ZrO2-8mol%Dy2O3固体电解质燃料电池性能

将强碱介质中用水热法合成的立方相ZrO2-8mol％Dy2O3纳米晶在较低的温度（1400℃）下烧结,制得了导电性固体电解质陶瓷样品。以该陶瓷作为固体电解质,Pt作电极材料组成氢．空气燃料电池,测定了不同pH介质中水热反应产物纳米晶的陶瓷样品在800～1000℃下的燃料电池性能。结果表明,该系列陶瓷样品的燃料电池均具有稳定的放电性能,燃料电池的短路电流密度随着水热反应介质pH值的减小而增大。在该系列陶瓷中,水热反应介质pH=9．95的陶瓷样品的燃料电池性能最高,在1000℃下,其短路电流密度为320mA／cm^2。     

Laβ-Al2O3固体电解质的导电性能

用直接合成法制备了Ｌａβ－Ａｌ２Ｏ３固体电解质。利用阻抗谱测定其电导率,研究了电导率与温度及掺物含量的关系,在４５０－１０００℃温度下电导率为１０＾－６－１０＾２Ｓ·ｃｍ＾－１,活经能为０．８９ｅＶ。用Ｗｅｇｎｅｒ极化电池法测定了电子电导率,在５００－９００℃温度下电子电导率为１０＾－７－１０＾－５Ｓ·ｃｍ＾－１,活化能为０．７４ｅＶ。电子迁移数小于０．０１。     

磷灰石型低温固体电解质材料的研究进展

近年来,一种新的氧离子导体-磷灰石型氧化物被发现,其结构和氧离子传输方式都不同于目前已发现的几种氧离子导体(如萤石型ZrO2、钙钛矿型氧化物等),在低温下就显示出了高离子电导率和低活化能,使固体氧化物燃料电池在低温下工作成为可能.本文就近年来国外对磷灰石型电解质材料结构和性能的研究进展进行了综述.     

掺杂AI2O3的CeO2材料显微形貌观察

对掺杂ＡＩ２Ｏ３的Ｃｅ民解质材料表面及断口形貌进行了扫描电子同镜观察。实验,ＡＩ２Ｏ３可以起到有效的强化晶界作用,使用断裂形式由昌断裂变为穿晶断裂为主。分析认为,ＡＩ２Ｏ３的强化得由于两方面的因素造成的,首先是掺杂ＡＩ２Ｏ３传导主缩性应力,其次是晶界处的ＡＩ２Ｏ３使微裂纹偏转。     

Sm,Gd共同掺杂的CeO2基电解质性能研究

用Ｓｍ２Ｏ３和Ｇｄ２Ｏ３共同掺杂ＣｅＯ２基电解质组分（ＣｅＯ２）０．９０（Ｓｍ２Ｏ３）０．０５（Ｇｄ２Ｏ３）０．０５）,可以在较低的温度（１４００－１４５０℃）烧结并较高电导率,８００℃时电导率约为７Ｓ．ｍ＾－１。     

ZrO2固体电解质在金属熔体中的应用研究

本文简要介绍了ZrO2固体电解质的制作工艺、参比电极的选择、固体电解质的工作原理及其在冶金生产过程中的几项应用.着重讨论了冶炼的终点控制、含铝钢中氧的控制、钢液无污染脱氧以及连续定氧技术的应用等.     

Li_2O掺杂Li_(3x)La_(2/3-x)TiO_3固体电解质的制备及性能

用高温固相法合成了一系列不同组成的固体电解质Li3xLa2/3-xTiO3(LLTO,x=0.06,0.10,0.12,0.16,摩尔分数),研究了不同Li2O掺杂量对LLTO显微结构和电导率的影响。对样品进行X射线衍射和扫描电子显微镜分析,用交流阻抗技术测试其电导率。结果表明:LLTO为超结构的立方晶体,在LLTO(x=0.12)陶瓷中有Li0.485La0.505TiO3相产生;1150℃烧结的样品晶粒分布较均匀且大部分为球形,1250℃烧结的样品致密度较高,晶粒的形状均匀,为片状,x=0.06时,LLTO的电导率最大,其室温电导率为1.1×10-6S/cm。     

