化学及纳米掺杂氧化锆材料的性能与应用

对化学及纳米掺杂的ZrO2材料，从它们的晶体结构、相变规律、离子导电机制和材料性能等及其应用进行了较全面的综述，分析了不同掺杂对ZrO2材料的烧结性能、电性能以及其他热物理性能的影响。结果表明：通过化学掺杂不同价态、不同含量的氧化物使ZrO2的各项性能得到显著改善，通过纳米掺杂可以提高ZrO2材料的烧结性能，降低晶粒电阻，提高材料的离子导电性能。另外还对ZrO2作为结构和功能材料在金属熔体及气体定氧的氧传感器、脱氧剂、燃料电池以及超高温陶瓷发热元件等不同领域的应用情况进行了概述。     

Synthesis and Electrical Conductivities of Sm2O3-CeO2 Systems

Solidoxidefuelcell(SOFC)hasattracteda greatattentionasapromisingtechniqueforelectrical powergeneration[1].Thecurrentstate of the art SOFCsusesyttriastabilizedzirconia(YSZ)electro lyte,operatesat800～1000℃duetothelowoxy genionicconductivityoftheYSZelect…     

固体氧化物燃料电池中的电解质

综述了固体氧化物燃料电池（SOFC）中固体电解质的研究概况,分析了ZrO2基、CeO2基、Bi2O3基固体电解质和掺杂的LaGaO3为代表的钙钛矿结构的固体电解质的优缺点以及作为SOFC电解质存在的问题,中低温度下稳定的高离子电导率的固体电解质的研制开发及固体电解质的薄膜化研究是降低S0FC工作温度的两个重要途径。     

稀土氧化物LnO1.5掺杂CeO2-δ固体电解质的缺陷与电导率

利用缺陷化学的知识,对定量求解稀土氧化物LnO1.5掺杂CeO2-δ固体电解质中氧离子空位的浓度进行了初步探讨.在此基础上,推导出了该固体电解质的离子电导率和电子电导率的表达式.并且得出了计算CeO2基固体电解质临界氧分压P*O2的公式,利用该公式对两个问题进行了简单分析.     

CeO2基固体电解质材料研究进展

稀土或碱土氧化物掺杂铈基电解质在中低温下具有高的离子电导率,被认为是一种很有前途的电解质材料.本文主要对各种掺杂铈基电解质材料研究及在固体氧化物中的应用进行了综述.对掺杂铈基电解质的制备方法进行简单介绍.     

Conductivity improvement of Ce0.8Gd0：2O1.9 solid electrolyte

Solid oxide fuel cells based on doped ceria electrolytes offer operating temperatures of 600 °C. During recent years much attention was aimed at successful powder preparation with high sinter activity and high conductivity. The properties of ceria electrolyte are very sensitive to impurities introduced during powder and electrolyte fabrication. One of the most successful and commercially available processes for the production of clean powders is based on the addition of several percent metallic cations that will react with impurities and segregate into the triple points of grain boundaries. In this work the results obtained from doping of CGO20 by 2% Ca and prepared by different routes were presented. The way of introducing Ca seemed to play an important role.     

LiF掺杂提升Li1.1Ta0.9Zr0.1SiO5固态电解质室温离子电导率

LiTaSiO₅（LTSO）是一种新型的快离子导体,但现今合成的该电解质样品室温离子电导率较低。采用固相合成法制备了Li_1.1Ta_0.9Zr_0.1SiO₅固态电解质, 研究LiF掺杂对Li_1.1Ta_0.9Zr_0.1SiO₅电解质材料结构和性能的影响。结果表明,LiF掺杂能改善晶体的结晶性能,促进晶体的生长和降低晶界的数量,并显著降低孔隙率,提高电解质样品的致密度,从而降低电解质样品的晶粒和晶界电阻,有利于锂离子在晶粒和晶界之中快速迁移,提高材料的整体离子电导率。当LiF加入量为0.4%（质量百分比）时,Li_1.1Ta_0.9Zr_0.1SiO₅电解质的相对密度达90.81%,总离子电导率为8.31×10-5 S/cm,扩散激活能为0.203 eV,比未掺杂样品的离子电导率高近2倍。      

Study of Bi_2O_3-based Rare Earth Solid Electrolyte Used in Fuel Cell

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锂空气电池固体电解质Li_(1+x)Al_xTi_(2-x)(PO_4)_3的制备研究

