阴极材料Ba0.5Sr0.5Co0.8Fe0.2O3-σ合成工艺优化

为了在较低温度下合成具有高纯度的阴极材料Ba0.5Sr0.5Co0.8Fe0.2O3-σ(BSCF),采用X射线、扫描电镜以及能谱分析等方法,研究了共沉淀合成法中溶液pH值和煅烧温度等工艺条件对产物的相结构、组成成分和颗粒形貌的影响.结果表明,pH值的升高使前驱体由草酸盐沉淀向氢氧化物沉淀转化,在pH=10条件下,前驱体1100℃煅烧2 h后形成了单一的立方型钙钛矿型结构,比在pH=6条件下的前驱体煅烧温度降低了约100℃,而且成分配比更为准确.研究认为前躯体溶液的pH值对煅烧产物的组成和形貌影响至关重要,这主要是由于pH值的不同改变了前驱体的组成和颗粒形貌造成的.     

Cr掺杂Ba0.5Sr0.5Co0.8Fe0.1Cr0.1O3-δ钙钛矿型膜的透氧性能研究

采用固相反应法合成了钙钛矿型Ba0.5Sr0.5Co0.8Fe0.2-xCrxO3-δ(x=0.00,0.10)透氧膜粉体。利用XRD和SEM研究了Ba0.5Sr0.5Co0.8Fe0.2-xCrxO3-δ(x=0.00,0.10)的晶体结构和烧结性能,考察了在700~850℃范围内Ba0.5Sr0.5Co0.8Fe0.2-xCrxO3-δ(x=0.00,0.10)膜片的氧渗透性能。结果表明,它们均显示出优良的透氧性能,850℃时的透氧量分别为1.05mL/(min.cm2)、0.85mL/(min.cm2)。透氧稳定性的研究表明,Cr掺杂Ba0.5Sr0.5-Co0.8Fe0.1Cr0.1O3-δ在800℃时显示出较高的稳定性,证实用Cr离子部分取代Ba0.5Sr0.5Co0.8Fe0.2O3-δ的Fe离子能明显提高钙钛矿的结构稳定性。     

La0.6Sr0.4Co0.2Fe0.8O3-δ基固体氧化物电解池复合阳极的制备及性能

采用丝网印刷工艺制备了带有SDC阻挡层的固体氧化物电解池La0.6Sr0.4Co0.2Fe0.8O3-δ(LSCF)基复合阳极,利用动电位扫描及电化学阻抗谱分析考察了该材料在800℃时的电化学性能,电化学阻抗谱的研究表明,O2-在电极发生氧化反应生成O2的反应速率由电极/阻挡层界面的电荷转移、阻挡层/电解质界面的电荷转移以及氧气的解离吸附或在电极表面的扩散等三个电极过程控制.扫描电镜分析表明,经过长时间的电化学测试及升降温,阻挡层与电解质及复合电极部分均结合紧密,无缺陷.通过与传统的LSM-YSZ复合阳极的极化性能的对比,显示出LSCF材料在SOEC阳极领域良好的应用前景.     

SrCo0.8Fe0.2O3-δ的制备及氧渗透性能表征

介绍了通过固相反应制备SrCo0.8Fe0.2O3-δ(SCF)陶瓷膜的研究,研究发现当选择合成SCF的固相反应温度在950℃以上,参加反应的将主要是一些活性物质,从而使所合成产品中SCF的转化率提高,这样合成的陶瓷膜样品的化学稳定性提高,它可以长期暴露在空气中而不发生变化,在氧分压梯度下的相组成也较为稳定;当在样品上施加2.1 ×104pa/1.2×103Pa氧分压梯度时,1.24mm厚的SCF样品在1000℃的氧渗透率为1.87×10-6mol·cm-2·s-1,并在819℃上下出现表观氧渗透活化能的变化,这表明在该温度有氧空位的有序无序相变发生.     

