Enhanced sintering of Ce0.8Nd0.2O2−δ-La0.8Sr0.2Ga0.8Mg0.2O3−δ using CoO as a sintering aid

Ce_0.8Nd_0.2O_1.9 (NDC) and La_0.8Sr_0.2Ga_0.8Mg_0.2O_3-δ (LSGM) electrolytes were prepared using a sol-gel method. NDC-LSGM composite electrolytes were subsequently prepared by adding 5% (w, mass fraction) precalcined LSGM powders to NDC sols. The electrolyte materials of NDC-Co and NDC-LSGM-Co were obtained by adding 1 mol% CoO to NDC sols and NDC-LSGM composite electrolytes, respectively. The microstructure and phase composition of the pellets were characterized using X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), and energy dispersive X-ray spectroscopy (EDS). The electrical conductivities of the pellets were measured using alternative current (AC) impedance spectroscopy. The results indicate that a single perovskite phase is observed for the LSGM ceramic, while NDC-Co, NDC-LSGM and NDC-LSGM-Co have a cubic fluorite structure similar to that of NDC. As a sintering aid, CoO can further promote grain growth and increase relative density (＞95%) of the NDC-LSGM composite electrolyte. The enhancement of the total conductivity is primarily attributed to the large increase in the conductivity of the grain boundary. However, the slight decrease of the grain boundary conductivity of the NDC-LSGM-Co electrolyte is caused by the presence of trace amounts of impurity phases in the grain boundaries.     

浸渍Gd0.2Ce0.8O1.9对固体氧化物燃料电池La0.8Sr0.2Co0.2Fe0.8O3-δ阴极铬中毒影响的研究

固体氧化物燃料电池连接体中存在铬元素,会对阴极材料产生毒化作用,严重影响了阴极的电化学性能.采用浸渍法制备了用于固体氧化物燃料电池的La0.8Sr0.2Co0.2Fe0.8O3-δ(LSCF)-Gd0.2Ce0.8O1.9(GDC)复合阴极,以电化学测试为基础,结合扫描电子显微镜、电感耦合等离子光谱、X射线光电子能谱等...     

Phase interaction and oxygen transport in La0.8Sr0.2Fe0.8Co0.2O3–(La0.9Sr0.1)0.98Ga0.8Mg0.2O3 composites

Composite ceramics made of two perovskite-type compounds, (La_0.9Sr_0.1)_0.98Ga_0.8Mg_0.2O_3−δ (LSGM) and La_0.8Sr_0.2Fe_0.8Co_0.2O_3−δ (LSFC) mixed in the ratio 60:40 wt.%, possess relatively high oxygen permeability limited by both bulk ionic conduction and surface exchange at 700−950 °C. Sintering at elevated temperatures (1320–1410 °C) necessary to obtain dense materials leads to fast interdiffusion of the components, forming almost single perovskite phase ceramics with local inhomogeneities. This phase interaction decreases the oxygen ionic transport in the composites, where the level of ionic conductivity is intermediate between those of LSGM and LSFC. The scanning electron microscopy (SEM) suggests a presence of Ga-enriched domains, probably having a high ionic conductivity. The size and concentration of these domains can be increased by decreasing sintering temperature or using preliminary coarsened LSGM powders. The maximum oxygen permeability is thus observed for the composite prepared under minimum sintering conditions sufficient to obtain gas-tight ceramics, including the use of LSGM, preliminary passivated at 1150 °C, and sintered at 1320 °C. The activation energy values for total conductivity, which is predominantly p-type electronic and slightly decreases due to component interaction, vary in the narrow range from 24.0 to 26.2 kJ/mol at 25–575 °C. The average thermal expansion coefficients (TECs) of LSGM-LSFC composites, calculated from dilatometric data in air, are (12.4–13.5)×10⁻⁶ K⁻¹ at 100–650 °C and (17.8–19.8)×10⁻⁶ K⁻¹ at 650–1000 °C.     

二步合成法制备0.8PMN-0.2PT粉体

以MgO、Nb2O5为原料,按照化学计量比,将原料混合均匀,在1100℃保温4小时生成前驱体MgNb2O6,再将前驱体与TiO2和Pb3O4进行混合均匀,在放入炉中反应制成铌镁酸铅钛酸铅粉末,并用X射线衍射和扫描电子显微镜对制备粉体的晶体结构、形貌进行了表征。结果表明：用两步合成法得到的0.8PMN-0.2PT粉体中含...     