Co掺杂对Ce0．85Y0.15O2-δ固体电解质材料性能的影响

采用固相反应法合成并在不同温度下烧结Ce0.85Y0.15-xCoxO2-δ(x=0、0.01、0.03和0.05)固体电解质材料,着重研究Co掺杂量对试样的体积密度和离子电导率的影响.采用X射线衍射(XRD)分析烧结后试样的晶体结构,Archimedes法测定烧结试样密度,电化学阻抗谱测量试样的离子电导率.结果表明:试样Ce0.85Y0.15-xCoxO2-δ(x=0、0.01、0.03和0.05)1 400℃烧结后均呈单一的立方萤石结构相,掺杂Co可以有效提高试样的体积密度,促进试样烧结.此外,一定量的Co还可以增加试样的离子电导率,相同烧结条件下试样Ce0.85Y0.14Co0.01O2-δ呈现出最高的离子电导率,1 450℃烧结,其离子电导率在800℃时达到0.083 1 s/cm.     

固体氧化物燃料电池电解质材料的研究进展

固体氧化物燃料电池(SOFC)被誉为21世纪最具有发展潜力的能源材料之一,它的热效率高、燃料的适应性强,能很好地满足区域供电、供热的需要,具有重要的经济和社会意义。本文综述了SOFC电解质的研究进展,指出在诸多的电解质材料中,尽管氧化铋系电解质拥有最高的电导率,但由于其化学稳定性很差,难以获得广泛的应用;氧化钇全稳定的氧化锆(YSZ)由于其中低温的电导率较低,只适用于高温SOFC;稀土掺杂的氧化铈和LaGaO3钙钛矿材料拥有较高的中低温电导率,性质较为稳定,是适用于中低温SOFC的电解质材料。     

Preparation of ZrO2/Gd2O3 composite ceramic materials by coprecipitation method

High burnup is a goal for further development of advanced nuclear power in the future. However, along with the increase of burnup, it becomes more diffidult to control reactor reactivity, which affects the operation safety of the nuclear reactor. Al₂O₃/B₄C burnable poison materials widely used in pressurized water reactor currently will not meet the requirements of burnable poison materials in high burnup nuclear power. Because of the better performance of ZrO₂/Gd₂O₃ burnable poison materials than that of Al₂O₃/B₄C, this paper studies the preparation of ZrO₂/Gd₂O₃ composite ceramic materials by the coprecipitation method. The experimental results show that at the sintering temperature of 1500–1650 °C, ZrO₂/Gd₂O₃ composite ceramic grains are small, compact and uniform with the generation of homogeneous solid solution. At 1600 °C, ZrO₂–10%Gd₂O₃ has the highest density and mechanical strength.     

Enhancement of density and ionic conductivity for garnet-type Li5La3Ta2O12 solid electrolyte by self-consolidation strategy

Garnet-type Li₅La₃Ta₂O₁₂ (LLTaO) solid electrolyte is a potential candidate component for future all-solid-state batteries due to its extraordinary stability against the reaction with molten lithium. In contrast with traditional cold isostatic pressing (CIP) method, which generally pursues ultra-high pressure, this paper tries to enhance the density and ionic conductivity of LLTaO by self-consolidation strategy without the assistance of any pressing operations. A LLTaO bulk with a relative density of 95% is obtained. SEM images reveal that the bulk sample is assembled by large dense particles in size of tens of microns indicating that the interstitial space among the particles has been dramatically minimized. Accordingly, the total ionic conductivity and the bulk ionic conductivity at 30?°C are promoted up about one order of magnitude higher to 2.63?× 10^?5 S?cm^?1 and 1.41?×?10^?4 S?cm^?1, respectively. Moreover, the lithium ionic migration network in the crystalline unit cell of LLTaO is first explored from its assembled way. A hexagon-like basic unit with tetrahedral Li1 joint sites and Li1- - Li1 edges is identified. The tetrahedral Li1 sites act as crucial junctions for the transportation of lithium ions. This work would significantly stimulate the development of LLTaO electrolyte membrane technology.     