Synthesis and characterization of nanofiber-structured Ba0.5Sr0.5Co0.8Fe0.2O3−δ perovskite oxide used as a cathode material for low-temperature solid oxide fuel cells

Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF) was synthesized in two forms: as a powder (by the sol-gel combined citrate-EDTA complexing (CC-EDTA) method) and as nanofibers (by electrospinning). Both forms were sintered at 950 °C for 5 h in air before their morphology and structure were characterized by field-emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), and specific surface area analysis based on the BET theory. Moreover, the mass loss and heat flow of as-electrospun BSCF nanofibers were analyzed by differential thermal analysis (DTA) and thermogravimetric analysis (TG). The results showed that these materials had a perovskite oxide crystal structure. The CC-EDTA method yielded BSCF in powder form, with a particle size of 1-10 μm and a specific surface area of 1.0 m²/g. On the other hand, BSCF obtained by the electrospinning technique was in the form of highly porous nanofibers with diameters in the range of 100-200 nm and a specific surface area of 2.4 m²/g. To demonstrate the potential applications of BSCF as a cathode material in low-temperature solid oxide fuel cells (LT-SOFCs), the electrochemical properties of the samples were determined using electrochemical impedance spectroscopy (EIS). The area specific resistance (ASR) of the BSCF nanofiber cathode was determined to be 0.094 Ω cm² at 600 °C, whereas that of the BSCF powder cathode was 0.468 Ω cm² under similar conditions.     

Significant improvement of the oxygen permeation flux of tubular Ba0.5Sr0.5Co0.8Fe0.2O3 − δ membranes covered by a thin La0.6Sr0.4Ti0.3Fe0.7O3 − δ layer

We present a new method to improve the oxygen flux properties and stability of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3 − δ tube membrane using a thin layer of La_0.6Sr_0.4Ti_0.3Fe_0.7O_3 − δ as protective coatings. The first relevant result is that the La_0.6Sr_0.4Ti_0.3Fe_0.7O_3 − δ protective layer had an extraordinary positive effect on improving the oxygen permeation flux of the tubular Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3 − δ membranes. La_0.6Sr_0.4Ti_0.3Fe_0.7O_3 − δ-coated Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3 − δ tubular membrane showed the highest oxygen permeability with the flux reaching ~ 3 ml cm⁻² min⁻¹ (oxygen purity > 99%) at 950 °C in static atmospheric pressure through a 1.0 mm thick membrane.     

Gd0.2Ce0.8O2包覆LaNi0.6Fe0.4O3-δ阴极材料抗铬污染性能

应用丝网印刷和共烧结制备LaNi_0.6Fe_0.4O_3-δ (LNF)/Sc_0.1Zr_0.9O_1.95(ScSZ)/LaNi_0.6Fe_0.4O_3-δ 对称电池.以硝酸铈和硝酸钆为原料、柠檬酸为燃料,采用燃烧法制备质量分数为21.3%的Gd_0.2Ce_0.8O₂(GDC)包覆的LNF阴极.电化学阻抗谱(EIS)表明:在750 ℃工作温度下,当无Cr基合金接触时,质量分数21.3%的GDC包覆的LNF经过1 200 h的搁置,其极化电阻由0.13 Ω·cm²增加至0.40 Ω·cm²,而纯LNF经过500 h的搁置,极化电阻由0.70 Ω·cm²增加至2.36 Ω·cm²,GDC的包覆加速了气体/阴极/电解质三相界面反应区的扩散过程,降低了阴极极化电阻;当有Cr基合金接触时,相对于质量分数为21.3%的GDC包覆的LNF阴极,LNF/ScSZ界面处沉积出大量Cr₂O₃,减缓了活性粒子在三相界面处的扩散,故其极化电阻远大于相同条件下质量分数为21.3%的GDC包覆的LNF阴极的极化电阻,质量分数为21.3%的GDC包覆的LNF阴极具有较佳的抗铬污染性能.     

Ba0.8Sr0.2Ti0.5Mn0.5O3纳米晶体的合成及气敏性质研究

采用复合碱媒介法(CHM),在合成BaMnO3和Ba0.5Sr0.5MnO3的基础上,以Sr(NO3)2、BaCO3以及MnO2和TiO2为原料,在200℃、24h的生长条件下,用20%的Sr离子替代20%的Ba离子,用50%的Ti离子替代50%的Mn离子成功合成了Ba0.8Sr0.2Ti0.5Mn0.5O3纳米晶体。采用XRD、SEM及EDS对产物的晶相、形貌和成分进行了分析,对Ba0.8Sr0.2Ti0.5Mn0.5O3制作的电极进行了气敏性质的测定。     