以Li_2CO_3、Al_2O_3、TiO_2、NH_4H_2PO_4为原料,采用固相烧结法制备锂空气电池固体电解质Li_(1+x)Al_xTi_(2-x)(PO_4)_3(LATP),研究了不同x值、不同烧结温度对电解质性能的影响。通过X射线衍射仪(XRD)、扫描电镜(SEM)和电化学阻抗谱(EIS)对所制备电解质的结构与性能进行表征。结果表明在x值等于0.2时得到纯相的LATP,最佳烧结工艺是350℃保温2 h,600℃保温2 h,1 000℃保温8 h,室温下的电导率为4.89×10~(-5)S/cm。     

CeO_2基固体氧化物燃料电池电解质研究

固体氧化物燃料电池(SOFCs)被誉为21世纪最具有发展潜力的能源技术之一.由于用稀土或碱土金属氧化物掺杂的CeO2在较低的温度下具有较高的氧离子电导率,是用作中低温固体氧化物燃料电池较理想的电解质材料.本文综述了近年来以掺杂的CeO2作电解质的SOFCs性能的研究情况,总结了提高、改善CeO2基固体电解质电性能的几种方法,并对今后的研究提出了自己的看法.     

Study on Electrolytes (CeO_2 )_( 0.7-x) (MO) _x (La_2O_3)_(0.3)(M=Mg,Ca, Sr)

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ZrO2基中温固体电解质材料的制备和性能研究

采用无机胶化工艺制备了球状的、分散性好且粒度分布较窄的几种ZrO2基粉末.经干压成型和烧结后制备成陶瓷质电解质材料.通过XRD显微结构等分析,显示所得的样品均为立方相结构.在1 450℃烧结的样品已近完全致密.1 450～1 550℃烧结的8YbSZ在450 ～700℃测试范围内具有比其他的ZrO2基材料更高的离子电导...     

钙钛矿型锂离子固体电解质Li2x?ySr1?xTi1?yNbyO3的性能

采用高温固相法成功制备了Li_2x?ySr_1?xTi_1?yNb_yO₃ (x=3y/4, y=0.25, 0.5, 0.6, 0.7, 0.75, 0.8)锂离子固体电解质,并通过X射线衍射（XRD）、扫描电子显微镜（SEM）、交流阻抗图谱、恒电位极化等分别研究了各个组分的晶体结构、微观形貌、离子电导率和电子电导率。XRD显示当y≤0.70时,材料为立方钙钛矿型结构,几乎没有杂质相生成。SEM表明随着掺杂含量的增加材料的晶粒尺寸逐渐增大。Li_0.35Sr_0.475Ti_0.3Nb_0.7O₃锂离子固体电解质有着高离子电导率,为3.62×10?5 S·cm?1,其电子电导率为2.55×10?9 S·cm?1,活化能仅为0.29 eV。使用以Li_0.35Sr_0.475Ti_0.3Nb_0.7O₃为隔膜的LiFePO₄/Li半电池经过100圈循环后,放电比容量仍有93.9 mA·h·g?1,容量保持率为90.72%。      

Electrochemical Performance of Solid Polymer Electrolyte PEO20-LiTf-Urea1.5

A new solid polymer electrolyte PEO<,20>-LiTf-Urea<,1.5> was prepared by solution casting technique. The energy of frontier orbitals for the components of the electrolyte was predicted by quantum chemistry calculations, and TG stability and electrochemical features were measured. Urea exhibited a lower HOMO energy than PEO, implying its enhanced stability against electrochemical oxidation. Experimentally addition of urea increases the ionic conduc- tivity, which guarantees conductivity requirement for lithium ion batteries. It also results in significant improved electrochemical stability with good thermal stability. Favorable lithium stripping/plating performance is yielded, and it confirms the good stability of the solid electrolyte interphase for the PEO<,20>-LiTf-Urea<,15> system.     

Cone-shaped cylindrical Ce_（0.9）Gd_（0.1）O_（1.95） electrolyte prepared by slip casting and its application to solid oxide fuel cells

A cone-shaped gadolinium doped ceria(Ce0.9Gd0.1O1.95,GDC) electrolyte cylinder with a thin wall was fabricated using slip cast-ing technique.The diameter of the larger open end of the cone-shaped cylinder was 0.85 cm,the length was 1.0 cm,and the thickness of the wall was 0.026 cm after sintering.Both the electrolyte and electrode powders were fabricated by using a glycine-nitrate process.A single solid oxide fuel cell(SOFC) was prepared with the cone-shaped electrolyte,NiO-GDC(70:30 wt.%) anode and Sm0.5Sr0.5CoO3(SSC) cathode.Its electrochemical performance(I-V curve) and electrochemical impedance spectroscopy(EIS) were studied with humidified hydrogen as the fuel and air as the oxidant.The maximum output power density was about 300 ?mW/cm2 at 700 oC.The EIS results showed that the dominant loss of the SOFC was from the ohmic resistance of the electrolyte.     

