Preparation and performance of Pr-doped Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ) cathode for IT-SOFCs

(Ba0.5Sr0.5)1-xPrxCo0.8Fe0.2O3-δ(BSPCFx;x=0.00-0.30) oxides were synthesized by a sol-gel thermolysis process using combination of PVA and urea,and were also investigated as cathode material for intermediate temperature solid oxide fuel cells(IT-SOFCs).X-ray diffraction(XRD) results showed that all the samples formed a single phase cubic pervoskite-type structure after being calcined at 950 oC for 5 h and the lattice constant decreased with the Pr content increasing.The electrical conductivity of Ba0.5Sr0.5Co0.8Fe0.2O3-δ(BSCF) was greatly enhanced by Pr-doping.The thermal expansion coefficient(TEC) of BSPCFx was increased with the content of Pr increasing,and all the thermal expansion curves had an inflection at about 250-400 oC due to the thermal-induced lattice oxygen loss and the reaction of Co and Fe ion.Ac impedance analysis indicated that BSPCFx possessed better electrochemical performance.The polarization resistance of the sample with x=0.2 was only ～0.948 Ω cm2 at 500 oC,significantly lower than that of BSCF(～2.488 Ω cm2).     

Preparation and characterization of La0.9Sr0.1Ga0.8Mg0.2O3–δ thin film deposited by radio frequency magnetic sputtering

La0.9Sr0.1Ga0.8Mg0.2O3-δ (LSGM) electrolyte materials were synthesized by the solid state reaction method.The conductivity of LSGM materials was detected by four probe method,and it was 0.08 S/cm at 850 ℃.Dense and uniform films of LSGM materials were deposited by the magnetic sputtering on substrates of Si and La0.7Sr0.3Cr0.5Mn0.5O3-δ (LSCM).The experimental results showed that the deposition rates dropped and the average grain sizes of the films enlarged with increase in the substrate temperatures.In the sputtering process,the LSGM film was deposited with preferred growth direction.After annealing,the preferred growth direction disappeared and the film surface became smoother and denser.Through observing the deposition process,deposition mechanism was proposed,which was consistent with a model of island growth.     

Synthesis kinetics and thermophysical properties of La_2（Zr_（0.7）Ce_（0.3））_2O_7 ceramic for thermal barrier coatings

La2(Zr0.7Ce0.3)2O7 (LZ7C3) ceramic was synthesized by solid state reaction with La2O3, ZrO2 and CeO2 as starting materials. The synthesis kinetics, phase structure, mass loss and microstructure were studied by thermo gravimetric-different thermal analyzer (TG-DTA), X-ray difference (XRD) and scanning electron microscopy (SEM). The thermal conductivity and thermal expansion coefficient were measured by laser-flash method and pushing-rod method, respectively. XRD results showed that LZ7C3 was a mixture of La2Zr2O7 (LZ, pyro- chlore) and La2Ce2O7 (LC, fluorite). The lowest synthesis temperature and time of LZ7C3 were 1400 oC and 5 h. There were no peaks of La2O3 when the powder granularity was about 0.82 μm in the synthesis process. The atom ratio La:Zr:Ce of prepared LZ7C3 powder was very close to 10:7:3 which was the theory value of LZ7C3. The thermal conductivity of LZ7C3 decreased gradually with the temperature increased up to 1200 oC, and was located within 0.79 to 1.02 W/(m·K), which was almost 50% lower than that of LZ, whereas its thermal expansion coefficient was larger and the value was 11.6×10-6 K-1.     

Effect of samarium doped ceria nanoparticles impregnation on the performance of anode supported SOFC with(Pr_(0.7)Ca_(0.3))_(0.9)MnO_(3-δ) cathode

Solid oxide fuel cell(SOFC) electrodes,after a high temperature sintering,may be impregnated to deposit nanoparticles within their pores to enhance the catalytic function.Samarium doped CeO2(SDC) nanoparticles were infiltrated into(Pr0.7Ca0.3)0.9MnO3-δ(PCM) cathode of anode supported SOFC cells.The cell with 2.6 mg/cm2 SDC impregnated in cathode showed the maximum power density of 580 mW/cm2 compared with 310 mW/cm2 of the cell without impregnation at 850 °C.The cells were also characterized with the impedance spectra,and the SDC impregnation significantly reduced the polarization resistance.After performance test the cells were characterized with scanning electron microscopy(SEM),and the cathode morphology showed the impregnated SDC particles were nanosized and were deposited on the surface of the PCM framework.The possible mechanism for the performance improvement was discussed.     