基于La0.75Sr0.25Mn0.5Co0.5O3-δ敏感电极的阻抗谱型NO2传感器的研究

利用浸渍技术在多孔YSZ中制备了钙钛矿型纳米颗粒材料La0.75Sr0.25Mn0.5Co0.5O3-δ(LSCM),并以其为敏感电极,YSZ为固体电解质组成了阻抗谱型NO2传感器.使用XRD和SEM研究了传感器敏感电极的相组成和微观结构.XRD分析结果表明,经前驱体溶液浸渍和热处理后,在YSZ多孔层中生成了钙钛矿结构的LSCM.扫描电镜分析表明敏感电极颗粒粒径为50～100nm,且与YSZ多孔层结合紧密.传感器敏感性能实验结果表明,在温度范围为450～600℃,NO2浓度范围为0～1000μL/L时,传感器对NO2有良好的敏感性,频率为0.1Hz时的总阻值与NO2的浓度之间呈良好的线性关系.在气体流速为400mL/min时,获得的传感器对NO2的真实响应时间约为40s,且响应信号稳定.传感器对O2和CO2具有良好的抗干扰性能.     

Nanoparticles of La0.8Ca0.2Fe0.8Ni0.2O3−δ perovskite for solid oxide fuel cell application

Polycrystalline samples of La_0.8Ca_0.2Fe_0.8Ni_0.2O_3−δ (LCFN) with perovskite type structure have been prepared by combustion, freeze drying, citrate-gel process and liquid mix method. The analysis of X-ray powder diffraction indicated that the samples were single phase and crystallized in an orthorhombic (space group, Pnma no. 62) structure.Transmission electron microscopy (TEM) analysis on the synthesized powder at 600 °C by liquid mix method showed clusters of 150 nm formed by nanoparticles of 20 nm. Electrochemical performance of LCFN cathodes, which are used for intermediate temperature solid oxide fuel cells, were investigated. The polarization resistance was studied using two different electrolytes: Y-doped zirconia (YSZ) and Sm-doped ceria (SDC). The dc four-probe measurement exhibits a total electrical conductivity, over 100 S cm⁻¹ at T ≥ 600 °C, pointing out that strontium can be substituted for the cheaper calcium cation without destroying the electrochemical properties. Experimental results indicate that nanoparticles have more advantages in terms of smaller particle size and better electrochemical performance.     

Ni0.5Co0.5Fe2O4铁氧体/氰酸酯-环氧树脂复合材料的制备和性能

采用水热法合成Ni_0.5Co_0.5Fe₂O₄铁氧体,并应用于氰酸酯-环氧树脂（CE-EP）复合材料的增韧改性,研究Ni_0.5Co_0.5Fe₂O₄铁氧体对CE-EP固化反应、力学性能及热稳定性的影响。XRD和SEM结果表明,所合成的Ni_0.5Co_0.5Fe₂O₄铁氧体结晶性好、纯净、呈块状,粒径约为20 nm。性能研究表明,Ni_0.5Co_0.5Fe₂O₄铁氧体的加入对CE和EP间的固化反应速度影响不大,且不会改变树脂基体的固化反应机制。与纯CE-EP树脂体系相比,Ni_0.5Co_0.5Fe₂O₄铁氧体/CE-EP复合材料在保持CE-EP玻璃化转变温度（T_g）的基础上明显改善了其韧性,当Ni_0.5Co_0.5Fe₂O₄铁氧体质量分数为3wt%时,其冲击强度和弯曲强度达到最大值,较纯CE-EP树脂基体分别提高了65%和30.3%;但其热分解温度略有降低,可能是由于Ni_0.5Co_0.5Fe₂O₄铁氧体对CE-EP树脂基体高温分解的催化作用造成的。      

Electrochemical performance of La2NiO4+δ-La0.6Sr0.4Co0.2Fe0.8O3−δ composite cathodes for intermediate temperature solid oxide fuel cells

The composite cathodes La₂NiO_4+δ-La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ were prepared for intermediate temperature solid oxide fuel cells. La₂NiO_4+δ and La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ powders were synthesized successfully by glycine-nitrate process. The effect of composition on the electrochemical performance of the composite electrodes was studied by AC impedance spectroscopy and the optimal calcination temperature was determined when the electrode showed the minimum area specific resistance. The addition of La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ to La₂NiO_4+δ electrode decreased the area specific resistance remarkably. The composite electrode with 30 wt% La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ calcined at 1150 °C exhibited the lowest area specific resistance of 0.125 Ω cm², about 60% of the area specific resistance of La₂NiO_4+δ electrode at 700 °C in air. The composite electrode with 30 wt% La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ can be a promising cathode material through the evaluation of electrical conductivity and thermal expansion behavior.     