Laser stereolithography of ZrO2 toughened Al2O3

Ceramic laser stereolithography is a manufacturing process suitable candidate for the production of complex shape technical ceramics. The green ceramic is produced layer by layer through laser polymerisation of UV curable ceramic suspensions. A number of critical issues deserve attention: high solid loading and low viscosity of the suspensions, high UV reactivity, prevention of interlayer delamination in the green and in the sintered body, good mechanical performance. In this work, ZrO₂-reinforced Al₂O₃ components have been obtained from an acrylic modified zircon loaded with alumina powders. The zircon compound is effective as organic photoactivated resin and allows the dispersion of a high volume fraction of Al₂O₃ powder (up to 50 vol.%) while keeping viscosity at reasonable low values. The zircon compound also represents a liquid ceramic precursor that converts to oxide after burning out of the binder. Thank to the good dispersion of the alumina powder in the zircon acrylate, a uniform dispersion of ZrO₂ submicron particles is obtained after pyrolysis. These are located at the grain boundaries between alumina grains. Formation of both monoclinic and tetragonal ZrO₂ occurs as evidenced by XRD. No delamination occurs in bending tests as evidenced by SEM fractography, satisfactory modulus and strength values were concurrently found.     

Mechanical properties of Al2O3/ZrO2 composites

In the present study, both t-phase zirconia and m-phase zirconia particles are incorporated into an alumina matrix. Dense Al₂O₃/(t-ZrO₂+m-ZrO₂) composites were prepared by sintering pressurelessly at 1600 °C. The microstructure of the composites are characterized, the elastic modulus, strength and toughness determined. Because the ZrO₂ inclusions are close to each other in the Al₂O₃ matrix, the yttrium ion originally in t-ZrO₂ particles can diffuse to nearby m-ZrO₂ particles during sintering, and the m-phase zirconia is thus stabilized after sintering. The strength of the Al₂O₃/(t-ZrO₂+m-ZrO₂) composites after surface grinding can reach values as high as 940 MPa, which is roughly three times that of Al₂O₃ alone. The strengthening effect is contributed by microstructural refinement together with the surface compressive stresses induced by grinding. The toughness of alumina is also enhanced by adding both t-phase and m-phase zirconia, which can reach values as high as two times that of Al₂O₃ alone. The toughening effect is attributed mainly to the zirconia t–m phase transformation.     

Yb2O3 and Gd2O3 doped strontium zirconate for thermal barrier coatings

Yb₂O₃ (10 mol%) and Gd₂O₃ (20 mol%) doped SrZrO₃ was investigated as a material for thermal barrier coating (TBC) applications. The thermal expansion coefficients (TECs) of sintered bulk Sr(Zr_0.9Yb_0.1)O_2.95 and Sr(Zr_0.8Gd_0.2)O_2.9 were recorded by a high-temperature dilatometer and revealed a positive influence on phase transformations of SrZrO₃ by doping Yb₂O₃ or Gd₂O₃. The results for the thermal conductivities of Sr(Zr_0.9Yb_0.1)O_2.95 and Sr(Zr_0.8Gd_0.2)O_2.9 indicated that both dopants can reduce the thermal conductivity of SrZrO₃. Mechanical properties (Young's modulus, hardness, and fracture toughness) of dense Sr(Zr_0.9Yb_0.1)O_2.95 and Sr(Zr_0.8Gd_0.2)O_2.9 showed lower Young's modulus, hardness and comparable fracture toughness with respect to YSZ. The cycling lifetimes of Sr(Zr_0.9Yb_0.1)O_2.95/YSZ and Sr(Zr_0.8Gd_0.2)O_2.9/YSZ double layer coatings (DLC), which were prepared by plasma spraying, were comparable to that of YSZ at operating temperatures <1300 °C. However, the cycling lifetime of Sr(Zr_0.9Yb_0.1)O_2.95/YSZ DLC was 25% longer, whereas Sr(Zr_0.8Gd_0.2)O_2.9/YSZ DLC had a shorter lifetime compared to the optimized YSZ coating at operating temperatures >1300 °C.     

Effect of ZrO2 on phase transformation of Al2O3

This study investigates the effect of ZrO₂ on phase transformation of alumina. Alumina and alumina–zirconia composite powders were produced by the precipitation method from aluminum sulfate and zirconium sulfate precursors. Precipitates obtained at 15 °C were dried at 80 °C for 72 h, and then calcinated at four different temperatures; 1000 °C, 1100 °C, 1200 °C and 1300 °C for 1 h. Powders calcinated at 1300 °C were pressed uniaxially and sintered at 1600 °C for 1 h. XRD and DSC analyses showed that the presence of zirconia retarded the transformation to α-alumina. SEM studies on the powders calcinated at 1300 °C revealed that both alumina and alumina–zirconia particles were 100–300 nm in size and of near spherical shape. Zirconia additions inhibited abnormal grain growth of alumina and provided homogeneous, equaxied grain structure.     

