掺杂对CeO2基电解质材料性能的影响研究进展

掺杂CeO₂基电解质是中低温固体氧化物燃料电池（SOFC）理想的电解质材料。首先阐述了掺杂CeO₂基电解质结构与性能的关系,接着介绍了金属离子掺杂对CeO₂基电解质晶体结构和电子结构的影响,重点综述了单元素掺杂和双元素掺杂对CeO₂基电解质性能的影响。通过分析得出：稀土金属元素单掺杂比碱土金属元素单掺杂更能显著提高CeO₂基电解质的导电性和可烧结性,但稀土氧化物的原料成本要远高于碱土氧化物;双元素掺杂比单元素掺杂具有更多的氧空位无序度和更小的氧离子迁移激活能,因此在提高CeO₂基电解质的离子电导率方面更有优势。总结了CeO₂基电解质材料的掺杂规律及构效关系,以期对制备出性能更加优异的CeO₂基电解质起到一定的指导作用。     

固体氧化物电池氧离子电解质研究进展

固体氧化物电池(SOCs)作为一种绿色、高效的全固态能量转换装置,既能在燃料电池模式下将氢、碳、烃、醇等燃料的化学能转化为电能,又能在电解池模式下分解水制氢,在缓解全球能源危机、实现碳中和等方面具有重要意义。然而,SOCs常用的Y₂O₃稳定的ZrO₂(YSZ)电解质材料在1 000 ℃以上才具有较高的离子电导率,但过高的工作温度会提高运行成本,限制材料选择,并降低系统稳定性。因此,降低工作温度一直是SOCs发展的核心问题之一,开发高电导率电解质材料和降低电解质膜厚度是实现SOCs中低温化应用的主要路径。本文从材料开发和薄膜制造两方面对中低温SOCs各类氧离子电解质的研究进展进行梳理,针对ZrO₂、CeO₂、Bi₂O₃及LaGaO₃基固体电解质,系统阐述了异价离子掺杂对提升氧离子电导率和稳定相结构的作用机制,介绍了电解质薄膜的制备技术和导电性能,为发展高性能固体氧化物电池电解质材料提供参考依据。     

掺杂氧化铈-碳酸盐复合电解质材料研究进展

固体氧化物燃料电池的中低温化要求其电解质材料在中低温范围内具有高的有效离子电导率和良好的稳定性,掺杂氧化铈-碳酸盐纳米复合材料正是这样一种有效离子电导率高,还原气氛下电子电导率的电解质材料。从组成出发简述了掺杂氧化铈-碳酸盐纳米复合材料的研究现状。     

氧化锆基固体电解质研究

电解质是固体氧化物燃料电池（SOFC）的核心部件,其性能的优良直接决定燃料电池的应用前景。氧化锆基陶瓷具有较高的离子电导率、良好的结构和化学稳定性,是理想的固体电解质材料。本文综合介绍了各种掺杂元素对氧化锆基固体电解质性能的影响,电解质薄膜制备方法和研究现状。并对氧化锆基固体电解质的研究方向进行了展望。     

固体氧化物燃料电池中的陶瓷材料

固体氧化物燃料电池(SOFC)也称为陶瓷燃料电池,其关键组成电解质、阴极和阳极均为陶瓷氧化物材料。致密电解质薄膜材料是核心,主要是(纯)氧离子导体,其电导率依赖于氧化物中的氧离子空位传导,氧空位主要来源于氧化物中低价金属离子掺杂;工业上主要使用萤石结构Y_2O_3掺杂的ZrO_2(YSZ)和Sc_2O_3掺杂的ZrO_2(ScSZ),更高氧离子电导率的材料包括掺杂的CeO_2、δ-Bi_2O_3和掺杂的LaGaO_3钙钛矿材料,有望在中低温下使用。电极都是多孔陶瓷材料,同时具有氧离子传导和电子传导性能。工业上阳极主要采用Ni-YSZ多孔金属陶瓷,具有混合离子电子导电性(MIEC)的钙钛矿材料是现在的研究热点。工业上阴极材料主要是掺杂LaMnO_3和YSZ复合陶瓷,在高温下具有良好的电化学性能和稳定性;中高温范围内被认可的材料是掺杂LaFeO_3基钙钛矿材料,以La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_3-δ为代表,具有良好的电化学活性和稳定性;优化材料组分和结构仍然是阴极材料的研究重点,也是SOFC领域必须突破的重要方向。     

