Electrical properties and redox stability of tantalum-doped strontium titanate for SOFC anodes

SrTa_xTi_1−xO₃ (STT) with x = 0.01, 0.05, and 0.10, has been investigated as a potential electron conductor for solid oxide fuel cell (SOFC) anodes. STT was found to be chemically stable under oxidizing and reducing conditions and chemically compatible with yttria-stabilized zirconia (YSZ). The coefficient of thermal expansion (CTE) was near that of YSZ, ranging from 11.3 to 11.8 × 10⁻⁶ K⁻¹. The conductive properties of bulk STT and porous STT-YSZ composites were studied under relevant SOFC operating temperatures and redox cycling conditions. In order to achieve reasonable conductivities, samples were initially reduced at 1673 K. Conductivity after redox cycling was higher for lower dopant concentrations. The redox stable conductivity of a porous composite with x = 0.01 was 1.1 S/cm at 1073 K in humidified H₂ (3% H₂O). Fuel cell tests indicated an anode impedance of 0.4 Ω cm² at 973 K in humidified H₂ for STT-YSZ anodes infiltrated with 3 wt.% CeO₂ and 1 wt.% Pd.     

Fabrication and performance of LaGaO3-Based tubular SOFC’s

Yttria stabilized zirconia (YSZ) is the most commonly used electrolyte material in solid oxide fuel cells (SOFC’s). However, doped lanthanum gallate is an interesting alternative for use at intermediate temperatures (typically 600 – 750 °C). Commercially available La_0.8Sr_0.2Ga_0.8Mg_0.2O_2.8 (LSGM) powder was mixed with a polymer-based binder system and extruded into two different size tubes. After sintering, the electrolyte tubes were approximately (a) 6 mm outside diameter, 0.55 mm wall thickness and 100–200 mm long and (b) 4 mm outside diameter, 0.22 mm wall thickness and 50–100 mm long. The tubes were then fabricated into SOFC’s, using a range of anode and cathode morphologies. The electrical performance of the cells was then tested using hydrogen as a fuel. A repeatable and constant power of over 2.5 W per cell was obtained at 800 °C and 0.7 V. The maximum power density of the tubular fuel cell with La_0.6Sr_0.4CoO₃ cathode, Ce_0.8Sm_0.2O_1.9 interlayer and a Ni anode was 482 mW/cm². This paper will present the fabrication procedure and parameters, fuel cell performance test results, and the effect of electrode morphologies on the performance of the fuel cells. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15 – 21, 2002.     

Characterization of surface defects formation in strontium titanate(100)

The electronic properties of SrTiO₃(100) surfaces after various treatments have been studied by electron energy loss spectroscopy and Auger electron spectroscopy. A stoichiometric surface without contamination can be obtained by annealing at 910 K under oxygen atmosphere of 5 × 10⁻⁵ Pa. The surface heated under ultrahigh vacuum (UHV) at 910 K exhibits a new surface state in the band gap region, which comes from oxygen vacancies at the top Ti-O₂ layer. This state is also produced by electron irradiation or Ar-ion bombardment.     

Quasi-ordered nanostructures on the surface of strontium titanate

The results of the investigation of the surface of strontium titanate single crystals after treatment with high-energy plasma are presented. The surface morphology of the strontium titanate single crystals and the change in its characteristics after plasma treatment have been studied using electron scanning and atomicforce microscopy. A change in the electronic state of a part of the titanium ions and a change in the stoichiometry in the modified near-surface layer have been found by the method of valence shift of X-ray lines. A preliminary analysis has been made of the conditions providing the formation of single- and two-level systems of ordered crystallites with sizes of 10⁻⁷–10⁻¹⁰ m on the surface of single-crystal strontium titanate with impurities of ions of the iron and lanthanum groups.     