Aging-induced change of photoluminescence in yttria-fully-stabilized ZrO2 with Sc2O3 or In2O3 doping

We report on the photoluminescence properties of Sc₂O₃- or In₂O₃-doped yttria-fully-stabilized zirconia (YSZ) by sub-bandgap photo-excitation to localized electronic states of oxygen vacancies, in order to clarify the mechanism for the aging-induced decrease of ionic conductivity via vacancies known in YSZ and suppressed by such doping. A new band emerged at 2.70 eV and remained even after the aging for the Sc₂O₃-doped samples at the doping concentration whereof the conductivity decrease was suppressed. On the other hand, a sharp and singular increase of the photoluminescence intensity was observed for the In₂O₃-doped samples at the range of the dopant concentration wherein a singular conductivity drop was observed and the suppression of conductivity decrease started. It is suggested that the suppression mechanism is different between Sc₂O₃-doped YSZ (Sc-YSZ) and In₂O₃-doped YSZ (In-YSZ).     

Transient studies of carbon dioxide reforming of methane over Pt/ZrO2 and Pt/Al2O3

The mechanism of the CO₂ reforming of methane reaction over the Pt/ZrO₂ catalyst was investigated using a temporal analysis of products (TAP) reactor system. For comparative purposes, the reaction pathway using a Pt/Al₂O₃ catalyst was also examined. A reaction sequence is suggested for both catalysts. Over both catalysts, methane decomposition takes place over platinum. The main difference between the two catalysts concerns the carbon dioxide dissociation. Over Pt/Al₂O₃ this step is assisted by hydrogen. Over Pt/ZrO₂ this step takes place over the zirconia support and involves surface vacancies. Moreover, large pools of formate and carbonate species are present on the zirconia. Transient studies conducted to determine the origin of carbon species accumulated during CO₂ reforming revealed that more than 99% of the carbon was derived from the methane molecule over both catalysts. Over the Pt/ZrO₂ catalyst, only a single very reactive carbon species was detected, while over the Pt/Al₂O₃ a second less active species was also formed.     

Preparation and properties of ceramic composites with oxygen ionic conductivity in the ZrO2-CeO2-Al2O3 and ZrO2-Sc2O3-Al2O3 systems

Powder precursors in the ZrO₂-CeO₂-Al₂O₃ and ZrO₂-Sc₂O₃-Al₂O₃ systems are prepared by the sol-gel synthesis. It is revealed that the electrical conductivity of the sample doped with scandium oxide is higher than the electrical conductivity of the sample doped with cerium oxide despite the higher content of the nonconducting phase Al₂O₃ (corundum). The thermal expansion coefficients are determined for all the ceramic samples under investigation. It is established that the Al₂O₃ dopant affects the thermal expansion coefficient. The ceramic materials studied can be used as solid-electrolyte sensors. Original Russian Text ? P.A. Tikhonov, M. Yu. Arsent’ev, M.V. Kalinina, L.I. Podzorova, A.A. Il’icheva, V.P. Popov, N.S. Andreeva, 2008, published in Fizika i Khimiya Stekla.     

The influence of pentavalent Nb substitution for Zr on electrical property of oxide-ion conductor Gd2Zr2O7

Gd₂(Zr_1−xNb_x)₂O_7+x (0 ≤ x ≤ 0.2) ceramics are prepared via the solid state reaction process at 1973 K for 10 h in air. Gd₂(Zr_1−xNb_x)₂O_7+x (x = 0.1, 0.2) ceramics exhibit an ordered pyrochlore-type structure, whereas Gd₂Zr₂O₇ has a defective fluorite-type structure. The electrical property of Gd₂(Zr_1−xNb_x)₂O_7+x ceramics is investigated by electrochemical impedance spectroscopy over a frequency range of 10 Hz to 8 MHz from 623 to 923 K. The electrical conductivity obeys the Arrhenius equation. The grain conductivity of Gd₂(Zr_1−xNb_x)₂O_7+x ceramics varies with doping different Nb contents, and exhibits a maximum at the Nb content of x = 0.1 in the temperature range of 623-923 K. The conductivity in hydrogen atmosphere is a little bit higher than in air in the temperature range of 723-923 K, which indicates that the doping of Zr⁴⁺ by Nb⁵⁺ can increase the proton-type conduction and reduce the oxide-ionic conduction. The conduction of Gd₂(Zr_1−xNb_x)₂O_7+x is not a pure oxide-ionic conductor.