La0.8Sr0.2MnO3涂覆液浓度对La0.8Sr0.2FeO3电极电化学性能的影响

研究了0.005、0.010、0.020、0.035和0.040 mol/L5种不同浓度的La0.8Sr0.2MnO3 (LSM)溶液涂覆La0.8Sr0.2FeO3 (LSF)电极后,其电化学性能的变化.X射线衍射结果表明:LSM和LSF化学相容性好.扫描电子显微镜观察可见:电极的晶粒尺寸和涂层厚度随着涂覆液浓度的增加而增加.电化学阻抗谱表明:在阳极极化条件下,经过0.010 mol/L LSM溶液涂覆处理后的LSF电极表现为最佳的电化学性能,其极化电阻在800℃仅为0.3Ω·cm2.而且无论在阳极极化还是阴极极化处理后,涂覆LSM后的LSF电极的极化电阻,1200 s内都呈现下降的趋势,LSM涂覆后的LSF电极具有一定的抗阳极极化的能力,归因于LSM涂层的良好催化特性.因此,0.010 mol/L LSM溶液涂覆处理后的LSF可以作为固体氧化物电解池的阳极材料.     

Ca^2＋掺杂对La0.8Sr0.2Ga0.8Mg0.2O3-δ电解质烧结活性及微结构的影响

用甘氨酸-硝酸盐法（GNP）合成了Ca^2＋掺杂的中温固体氧化物燃料电池电解质粉体La0.8Sr0.2Ga0.8Mg0.2O3-δ（LSCGM）（x=0．02,0．04,0．06,0．08,0．10）。用SEM和XRD等手段对产品的成相过程及微结构进行了表征,用Archimedes排水法进行样品的密度测试。研究结果表明：在La0.8Sr0.2Ga0.8Mg0.2O3-δ体系中引入Ca^2＋可提高粉体的烧结活性,促进坯体的致密化。随着Ca^2＋含量的增加,材料的烧结致密度逐渐提高,x=0．10时相对密度最大。     

La0.8Sr0.2Co1-xFexO3结构特征的研究

采用溶胶—凝胶(sol—gel)法制备固体氧化燃料电池(SOFC)阴极材料La0.8Sr0.2Co1-xFexO3(x=0,0.1,0.2,0.3,0.4),从结构特征进行了研究。利用XRD研究发现,晶格常数a基本保持不变,晶格常数c先减小后增大,这主要和样品中氧的非化学计量比和制备方法有关;根据谢乐公式l=-0.89/λd(2θ)cosθ,随着Fe含量的增加,晶粒尺寸在不断的减小。     

碳包覆对LiFe0.8Mn0.2PO4性能的影响

为保证锂离子电池的正极材料磷酸亚铁锂具有优良的电化学性能,采用了碳包覆和锰元素掺杂的方法提高初始容量和充放电性能.以醋酸锰为Mn源,葡萄糖为C源,采用高温固相法合成碳包覆的LiFe0.8Mn0.2PO4/C,用XRD、恒流充放电研究了材料的结构和电化学性能.结果表明:包覆后的材料仍然具有橄榄石型晶体结构,并且包覆碳后材...     

锂离子电池正极材料LiNi0.8M0.2O2的制备

在增加氧气压力的条件下，采用固相反应制得一系列掺杂不同元素M的锂离子电池正极材料LiNi0.8M0.2O2. 研究发现，掺杂Al, Mn, Ti可以改善材料的耐过充性和循环性能，在充电电压为4.2~4.8 V的范围内循环3次，材料的放电容量没有显著的改变. X射线衍射和扫描电镜分析表明，掺杂Al, Mn, Ti提高了镍酸锂材料的六方菱型结构的有序性，维持了在充放电过程中的层状结构的稳定性. 其它掺杂元素降低了材料结构的有序性，影响了其电化学性能. 说明形成完整的晶体结构是掺杂元素的选择依据.     

La_(0.2)Sr_(0.8)Co_(0.8)Fe_(0.2)O_(3-z)钙钛矿型混合导电体透氧性能

以稳态法（ＳｔｅａｄｙＳｔａｔｅＰｅｒｍｅａｔｉｏｎＭｅｔｈｏｄ）对Ｌａ０．２Ｓｒ０．８Ｃｏ０．８Ｆｅ０．２Ｏ３－ｚ（ＬＳＣＦ）混合导电体在８５０℃～７００℃间的透氧性能作了测试;同时,以暂态热重法（ＴｒａｎｓｉｅｎｔＴＧＡ）研究了ＬＳＣＦ在８１５℃Ｏ２→Ｎ２→Ｏ２交变气流中的脱氧、吸氧过程,并对其透氧性能作了估算。结果表明,ＬＳＣＦ是一种具有实际应用价值的致密透氧膜;在暂态热重测试条件下,ＬＳＣＦ的吸氧、脱氧过程是可逆的,且整个表面反应受氧脱附过程控制;由暂态热重数据估算出的材料透氧性能比稳态法的推算值低,其值分别为１．５６×１０－７ｍｏｌ／ｃｍ２·ｓ和６４０×１０－６ｍｏｌ／ｃｍ２·ｓ。     