Doping effect on crystal structure and conduction property of fast oxide ion conductor LaGaO3-based perovskite

In order to discuss oxide ion conduction mechanism for LaGaO₃-based perovskite compounds, doping effects were investigated using two kinds of solid solutions whose oxygen vacancy concentrations are the same: one is La_0.9Sr_0.1Ga_0.9Mg_0.1O_2.9 with A-site and B-site substitutions and the other is LaGa_0.8Mg_0.2O_2.9 with only B-site substitution. Conductivity measurements showed that La_0.9Sr_0.1Ga_0.9Mg_0.1O_2.9 had a circumstance whereby oxide ion could more easily diffuse in the perovskite structure than in LaGa_0.8Mg_0.2O_2.9. Structural analyses using neutron diffraction found out the following three differences: the first finding was that the saddle point formed by two A-site cations and one B-site cation in La_0.9Sr_0.1Ga_0.9Mg_0.1O_2.9 was larger than that in LaGa_0.8Mg_0.2O_2.9 due to larger displacements of A-site and B-site cations; the second was that the doubly doping with Sr and Mg was more effective for reduction of GaO₆ octahedral tilt angles than the doping with Mg; the last was that La_0.9Sr_0.1Ga_0.9Mg_0.1O_2.9 had larger oxygen displacement than LaGa_0.8Mg_0.2O_2.9. It was considered that these structurally related parameters dominated the high oxide ion conduction in LaGaO₃-based perovskite compounds.     

Sites for catalysis and electrochemistry in solid oxide fuel cell (SOFC) anode

Fuel cells represent a challenging overlap of catalysis and electrochemistry. This is illustrated by anode reactions in a solid oxide fuel cell. The sites for catalytic conversion of methane and electrochemical conversion of hydrogen on an SOFC anode appear not to be the same. The fuel (methane, hydrogen, etc.) is activated by chemisorption on the nickel surface of the anode. This is linked to the electrochemical reaction at the interface of the electrolyte and the nickel crystals converting oxygen ions into electrons and water by reactions with adsorbed hydrogen atoms resulting from the activation of the fuel. The sites for these reactions appear not to be the same. This is reflected by different sensitivities of the two steps to sulphur poisoning. The role of different sites on the nickel surface for the steam reforming reaction is well understood in terms of impact on activity for methane activation, carbon formation and sintering. The study is supplemented by an analysis of anodes having been exposed to 13000 of operation using a number of characterisation methods. PACS 82.47.Ed; 82.45.-h; 82.65.-s     

Evaluation of Sr- and Mn-substituted LaAlO3 as potential SOFC anode materials

Lanthanum–aluminate-based oxides, (La_0.8Sr_0.2)_1−yAl_1−xMn_xO_3−δ (x = 0, 0.3, 0.5; y = 0 or 0.06) (LSAM), were synthesized and evaluated in detail as potential anode materials for solid oxide fuel cells (SOFCs). The electrical conductivity of LSAM (Mn ≥ 30 mol%) is dominated by p-type electronic conduction and can be treated as a diluted system of lanthanum manganites, (La,Sr)MnO₃. At 810 °C, the electrical conductivity of (La_0.8Sr_0.2)_0.94Al_0.5Mn_0.5O_3−δ (LSAM8255b) reaches 12 S/cm in air and 2.7 S/cm in humidified Ar/4% H₂ (p(O₂) ≈ 10^− 18 bar). The thermal expansion coefficients of LSAM8255a and LSAM8255b match YSZ very well and no chemical reaction was observed between these two perovskite materials and YSZ up to at least 1400 °C. Fairly good electrochemical performance was observed for an LSAM8255b–YSZ composite anode. At 850 °C, the polarization resistances are only 0.34 and 0.50 Ω cm² in wet (∼3% H₂O) Ar/20% H₂ and wet Ar/20% CH₄, respectively. In addition, an exposure to Ar/20% CH₄/3% H₂O for 35 h did not cause any apparent carbon deposition on the electrode. However, the chemical stability of LSAM8255a and LSAM8255b in a typical anode environment under open circuit conditions does not seem sufficient, leading to performance degradation with time in wet Ar/20% H₂ or wet Ar/20% CH₄. Furthermore, relatively large chemical expansion (0.3–0.5%) was observed when the atmosphere was switched from air to wet Ar/4% H₂, which might cause intolerable stress on the thin film electrolyte layer for a large-area anode-supported planar SOFC, but which might be tolerable for small geometries or electrolyte-supported SOFCs.     