锂离子电池聚合物基复合金属氧化物固态电解质研究进展

随着电动汽车的不断普及,锂离子电池（LIBs）的安全性备受关注。目前固态锂离子电池具有能量密度高和安全性好的优势,被认为是解决传统液态锂金属电池安全隐患和提高其循环性能的关键材料。然而,单一形式的固态电解质存在离子电导率低、界面阻抗大等问题,限制了固态锂离子电池的发展。近年来,基于无机填料与聚合物电解质的有机-无机复合电解质受到了广泛关注,有机-无机复合固态电解质兼有聚合物与无机填料的优点,一方面可以提高柔韧性,另一方面可以有效提高电池的机械性能。本文归纳总结了有机聚合物与无机金属氧化物复合固态电解质的不同类型,分析了基于不同聚合物与无机金属氧化物复合形成的有机-无机复合固态电解质对锂离子电池复合界面行为、离子电导率、电池机械性能的影响,并对复合固态电解质制备和应用过程中存在的问题和解决方法进行了梳理。最后对聚合物基复合金属氧化物固态电解质未来要重点解决的问题和发展方向进行了预测。     

Formation and Characterization of Li0.24 ＋ 2x La0.59-x Mx TiO3-LaPO4 （M = K, Na） System

Ionic conductingsolid materials has received con-siderable attention in the last few years due to theirpotential utilityin high energy batteries and other elec-trochemical devices . Several systems of lithium fastion conductors ,such as γ-Li3PO4-type sol…     

Oxygen probes based on calcia-doped hafnia or calcium zirconate for use in metallic melts

Up to the present, fully or partially stabilized zirconia has been used as a solid electrolyte material in probes for the determination of oxygen in metallic melts. In the present study, the ionic conduction behavior of HfO₂ (CaO) solid solutions and the compound calcium zirconate CaZrO₂ have been investigated. Both polarization experiments and EMF measurements on oxygen concentration cells point out that these two highly refractory oxide materials are also most suitable solid electrolytes. Their use is particularly recommended for oxygen probe measurements in deoxidized steel melts where extremely high chemical stability and low partial electronic conductivity of the solid electrolyte is required. In the paper, properties such as crystal structure, free energy of formation, thermal expansivity, ionic and total electrical conductivity are summarized and compared for fully and partially stabilized ZrO₂, calcium zirconate CaZrO₃, HfO₂ (CaO), and ThO₂ (Y₂O₃) solid solutions.     

Cathode Materials for Solid Oxide Fuel Cells(SOFC)

A detailed overview has been given concerning the use of rare earth materials in cathode fabrica-tion of solid oxide fuel cells(SOFC).It is focused on the various synthesis methods of the perovskite-typemixed rare earth oxides and the physical and chemical properties of the materials for cathode application ofSOFC.Also discussed is the doping mechanism of the related materials.Documented investigations showthat lanthanide of transition metals,especially manganese,chromium doped with strontium are most advan-tageous for the application.The crystallography,defect structure,conductivity and thermal matching withthe electrolyte and high temperature stability of cathode in oxidative gases are particularly emphasized.     

Low Temperature Preparation of Ceria Solid Solutions Doubly Doped with Rare-Earth and Alkali-Earth and Their Properties as Solid Oxide Fuel Cells

Solidoxidefuelcells (SOFCs)haveseveraldis tinctadvantages ,e .g .,highenergyconversioneffi ciency ,wideadaptabilitytofuels ,theusageofnon preciousmaterials ,noliquids ,nocorrosions ,modularconstructionandmuchlowerproductionofNOx,SOxandnoise .Therefore ,theyreceiveincreasingatten tion[1,2 ] .AtypicalSOFCwhichutilizesyttria stabi lizedzirconia (YSZ)astheelectrolyterequireshighoperationtemperaturesuchas 10 0 0℃togainhighe noughionicconductivity .Loweringtheoperationtem peratureto 80 0℃wou…