Ta、Ba共掺杂石榴石型Li7La3Zr2O12电解质的制备及性能研究

传统锂离子电池采用有机电解液体系,能量密度难以进一步提升,同时存在一定的安全隐患。采用无机固体电解质构建全固态锂电池,在提高电池能量密度同时可兼顾安全性问题。在众多无机固体电解质中,Li₇La₃Zr₂O₁₂(LLZO)石榴石电解质具有离子电导率高、与金属锂接触稳定等优势,成为受人关注的材料。为了进一步提高该材料的导电性,采用固相法合成Ta、Ba共掺杂LLZO(Li_7-x+yLa_3-yBa_yZr_2-xTa_xO₁₂)电解质,采用X射线衍射、扫描电子显微镜和电化学阻抗法分析样品的物相结构、微观形貌及离子电导率。结果表明,Ta⁵⁺掺杂能够稳定立方相结构,Ba²⁺作为掺杂剂和烧结剂,促进晶粒生长和陶瓷致密化,从而降低总电阻。其中,Li_6.45La_2.95Ba_0.05Zr_1.4Ta_0.6O₁₂样品在室温下的总电导率为1.07×10^-3 S·cm^-1,活化能为0.378 eV。Ta⁵⁺/Ba²⁺共掺杂有利于制备高致密度和高电导率的石榴石型电解质材料。     

低温燃烧法制备Ce_(0.9)Gd_(0.1)Y_(0.1)O_(1.9)粉体与性能研究

氧化钇稳定的氧化锆(YSZ)具有氧离子电导率,但稀土氧化物掺杂CeO_2基电解质电导率更高。钆和钇共掺杂的氧化铈Ce_(0.9)Gd_(0.1)Y_(0.1)O_(1.9)(GYDC)粉末通过甘氨酸硝酸盐法合成。GYDC的制备通过使用相应的粉体来压制成颗粒并在空气中烧结他们。GYDC固体氧化物燃料电池的测试通过XRD、BET激光粒度等方法对合成的固溶体进行表征。XRD结果表明600℃焙烧产物有立方萤石结构。以甘氨酸为还原剂,金属硝酸盐作为氧化剂,采用低温燃烧法制备双掺杂CeO_2基超细粉体GYDC。按照低温燃烧反应的特点,系统地研究了不同的甘氨酸与金属硝酸盐的物质的量比(G/N)对燃烧反应历程,产物的性能和产率的影响。     

燃料电池固体氧化物电解质研究进展

本文对当前燃料电池用固体电解质材料的研究进展进行了综述.首先介绍了固体氧化物燃料电池的发展趋势及其与电解质材料性能的关系,然后分别对Y2O3稳定ZrO2(YSZ)、Sc2O3稳定ZrO2(ScSZ)、Ce基材料和其他一些电解质材料如Bi2O3、LaGaO3的制备、掺杂和电导率性能等方面进行了总结.最后,提出了今后电解质材料研的几个重要方向.     

具有复合电解质的低温固体氧化物燃料电池研究进展

高温固体氧化物燃料电池(SOFC)的低温化对于解决材料的稳定性、提高系统运行寿命和降低电池成本具有重要的意义,已成为近几年的研发热点。在实现SOFC低温化方面,目前国内外研究学者提出了不同的解决策略。综述了低温固体氧化物燃料电池(LT-SOFC)中复合电解质的研究进展,其包括引入碳酸盐材料作为第二相进行复合,构建类熔融碳酸盐固体氧化物燃料电池;引入过渡金属氧化物材料作为第二相进行复合,制备单组分燃料电池消除电极与电解质界面电阻提高电池性能,尤其是全氧化物复合电解质提高电池稳定性策略;引入半导体材料复合进一步提升LT-SOFC的电化学性能等几个方面。最后阐述了通过制备新型纳米复合材料进一步提升电解质离子电导率,改善界面接触问题以及探索新的电极材料对LT-SOFC电化学性能的影响。     