Electrical second harmonic generation in the autostabilized state of ferroelectric solid solutions (lead,strontium) titanate and (lead,calcium) titanate

tandel effect and second harmonic generation studies on ferroelectric solid solutions (lead, strontium) titanate and (lead, calcium) titanate were carried out near the Curie temperature. The generated second harmonics are linear for low biasing fields with a zero off-set, while they decrease sharply at higher biasing fields. In the autostabilized state, thetandel elements adjust their impedance against the variations of a.c. field. Zero off-set might have been caused due to the presence of delects giving rise to an internal bias which in turn generates second harmonic.     

Electrical properties of yttrium doped strontium titanate with A-site deficiency as potential anode materials for solid oxide fuel cells

Yttrium doped strontium titanate with A-site deficiency ((Y_0.08Sr_0.92)_1 ? xTiO_3 ? δ) was synthesized by conventional solid state reaction. The deficiency limit of A-site in (Y_0.08Sr_0.92)_1 ? xTiO_3 ? δ is below 6 mol% in Ar/H₂ (5%) at 1500 °C. The sinterability of (Y_0.08Sr_0.92)_1 ? xTiO_3 ? δ samples decreases slightly with increasing A-site deficiency level (x). The ionic conductivity of (Y_0.08Sr_0.92)_1 ? xTiO_3 ? δ samples increases while the electronic conductivity decreases with increasing A-site deficient amount. The defect chemistry analysis indicates that the introduction of A-site deficiency results in not only the increase of oxygen vacancy concentration but also the decrease of Ti³⁺-ion concentration. The latter plays the main role in the electrical conduction. (Y_0.08Sr_0.92)_1 ? xTiO_3 ? δ shows good thermal-cyclic performance in electrical conductivity and has an excellent chemical compatibility with YSZ electrolyte below 1500 °C.     

Effect of zero-point energy on the dielectric behavior of strontium titanate

Barrett formula has been obtained in the framework of the effective field approach by including the zero-point energy. By fitting with experimental data of dielectric constant of SrTiO₃, we find that they agree in the whole temperature range fairly well if the zero-point energy is assumed to change from a small value at low temperature to a large value at high temperature.     

Thermostable ferroelectric capacitors based on graded films of barium strontium titanate

Technical Physics - The influence of the pressure of working gas during the ion–plasma sputtering on properties of deposited ferroelectric barium strontium titanate coatings has been...     

Solid state (47,49)Ti, (87)Sr and (137)Ba NMR characterisation of mixed barium/strontium titanate perovskites

Solid state ^47,49Ti, ¹³⁷Ba, ⁸⁷Sr NMR spectra have been recorded on Ba_xSr_1−xTiO₃ (0 x 1) perovskite samples prepared by the powder sintering method. Multinuclear solid state NMR shows great potential for characterising such systems since the quadrupolar parameters are very sensitive to any geometric deformation around the studied nucleus. ^47,49Ti NMR powder lineshapes appear strongly influenced by the presence of even a small amount of barium (or strontium) in the coordination second sphere of the probed titanium site: substitution of strontium by barium induces the broadening of the peaks, due to quadrupolar effects, while the isotropic chemical shift increases. ¹³⁷Ba NMR spectra exhibit a distribution of the quadrupolar interaction, that could be tentatively quantified, C_Q increasing with the amount of strontium. Preliminary results were also obtained on ⁸⁷Sr NMR showing behaviour comparable to ¹³⁷Ba NMR, i.e. a broadening of the peaks due to an increasing quadrupolar interaction with the amount of barium distorting the environment of the strontium sites.     

Domain epitaxial growth of ferroelectric films of barium strontium titanate on sapphire

A model of the epitaxial growth of crystalline multicomponent films on single-crystal substrates with a domain correspondence is presented using a solid solution of barium strontium titanate on sapphire substrates (r cut). The domain epitaxial growth suggests the matching of the lattice planes of the film and the substrate having similar structures by comparison of domain multiple of an integral number of the interplanar spacings. Variation of the component composition of the solid solution enables changes in the domain size in the range sufficient for epitaxial growth. This method can be used to project the epitaxial growth of films of various solid solutions on single-crystal substrates.     