La_(0.8–x)Ba_xSr_(0.2)Co_(0.8)Fe_(0.2)O_(3–δ)阴极材料的结构与性能

采用溶胶–凝胶法制备了La0.8–xBaxSr0.2Co0.8Fe0.2O3–δ(LBSCF)阴极粉体。对LBSCF的晶体结构、材料表面的化学状态、烧结体的断面微结构及电导率进行了表征。用交流阻抗谱法在550~700℃范围测试了LBSCF-30%SDC(Sm0.2Ce0.8O1.9)复合阴极的电化学性能。结果表明:LBSCF粉体主晶相为六方晶系钙钛矿结构,存在少量的第二相。XPS结果显示,Ba2+掺杂不影响A位离子(La3+、Ba2+、Sr2+)的价态,但对B位离子的价态有不同的影响:x=0.10的样品中,钴离子以Co3+和Co4+混合价态存在,其余样品中以低氧化态(Co3+和Co2+混合价)或Co3+价存在;铁离子以高氧化态(Fe3+和Fe4+)存在。在500~700℃空气气氛中,LBSCF的电导率均超过700 S/cm,在同一温度下,电导率随着Ba2+掺杂量的增加而增大。x=0.20的样品在500℃时,电导率最大可达1.59×103 S/cm。随着Ba2+含量增加,极化电阻减小,x=0.20时,复合阴极LBSCF-30%SDC的极化电阻最小,700℃时的极化电阻为0.20?·cm2。     

高密度LiNi_(0.8)Co_(0.2)O_2的合成

以二次干燥化学共沉淀法制得高密度前驱体Ni0.8Co0.2(OH)2,再与LiNO3混合,经600℃恒温6 h,800℃恒温24 h两个恒温阶段烧结,得到高密度LiNi0.8Co0.2O2,探讨了锂源、镍源、Li/(Ni+Co)摩尔比、合成温度等因素对产品的影响,优化了LiNi0.8Co0.2O2的合成工艺。所得非球形LiNi0.8Co0.2O2粉末振实密度高达3.15 g/cm3,大幅度地提高正极材料的体积比能量。X射线衍射分析表明,合成的LiNi0.8Co0.2O2具有规整的层状NaFeO2结构,充放电测试表明,材料具有良好的电化学性能。     

Ce_(0.8)Sm_(0.2)O_(1.9)-BaCe_(0.8)Sm_(0.2)O_(2.9)复合电解质的晶界电导

分别采用机械混合法和一步溶胶-凝胶法制备摩尔比为1:1的Ce_(0.8)Sm_(0.2)O_(1.9)(SDC)-BaCe_(0.8)Sm_(0.2)O_(2.9)(BCS)复合电解质,研究了不同制备方法对复合电解质SDC-BCS的显微结构以及电化学性能的影响。结果表明:相比于机械混合法,一步溶胶-凝胶法制得的复合电解质中的SDC和BCS两相的分布更加均匀;且与单相电解质SDC相比,复合电解质中SDC和BCS的相界能够为质子和氧离子提供传输通道,有利于晶界电导率的提高。另外,一步溶胶-凝胶法制备的复合电解质制作的单电池,具有较高的开路电压和最大功率密度,在700℃时分别达到0.914 V和0.281 W/cm~2。     

Au改性La0.8Sr0.2MnO3催化剂的催化燃烧性能

采用共沉淀（CP）和沉积-沉淀法（DP）分别制备了0.5%(质量分数)金掺杂的Au-LSM和Au/LSM钙钛矿催化剂,以甲苯催化燃烧为模型反应测试催化剂活性,并用XRD、BET、H₂-TPR对其进行表征。结果表明,Au掺杂并不改变La_0.8Sr_0.2MnO₃催化剂的织构性质,但明显增强了催化剂表面氧的活动性,提高了其低温催化氧化活性。与DP法制备的Au/LSM相比,Au-LSM表现出更好的催化性能,其催化活性与商业贵金属Pd/Al₂O₃相当。通过对焙烧温度考察以及50 h的变温活性测试,Au-LSM催化性能并没有发生较大变化,催化剂具有良好的稳定性。     