纳米氧化石墨烯/芒硝基复合相变材料的制备及其热性能

针对芒硝相变材料因过冷度大、相分层严重导致相变潜热存储循环寿命缩短的问题,以Na₂SO₄·10H₂ONa₂CO₃·10H₂O-NaCl相变材料体系为基体、改进的Hummers法结合冷冻干燥和球磨工艺改性制备的亲水性纳米氧化石墨烯（Nano-GO）为添加剂,制得纳米氧化石墨烯/芒硝基复合相变材料（GO-MCPCMs）。结果表明：氧化处理过的纳米氧化石墨烯中O/C比例增加了65.75%,结构缺陷水平由0.224增至1.088,无团聚现象;纳米氧化石墨烯/芒硝基复合相变材料的结晶相变温度增至约23℃、过冷度减小至0℃、相分层消除,该复合相变体系中Na₂SO₄结晶体全部结晶为晶粒长度尺寸近于2 cm的Na₂SO₄·10H₂O;500次固-液循环前后含氧化石墨烯质量分数为0.075%的GO-MCPCMs结晶潜热值分别为156.7 J/g和149.9 J/g,...     

Doping of scandia-stabilized zirconia electrolytes for intermediate-temperature solid oxide fuel cell: A review

The shortcomings of high-temperature solid oxide fuel cells necessitate research on SOFCs designs that are capable of operation at intermediate temperatures (600–800 °C), the so-called intermediate-temperature SOFCs. One of the limitations for the efficient operation of these fuel cells lies in insufficient ionic conductivity of the electrolyte material. This review briefly covers the types of ceramic electrolytes used in intermediate-temperature SOFCs and focuses on scandia-stabilized zirconia (ScSZ) electrolytes. It explores possibilities of control of phase stability and ionic conductivity of ScSZ by co-doping by various oxides, such as ceria, bismuth oxide, yttria, ytterbia, and several other co-dopants. It also covers a range of novel techniques applied to preparation of ScSZ electrolytes, which can be used to influence microstructure and phase composition of the electrolytes. The recommendations on the optimal ScSZ co-doping scheme are developed in the course of the present work.     

Synthesis and Characterization of Nano-Hetero-Structured Dy Doped CeO2 Solid Electrolytes Using a Combination of Spark Plasma Sintering and Conventional Sintering

Doped ceria (CeO₂) compounds are fluorite-type oxides that show oxide ionic conductivity higher than yttria-stabilized zirconia in oxidizing atmosphere. As a consequence of this, considerable interest has been shown in application of these materials for "low" (500°–650°C) temperature operation of solid oxide fuel cells (SOFCs). To improve the conductivity in dysprosium (Dy) doped CeO₂, nano-size round shape particles were prepared using a coprecipitation method. The dense sintered bodies with small grain sizes (<300 nm) were fabricated using a combined process of spark plasma sintering (SPS) and conventional sintering (CS). Dy-doped CeO₂ sintered body with large grains (1.1 μm) had large micro-domains. The conductivity in the sintered body was low (−3.2 S/cm at 500°C). On the other hand, the conductivity in the specimens obtained by the combined process was considerably improved. The micro-domain size in the grain was minimized using the present process. It is concluded that the enhancement of conductivity in dense specimens produced by the combined process (SPS+CS) is attributable to the microstructural changes within the grains.     

固态无机电解质Li7La3Zr2O12的改性研究进展

作为一种固态无机电解质材料,石榴石型立方相Li₇La₃Zr₂O₁₂具有较高的室温锂离子电导率、较宽的电化学窗口和优良的热稳定性等特点,是高安全性、高能量密度固态锂离子电池实现商业化应用的关键。阐述了Li₇La₃Zr₂O₁₂的晶体结构与锂传导机理,综述了元素掺杂、聚合物电解质复合、烧结助剂引入、表面包覆或修饰等方式对Li₇La₃Zr₂O₁₂的物相结构稳定性、界面阻抗与相容性、烧结活性、离子电导率等进行改性的最新研究进展。最后,针对Li₇La₃Zr₂O₁₂在产业化应用中所面临的障碍与挑战,提出了制备新工艺的开发、离子电导率的多重改性以及柔性复合电解质膜的结构设计与优化等应对策略,为推动高性能固态锂离子电池的发展提供依据。     

Preparation of an Alkali-Element-Doped CeO2-Sm2O3 System and Its Operation Properties as the Electrolyte in Planar Solid Oxide Fuel Cells

The ionic conductivity of the ceria-samaria (CeO₂-Sm₂O₃) system is higher than that of yttria-stabilized zirconia and other CeO₂-based oxides. In this study, a small amount of alkali-element-doped CeO₂-Sm₂O₃ solid solution was prepared. This solid solution was characterized by measuring the powder density and the chemical composition. Moreover, its electrochemical properties were investigated in the temperature range from 700° to 1000°C. It was found that a small amount of alkali-element-doped CeO₂ solid solution enhanced the ionic conductivity. The power density of an oxygen-hydrogen fuel cell for alkali-element-doped CeO₂-Sm₂O₃ ceramics exhibited high values at low temperatures such as 700° to 800°C. It is concluded that the improved fuel cell performance can be attributed to the high stability of this composition in the fuel atmosphere.     