(Zn,Ca) Solid-Solution Behavior and Its Effect on Luminescence Properties in Ca_(1-x)Zn_xTiO_3∶0.002Pr~(3 ) Phosphors

Compared withthe classical sulfides MS∶Eu2 (M=Ca,Sr,Ba)red phosphor and ZnS∶Eu2 greenphosphor,the alkali-earth aluminate phosphors havesuperior blue-green long afterglowproperties,such asblue phosphors CaAl2O4∶(Eu2 ,Nd3 ),green phos-phor SrAl2O4∶(Eu2 …     

Synthesis and electrochemical properties of Ce-doped LiNi_（1/3）Mn_（1/3）Co_（1/3）O_2 cathode material for Li-ion batteries

The layered material of Ce-doped LiNi1/3Mn1/3Co1/3O2 with α-NaFeO2 was synthesized by a co-precipitation method. X-ray diffraction (XRD) showed that Ce-doped LiNi1/3Mn1/3Co1/3O2 had the same layered structure as the undoped LiNi1/3Mn1/3Co1/3O2. The scanning electron microscopy (SEM) images exhibited that the particle size of Ce-doped LiNi1/3Mn1/3Co1/3O2 was smaller than that of the undoped LiNi1/3Mn1/3Co1/3O2. The Ce-doped LiNi1/3Mn1/3Co1/3O2 samples were investigated on the Li extraction/insertion performances through charge/discharge, cyclic voltammogram (CV), and electrochemical impedance spectra (EIS). The optimal doping content of Ce was x=0.02 in the LiNi1/3-xMn1/3Co1/3CexO2 samples to achieve high discharge capacity and good cyclic stability. The electrode reaction reversibility was enhanced, and the charge transfer resistance was decreased through Ce-doping. The improved electrochemical performances of the Ce-doped LiNi1/3Mn1/3Co1/3O2 cathode materials were attributed to the addition of Ce4+ ion by stabilizing the layer structure.     

Study on Rare Earth Electrolyte of Ce_(0.9)RE_(0.1)O_(2-δ) (RE=Pr, Nd, Sm, Gd, Dy)

Thesolidelectrolyteisakeycomponentofsolidoxidefuelcell (SOFC) .Dopedceriaisoneofpromis inghigh conductingsolidelectrolyteinSOFC[1,2 ] .Butitiswell knownthatitisdifficulttosinterdopedceriabysolidstatereactioninair .TheCe0 .9RE0 .1O2 -δelectrolytematerialswerepreparedbythesol gelmethod .Thesinteringtemperatureofthesamplescandecreasetoabout 4 0 0K .Theionicconductivityandlinearthermalexpansionpropertiesofsol gelpreparedCe0 .9RE0 .1O2 -δinawidetemperaturerangewerein vestigated .Thepowder…     

Synthesis and characterization of Ce_(0.6)Sr_(0.4)Fe_(0.8)Co_(0.2)O_(3–δ) perovskite material:Potential cathode material for low temperature SOFCs