草酸盐共沉淀法制备Ce0.8Y0.2O1.9超细氧化物固溶体

实验采用草酸二乙酯、Ce(NO_3)_3·6H_2O、Y(NO_3)_3·6H_2O为原料,以尿素为pH值调节剂,利用均相共沉淀法制备了20%(摩尔分数)Y_2O_3掺杂CeO_2(Ce_(0.8)Y_(0.2)O_(1.9))的氧化物前驱体,通过优化沉淀反应过程中尿素用量、pH值及沉淀物醇洗和干燥处理等制备工艺条件,实现对草酸盐沉淀物的制备过程中的团聚控制,得到分散良好的亚微米级草酸盐共沉淀物,进一步选择合适的热处理温度,得到亚微米级的超细Ce_(0.8)Y_(0.2)O_(1.9)粉体。     

固体氧化物燃料电池La0.6Sr0.4Co0.2Fe0.8O3–δ–Ce0.8Sm0.2O1.9纳米结构复合阴极的性能衰减行为

利用浸渍法制备了以La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3–δ)(LSCF)为催化相、Ce_(0.8)Sm_(0.2)O_(1.9)(SDC)为骨架的纳米结构复合阴极,并将LSCF–SDC复合阴极在600℃保温500 h,随后再用HCl腐蚀,研究了LSCF–SDC纳米结构复合阴极性能衰减的机理。结果表明:LSCF–SDC纳米结构复合阴极在600℃保温处理500 h后,阴极的极化电阻从0.21Ω·cm~(–2)增加到0.25Ω·cm~(–2),增加了19%,对其腐蚀处理后阴极极化电阻降为0.15Ω·cm~(–2),阴极催化活性的降低主要与氧在阴极表面的吸附与解离过程有关;阴极相组成和表观形貌没有明显的变化;保温处理后Sr~(2+)在阴极表面以SrO的形式富集。     

Effect of the reactive surface area of proton-conducting NiBa0.8Sr0.2Ce0.6Zr0.2Y0.2O3-δ anodes on cell performance

To determine the optimal combination of NiO and Ba_0.8Sr_0.2Ce_0.6Zr_0.2Y_0.2O_3-δ (BSCZY) for fabricating anode materials, Ni-BSCZY samples were prepared using the solid state reaction process. The porous structure of anode substrates not only provides mechanical strength to the fuel cells to enable fuel gases to flow to the electrolyte membrane but also creates an excess surface area on which to form a larger triple-phase boundary when NiO is added to the anode sample. The effect of NiO content on the microstructures, surface area, and electric conductivity of these Ni-BSCZY (NiO55-BSCZY, NiO60-BSCZY, and NiO65-BSCZY) anode materials were systematically investigated using X-ray diffraction, scanning electron microscopy, an analytic technique based on the Brunauer–Emmett–Teller surface area theory, and four-probe conductivity analysis. In addition, three anode-supported cells containing identical electrolytes but various combinations of NiO and BSCZY anode materials were fabricated and used for performance and electrochemical impedance measurement. The results revealed that the reactive surface area of the anode in contact with the electrolyte plays a crucial role in total cell performance. The cell containing the anode material (NiO60-BSCZY) with the highest surface area of 6.91 m² g⁻¹ and the lowest total resistance of 2.19 Ω cm² exhibited the highest power density of 169.2 mW cm⁻² at 800 °C.     

复合电解质BaCe_(0.8)Y_(0.2)O_(2.9)–Ce_(0.8)Gd_(0.2)O_(1.9)的化学稳定性

采用溶胶―凝胶燃烧法制备BaCe_(0.8)Y_(0.2)O_(2.9)(BCY)和Ce_(0.8)Gd_(0.2)O_(1.9)(GDC)粉末,并通过机械混合法制备不同摩尔比的BCY―GDC复合电解质粉末,在1 450℃烧结5 h获得BCY―GDC复合电解质。研究了复合电解质的化学稳定性及电化学性能稳定性。结果表明:BCY–GDC复合电解质在CO_2和沸水中的稳定性均高于单相BCY;当BCY―GDC复合电解质中的BCY摩尔分数小于70%时,试样在CO_2气氛和沸水中都具有良好的化学稳定性。基于BCY:GDC摩尔比为1:1的BCY―GDC复合电解质的单电池,在700℃工作20 h内的最大功率密度的稳定性高于基于BCY电解质的单电池。