Enhanced Sintering of Yttrium-Doped Barium Zirconate by Addition of ZnO

The influence of transition metal oxides additives, especially zinc oxide, on the densification and electrical properties of doped barium zirconate have been examined. With the use of zinc oxide as a sintering aid, BaZr_0.85Y_0.15O_3–δ was readily sintered to above 93% of theoretical density at 1300°C. Scanning electron microscopic investigations showed Zn accumulation in the intergranular regions. Thermogravimetric analysis of the material under flowing CO₂ showed ZnO-modified barium zirconate to exhibit excellent chemical stability. The conductivity, as measured by A.C. impedance spectroscopy under H₂O saturated nitrogen, was slightly lower than that of unmodified barium zirconate. Electromotive force measurements under fuel cell conditions revealed the total ionic transport number to be ∼0.9 at 600°C. The combination of electrical and chemical properties and good sinterability render ZnO-modified barium zirconate an excellent candidate for reduced temperature solid oxide fuel cell applications.     

Fabrication of electrolyte materials for solid oxide fuel cells by tape-casting

In this research, solid oxide fuel cell electrolytes were fabricated by aqueous tape-casting technique. The basic compositions for SOFC electrolyte systems were focused on yttria-stabilized zirconia (YSZ) system. The powders used in this study were from different sources. ZrO₂-based system doped with 3, 8, and 10 mol% of Y₂O₃, and 8YSZ electrolyte tape illustrated the desirable properties. The grain size of the sintered electrolyte tapes was in the range of 0.5–1 μm with 98–99% of theoretical density. Phase and crystal structure showed the pure cubic fluorite structure for 8–10 mol% YSZ and tetragonal phase for 3 mol% doped. The electrolyte tapes sintered at 1450 °C for 4 h had the highest ionic conductivity of 30.11 × 10⁻³ S/cm which was measured at 600 °C. The flexural strengths were in the range of 100–180 MPa for 8–10 mol% YSZ, and 400–680 MPa for 3 mol% YSZ.     

金属氧化物掺杂高岭土纳米 二氧化钛光催化复合材料研究

以高岭石为载体,以钛酸四丁酯为前驱体,采用溶胶-凝胶法制备金属氧化物掺杂高岭土纳米二氧化钛光催化复合材料。采用X射线衍射（XRD）、红外光谱（FT-IR）和拉曼光谱（Raman）对复合材料进行表征,并通过在紫外光下降解云母珠光工业废水来考察其光催化性能。研究了不同金属氧化物掺杂浓度对复合材料光催化活性的影响。实验结果表明：金属氧化物三氧化二铁、氧化锌掺杂使锐钛矿二氧化钛晶相特征衍射峰宽化,掺杂生成钛铁矿、红锌矿新相,影响锐钛矿二氧化钛结晶度。在紫外光下降解6 h,掺杂质量分数为0.5%的三氧化二铁对废水降解率为98.8%,掺杂质量分数为1.5%的氧化锌对其降解率为91.4%。     

Cu-Mn氧化物催化N_2O直接分解性能

分别以Cu(NO_3)_2·3H_2O和50%Mn(NO_3)_2水溶液为铜源和锰源,K_2CO_3为沉淀剂,采用沉淀法和共沉淀法制备单一Cu、Mn氧化物催化剂和Cu-Mn-O复合氧化物催化剂,用于催化N_2O直接分解反应,并利用N_2物理吸附-脱附、XRD、FT-IR和TPR等进行表征。结果表明,单一Cu和Mn氧化物分别以体相CuO和Mn2O_3物相形式存在,Cu-Mn-O复合氧化物中除形成CuMn_2O_4尖晶石物相外,还有一定量小晶粒CuO,较单一氧化物具有更加优异的还原性能,表现出较高的催化N_2O直接分解活性。在空速10 000 h~(-1)和N_2O体积分数0.1%条件下,Cu-Mn-O复合氧化物催化剂可在440℃催化N_2O完全分解,分别较单一Cu和Mn氧化物催化剂降低了40℃和60℃。