A sol-gel method and a modified chemical vapour deposition technique were used to produce nanostructured Ce_(0.6)Sr_(0.4)Fe_(0.8)Co_(0.2)O_(3–δ) materials at temperatures as low as 400 °C. Powders were characterized using Fourier transform infrared spectroscopy(FTIR), Raman spectroscopy, thermo gravimetric analysis, powder X-ray diffraction(XRD), scanning electron microscopy(SEM) with energy dispersive X-ray spectroscopy, high resolution transmission electron microscopy(HRTEM), and nitrogen sorption at 77 K. FTIR spectra showed that the sol-gel method resulted in residual carbon groups on the materials after calcination, while the Raman and XRD analysis confirmed that both synthesis methods resulted in cubic perovskite structure. However, the chemical vapour deposition(CVD) method resulted in materials with a smaller crystallite size when compared to those prepared via the sol-gel route. The overall morphology of the powders was irregularly shaped aggregated particles as observed by SEM and HRTEM. In addition, HRTEM analysis showed that the materials were highly crystalline. Textural analysis revealed the powders had some mesoporosity, and the surface areas were 76.69 and 65.90 m~2/g for materials synthesized using the CVD and sol-gel methods, respectively. The synthesized perovskite powders were used to fabricate button cells employing samarium doped ceria(SDC) as the electrolyte and NiO/SDC as the anode materials. As cathode materials, the maximum power density observed was 308.4 mW/cm~2 at 500 oC.     

Study on Preparation and Electrical Properties of Ba_(1.03)Ce_(0.8)Eu_(0.2)O_(3-α) Solid Electrolyte

SomeBaCeO3 basedsolidoxideelectrolytesdopedwithrareearthshavearousedmuchinterestow ingtotheirspecialdefectstructuresandgoodprotonicconductivities.Theyhaveavastrangeofperspectiveforapplicationsaselectrolytesinhydrogen airfuelcell;hydrogensensor ;preparation ,separationandpurificationofhydrogen ;hydrogenationanddehydro genationofsomeorganiccompounds ;andammoniasynthesisatatmosphericpressureandintermediatetemperature ,etc .[1～ 3] .TheperformancesofBaxCe1-yREyO3-αhavecloserelationtothecontent…     

ABO_3型稀土复合氧化物结构特征和导电性的研究

用Ｘ－射线光电子能谱（ＸＰＳ）对钙钛矿型稀土复合氧化物ＬａＭＯ３（Ｍ＝Ｃｒ、Ｆｅ、Ｃｏ、Ｎｉ）的结构性质进行了表征，发现ＬａＭＯ３中金属离子Ｍ的ｄ电子具有程度不同的离域性，且随着Ｍ的不同，离域程度递变规律为ＬａＮｉＯ３＞ＬａＣｏＯ３＞ＬａＣｒＯ３＞ＬａＦｅＯ３，这与其导电性大小顺序相一致。     

Structure and Electrical Conductivity of Compositely Doped Oxide Solid Electrolyte La0.8Sr0.2Ga0.8Mg0.12Co0.08O2.8

(La, Sr) (Ga, Mg) O3-δ, (LSGM) perovskite compositions doped with transition metal Co on the B-site were prepared by solid state reaction. The effect of partial substitution of Ga for Co, La0.8Sr0.2Ga0.8Mg0.12Co0.08O2.8 (LSGMC2008) on the electrical conductivity was discussed. The results showed the compacted samples sintered at 1350℃ possesses increased electrical conductivity at low temperatures. The XRD patterns of the title materials indicated that LSGMC2008 possessed orthorhombic perovskite-type structure. The grains distributed relatively uniform from SEM photo. The Arrhenius plots of ionic conductivity in air of the LSGMC2008 exhibited differing slopes in the low-and high-temperature regions, and the corresponding Ea values were much lower than that of LSGM2020. All of these suggested that even at low sintering temperature, proper amount Co doped was beneficial to improve ionic conductivity of LSGM.     

稀土复合掺杂钙钛矿型阴极材料制备工艺的研究

采用传统固相反应法制备了中温固体氧化物燃料电池中的稀土复合掺杂钙钛矿型阴极材料。借助XRD、DTA、SEM等分析仪器研究和讨论了不同元素、不同成分、不同焙烧温度、不同保温时间对所制备材料性能的影响。结果表明:该类材料的固相反应温度范围为:1000℃～1300℃;适宜的保温时间为10h;反应物经混合、压片、烧成和研磨可以合成晶粒尺寸为1nm～5nm的粉料,对ABO3型LaMnO3进行复合掺杂,表明A位Sr2+、Ca2+共同掺杂取代部分La3+以及B位Co3+、Fe3+双掺杂都能够提高材料的电导率。     

Phase Behavior and Crystal Structure of Perovskite-Type Rare Earth Complex Oxides