Redistribution of excess space charge in structures based on single-crystal strontium titanate

A band mechanism for transport in single-crystal strontium titanate (STO) is used as a basis for estimating the parameters characterizing the localization and redistribution of space charge in STO for T<100 K. A comparison of the experimental and calculated temperature dependences of the charge carrier concentration yield an estimate for the location of the Fermi level in STO at T=4.2 K with E _F-E _v∼10 meV. The phenomena at metal/STO and YBCO/STO contacts are discussed. Fiz. Tverd. Tela (St. Petersburg) 39, 349–352 (February 1997)     

基于钛酸锶钡介电非线性效应的可调谐太赫兹人工电磁媒质

数值仿真研究了内嵌钛酸锶钡薄膜夹层的金属网格谐振单元人工电磁媒质的谐振行为. 垂直电磁波激励下, 电磁响应频率随着内嵌夹层钛酸锶钡薄膜介电常数的变大呈现红移, 调谐率为22.6%. 本文提出的人工电磁媒质调谐方法只需要以结构单元的上下两层金属图形本身作为电极对内嵌夹层钛酸锶钡薄膜施加电压, 极大地简化了可调谐人工电磁媒质的制备及应用, 在太赫兹人工电磁媒质调制器等方面具有潜在的应用. 关键词： 人工电磁媒质 钛酸锶钡薄膜 介电非线性 调谐     

I-V and C-V characteristics of ceramic materials based on barium strontium titanate

The properties of ferroelectric ceramics based on barium strontium titanate and doped by admixtures with low permittivity and dielectric loss tangent are studied experimentally. These ceramics are viewed as a promising material for microwave devices applied in the acceleration technology. Ceramic samples the I-V characteristics of which contain long horizontal segments are found to have good insulating properties. Various conductivity mechanisms in these ceramics are discussed, and their effect on the amount and character of dielectric hysteresis in these samples is considered.     

Properties of strontium titanate in the SrTiO3/CeO2/Al2O3 multilayered structure

Studies of the crystal structure, elemental composition, and dielectric properties of strontium titanate films in SrTiO₃/CeO₂/Al₂O₃ multilayered structures are reported. Data on the crystal lattice and impurity contents have been obtained, and temperature and electric field dependences of the dielectric properties of SrTiO₃ films in the microwave range have been measured. An analysis of the results is made to establish the reason for the nonmonotonic dependence of the small-signal dielectric permittivity of SrTiO₃ films on temperature. Fiz. Tverd. Tela (St. Petersburg) 39, 1024–1029 (June 1997)     

Synthesis and electrical conductivity of Sr- and Mn-substituted LaAlO3 as a possible SOFC anode material

Single phase (La,Sr)(Al,Mn)O₃ perovskites were synthesized and their electrical conductivity was studied as a function of temperature and oxygen partial pressure. The electrical conductivity was found to increase with Mn content, temperature and oxygen partial pressure, thus (La, Sr)(Al, Mn)O₃ may be regarded as a diluted system of (La,Sr)MnO₃. The highest electrical conductivity at 810 °C in air and humidified Ar/4% H₂ was observed for (La_0.8Sr_0.2)_0.94Al_0.5Mn_0.5O₃ and reached 12 and 2.7 S/cm, respectively.     

Effect of annealing on the dielectric permittivity of strontium titanate films in the SrTiO3/Al2O3 structure

The paper reports an experimental study of the structure of a strontium titanate film on a sapphire substrate and of the dielectric properties of capacitors based on a SrTiO₃/Pt/Al₂O₃ multilayer system before and after a high-temperature anneal. The macro-and microstructure of SrTiO₃ films and its variation induced by the annealing have been investigated. The temperature and field dependences of the dielectric permittivity of strontium titanate films have been determined, and their comparison with similar data for single crystals carried out. The mechanisms by which annealing can affect the capacitor capacitance and the properties of SrTiO₃ films are discussed. Fiz. Tverd. Tela (St. Petersburg) 40, 1473–1478 (August 1998)     

Preparation of barium strontium titanate Ba(1-x)Sr(x)TiO(3) (0<or= x <or=0.2) single-crystal nanorods by a novel combined method

An ultrasonic irradiation method was applied to the sol/gel synthesis of the single-crystal cubic barium strontium titanate Ba(1-x)Sr(x)TiO(3) (0相似文献