,具有可调的光物理性质,包括更高的激子结合能、多重量子阱结构、自然级联能量漏斗和带隙可调性,这使其成为有前途的下一代发光二极管(Light-emitting diodes,LED)侯选材料。调控准二维钙钛矿的相分布是实现高效钙钛矿LED的关键。本文基于课题组的研究工作,深入讨论了通过精准调控相分布实现高效准二维钙钛矿LED的策略和应用。

钙钛矿LaNiO_(3)热烧结过程中相转变机理的研究

本文针对钙钛矿结构的LaNiO_(3)在热烧结过程中物相转变机制,利用离位及原位电镜结合宏观光谱进行了观测和分析研究。实验结果表明,通过静电纺丝法制备的PVP/PAN/Ni(NO_(3))_(2)/La(NO_(3))_(3)前驱体纤维能够通过高温烧结形成LaNiO3的钙钛矿结构。研究发现在温度作用下,晶体生长过程中碳聚合物基体不断受热分解,浸渍在聚合物基体上的金属离子受热与气氛中的氧结合,形成氧化物晶胚,呈现典型的奥斯瓦尔德熟化生长过程,在600℃左右,LaNiO_(3)的晶体相生成,随着温度的进一步升高,晶粒互相融合形成了纳米颗粒堆垛成的一维LaNiO_(3)纳米线。实验揭示了LaNiO_(3)纳米线的微观生长机制,为材料的生长调控和性能改性提供了思路。

钙钛矿相PbTiO_(3)-CdS微米片复合光催化剂的制备及其分解水产氢性能研究

为实现钙钛矿基半导体复合材料的高效光解水产氢,以钙钛矿相钛酸铅(PbTiO_(3),PTO)微米片为衬底,采用水热法制备钙钛矿相钛酸铅-硫化镉(PTO-CdS)微米片复合材料。探究水热温度和CdS负载量对复合材料的形貌及物相的影响;通过TEM、XPS及UV-Vis对复合材料的微结构、表面化学状态和光吸收特性进行表征;通过光解水产氢实验对复合材料的光催化活性进行测定和分析。结果表明:水热条件下,钙钛矿相PTO微米片对CdS的生长具有显著调控作用,与单独生长时尺寸约3μm的枝杈晶形貌不同,PTO-CdS微米片复合材料中的CdS为三角形纳米颗粒,尺寸约50 nm,均匀分散地生长在PTO微米片表面,且PTO与CdS之间界面清晰;水热温度和CdS负载量对复合材料的形貌和物相影响显著,水热温度为160℃、CdS负载量为6%时制备的PTO-CdS微米片复合材料尺寸均一,负载均匀,纯度和结晶度良好;PTO-CdS微米片复合材料在模拟太阳光下表现出光催化分解水产氢特性,其中PTO-CdS-6%的产氢速率达到141.45μmol/h/g,是PTO微米片产氢效率的17倍,是CdS枝杈晶产氢效率的53倍。该研究为高效钙钛矿基半导体复合光催化剂的设计提供了思路。

低温环境下PbTiO_(3)钙钛矿晶粒的演化过程

利用透射电子显微镜研究了PbTiO_(3)钙钛矿在低温条件下的晶体结构及晶粒演化过程。结果表明:低温条件下,PbTiO_(3)钙钛矿未出现明显的相转变;在电子束辐照条件下,PbTiO_(3)晶体出现细晶化现象,说明电子束对其结构变化存在诱导作用;在室温和低温环境下,PbTiO_(3)晶体均未产生位错缺陷,且低温环境使晶粒细化过程变慢;电子辐照作用使材料的表面能变大,导致晶粒尺寸变小,从而出现细晶化现象。