Several compounds of rare earth complex oxides containing manganese and titanium were synthesized in Ar, and their crystal structures were analyzed by powder X-ray diffraction data and Rietveld method. Structures of A0.67Ln0.33 Mn0.33Ti0.6703（A = Ca or Sr and Ln = rare earth） were found to have orthorhombic symmetry with the space group Pnrna, and their interatomic distances and bond angles were obtained. This space group was also derived from electron microscopic study. Electrical conductivity of Cao.67Ln0.33Mn0.33Ti0.6703 for several rare earth elements showed a semiconducting property with the activation energy of 0.4 eV. Some of these compounds of the strontium system show the antiferromagnetic properties below 10 K.     

Phase Behavior of Rare Earth Manganites

Among complex oxides containing rare earth and manganese BaLn2Mn2O7(Ln=rare earth) with the layered perovskite type and Ln2(Mn,M)O7 with pyrochlore-related structure were studied since these compounds show many kinds of phases and unique phase transitions. In BaLn2Mn2O7 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 BaEuzMn207 at least five phases have been identified from the re-sults of X-ray diffraction analysis with the space group P42/mnm, Fmmm, Immm and A2/m in addition to the fundamental tetragonal 14/mmm phase. In the pyrochlore-related type compounds, LnzMn2-xMxO7(M=Ta,Nb,W etc),there also appear several phases with different crystal structures. With regard to every rare earth, Ln2MnTaO7 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 (P3121 space group). On the other hand Ln2Mn2/3Nb4/307 phase has monoclinic (C2/c space group)and zireonolite 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.     

掺杂稀土离子钨酸盐的固相合成及发光特性研究进展

本文从单钨酸盐、混合碱土金属钨酸盐、氟钨酸盐、同多钨酸盐、杂多钨酸盐等方面综述了掺杂稀土离子钨酸盐的固相合成及发光特性研究进展。     

邻苯二甲酸与氯化稀土配合物的固相合成及性质研究

应用低温固相反应法合成了稀土氯化物和邻苯二甲酸的三种配合物,并对它们进行了组成分析、TG-DTA、红外光谱、荧光光谱和摩尔电导等的测定,确定配合物的组成为RE2(HL)3C l3.16H2O(RE=N d,Eu,T b;HL=o-C6H4(COOH)(COO-)),与文献报道的液相反应所得的产物组成不同[1,2]。从配合物的荧光激发和发射光谱可以发现,铕、铽的邻苯二甲酸配合物均具有很好的发光性能,且铽的发光性能比铕的发光性能更好。另外,溶解性实验表明配合物可以溶于水、乙醇,不溶于乙醚、丙酮。     

Magnetic Behavior of Some Rare-Earth Transition-Metal Perovskite Oxide Systems

Magnetic properties were investigated for the rare-earth 3d-transition metal oxides with the perovskite structure. Intriguing magnetic phenomena were reviewed for a few systems:magnetization peak effect in the titanates, magnetization reversal in the chromites and metallic ferromagnetism in the cobahites. The results suggest an important role of the rare-earth ions for the magnetic properties of such complex oxides.     

Crystal structure and thermal expansion of perovskites containing uranium（VI） and rare-earth elements

By the method of high-temperature reactions in solid phase, compounds with the general formula MII(AIII2/3U1/3)O3 (MII=Sr, AIII=Sc, In; MII=Ba, AIII=Sc, In, Y, Nd-Lu) were synthesized. Their structures (space groups Fmm and Pnma) were refined by the Rietveld method and morphotropic transition in Ba(Ln2/3U1/3)O3 on the border of Gd-Tb was discovered. By means of high-temperature X-ray diffraction, phase transitions were studied and thermal expansion coefficients were determined.     

混合稀土氧化物微粉的制备与表征

用氨水调ｐＨ共沉淀法制备混合稀土氧化物微细粉末。初步探讨了制备工艺中的有关影响因素，对粉末进行了热重、差热、扫描电镜、红外光谱等表征。结果表明：在选定的条件下，制得了粒径为１～２μｍ的混合稀土氧化物微粉。