La0.8Sr0.2CoO3的拉曼光谱特性研究

采用柠檬酸盐法制备了斜方六面体型(rhombohedral)钙钛矿材料La0.8Sr0.2CoO3,测量了它的拉曼光谱,我们发现随着测量用激光的激发功率的增加,705cm-1附近的拉曼振动峰不断移动,且拉曼峰的强度也不随激发功率的增加而线性增加,当激发功率达到1.5mW时,材料出现荧光,随激发光增强,荧光快速增大,同时拉曼峰消失.     

La0.3Sr0.7Fe0.7Cu0.2Mo0.1O3-δ钙钛矿超细陶瓷粉体制备与催化性能研究

采用溶胶低温燃烧法制备了单一组成的La0.3Sr0.7Fe0.7Cu0.2Mo0.1O3-δ(LSFCM)超细钙钛矿陶瓷粉体。用XRD,SEM以及TA等方法对粉体的物相、形貌、粒度以及导电性能等进行了表征。考察了LSFCM陶瓷粉体对甲烷部分氧化(POM)制备合成气的催化活性与稳定性。结果表明:溶胶燃烧粉末经800℃下煅烧4h可得到平均粒径小于35nm的立方钙钛矿结构LSFCM陶瓷粉体,相对密度为96.7%的LSFCM烧结体在空气气氛600℃温度下电导率达到26.27S·cm-1,在950℃、CH4/O2比为1.5~2.0时,甲烷转化率及一氧化碳与氢气选择性均达到90.0%以上;反应43h后虽产生少量积炭,但仍能保持钙钛矿结构,表明LSFCM粉体对甲烷部分氧化制合成气反应具有良好的催化活性和稳定性。     

Si衬底上La0.8Sr0.2MnO3/SrMnO3双层结构研究

利用磁控溅射方法在Si(100)衬底上首先生长SrMnO3(SMO)作为缓冲层,再沉积La0.8Sr0.2MnO3(LSMO)薄膜,得到(110)面择优生长的LSMO/SMO双层结构.利用X射线衍射仪分析了SMO缓冲层的结构特征对LSMO薄膜择优取向生长的影响;利用Rutherford背散射(RBS)分析了LSMO/SMO间的界面情况.结果表明以SMO作为单一缓冲层时,不仅可以实现LSMO薄膜在Si(100)衬底上的(110)面的择优生长,而且LSMO/SMO的界面扩散现象也不明显.     

La0.8Sr0.2CoxFe1-xO3型氧扩散障层材料的制备及结构性能研究

采用共沉淀-凝胶方法制备La0.8Sr0.2CoxFe1-xO3(x=1.0、0、0.3)氧扩散障碍层材料的前驱体,分别用X射线衍射分析、透射电镜、扫描电镜和交流阻抗谱仪对三种不同粉体及其陶瓷结构和性能进行研究.结果表明:在870℃下焙烧制备的La0.8Sr0.2CoxFe1-xO3(x=1.0、0、0.3)粉末具有钙钛矿相结构,无硬团聚,颗粒大小在20～60 nm.此粉末经冷等静压250MPa成型后,在1120℃下烧结6h,La0.8Sr0.2CoO3和La0.8Sr0.2FeO3混合导体的电导率在10—1S/cm数量级,而La0.8Sr0.2Co0.3Fe0.7O3导电率最高达100 S/cm数量级.三种陶瓷都是电子电导远大于离子电导的混合导体,电导率最高值在200～300℃范围,偏向低温.     

BaCo0.2Fe0.6Ti0.2O3-δ的制备、氧非化学计量和电子输运性能研究

采用修饰的Pechini方法制备了纯相BaCo0.2Fe0.6Ti0.2O3-δ(BCFT)样品.X射线衍射(XRD)证明了该方法制备的陶瓷粉体及烧结样品为单一的六方钙钛矿相结构.扫描电镜(SEM)观察显示BCFT烧结样品具有均匀的微结构.电导测量显示在570℃以下具有电阻负温度系数(NTC)特征,而在570～1000℃则呈电阻正温度系数(PTC)特征,结合碘滴定对BCFT样品在不同温度下的氧非化学计量测量结果,分析认为该电导出现极值的现象是因为高温晶格氧析出导致样品空穴载流子浓度降低所致.对电阻负温度系数温度段的电子输运性能和稳定性的研究表明,BCFT在200～300℃之间具有较好的阻温特征和重复性,有望作为一种在该温度段使用的新型NTC材料.     

Sol–gel formation,Mössbauer studies,optical absorption and impedance characteristics of Ba0.5Sr0.5Zn0.2Fe0.8O3−ξ powder

ABO_3−ξ-type oxides have gained prominence because of their usefulness in gas separation, solid oxide fuel cell, gas sensor, etc. Of particular interest is barium and zinc substituted strontium ferrite – an alternative cathode material due to its high structural stability, accommodation of considerable anion deficiency, and good oxygen permeability. An attempt has therefore been made to synthesize Ba_0.5Sr_0.5Zn_0.2Fe_0.8O_3−ξ powder by a novel oxalate sol–gel route to investigate its formation, nature of iron species, optical absorption, and impedance behaviour. The synthesis process involves gel formation, digestion for 6 h, drying at 150 °C for 24 h, and decomposition of oxalate at 950 °C for 15 h in air. The product is shown to exhibit (i) a perovskite-type cubic phase with a = 3.975 ± 0.002 Å, Z = 1, and space group Pm3m, (ii) Fe³⁺_0.5 and Fe⁴⁺_0.3 ions, (iii) oxygen deficiency parameter ξ ∼ 0.45, and (iv) optical absorption at ∼370 nm (∼3.4 eV) and ∼797 nm (∼1.56 eV) – arising due to charge transfer transition from O²⁻(2p) to Fe³⁺(3d) and octahedral crystal field splitting of iron t_2g and e_g orbitals, respectively. Moreover, the high impedance values observed below 10 kHz over a temperature range of 303–413 K have been attributed to space charge polarization; activation energy of the relaxation process being 0.2 eV. The motion of induced polarons is possibly responsible for the decrease of impedance with increase of temperature in the range 303–413 K.     

X-ray photoelectron study on Ba0.5Sr0.5CoxFe1?xO3?δ (BSCF: x?=?0.2 and 0.8) ceramics annealed at different temperature and pO2

X-ray diffraction (XRD) and the X-ray photoelectron spectroscopy (XPS) were measured for the sintered BSCF ceramics (Ba_0.5Sr_0.5Co _x Fe_1−x O_3−δ, x = 0.2 and 0.8: BSCF5528 and BSCF5582, respectively), which were annealed at different temperatures (700 and 950 °C) and gases (O₂ and Ar). The unit cell of the annealed BSCF5528 at 950 °C under Ar expanded by 0.8%, while contracting by 0.45% under O₂. The cubic and rhombohedral phases coexist in the BSCF5582 annealed at 700 °C under O₂. The XPS peak areas of lattice oxygen (O²⁻) in O_1s , ~528 eV, and the shoulder peak of Co_2p /Ba_3d in BSCF5582 (~778 eV) increased significantly after being annealed in O₂. The areas of the peaks for BaCO₃ (87.9/90.2 eV) in Ba_4d preferentially were shown to decrease in Ar and increase in O₂.     

Mn离子掺杂Pr0.5Ba0.5Fe0.9Mn0.1O3-δ钙钛矿SOEC阴极电解CO2性能研究

固体氧化物电解池(SOEC)电解CO₂时其阴极是CO₂还原反应发生的场所,也是SOEC取得高性能的关键环节。研究了Mn离子掺杂的Pr_0.5Ba_0.5Fe_0.9Mn_0.1O_3-δ(PBFM)钙钛矿材料作为SOEC阴极电解纯CO₂的性能。结果表明在850℃、1.8 V的电解电压下基于PBFM阴极的SOEC电流密度可达1.7 A·cm^-2,较使用未掺杂的Pr_0.5Ba_0.5FeO_3-δ(PBF)阴极提升了约30%;同时,电池的极化阻抗下降约60%,电化学性能增长主要来源于掺杂后氧空位浓度的增加。在800℃、1.3 V恒压的条件下70 h的长期测试中,PBFM电池没有表现出明显的衰减,且长期测试后的电极没有积碳现象。研究证明PBFM是一种有前景的电解CO₂ SOEC阴极材料。