Synthesis,structure and electrochemical performance of cobaltite‐based composite cathodes for IT‐SOFC

The development of novel and high‐performance cathodes is a critical issue to be addressed in order to reduce Solid Oxide Fuel Cells (SOFCs) operation temperature to the 600‐800 °C range or less. The performance of CeO₂‐based composite cathodes is very attractive to such operational temperatures. In this work, La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF) and Ce_0.8Sm_0.2O_1.9 (SDC) powders were synthesized by different synthesis methods and mechanically mixed to prepare LSCF‐SDC composite cathodes. Screen‐printed LSCF‐SDC/CGO/LSCF‐SDC symmetrical cells were sintered at 1150 °C for 4 h and characterized by electrochemical impedance spectroscopy in static air. X‐ray diffraction and scanning electron microscopy were employed to characterize the powders. Area specific resistance values of 0.72 and 2.77 Ω cm² at 800 °C were found for composite cathodes containing SDC powder synthesized by modified Pechini and microwave‐assisted combustion methods, respectively. Furthermore, the activation energy of the composite cathode containing SDC derived from modified Pechini method is 1.18 eV, i.e., much lower than 1.73 eV, value determined for LSCF with SDC from microwave‐combustion method.     

Gel-glass transformation in the SiO2Fe2O3 system

Gel-glass transformation has been studied by Mössbauer spectroscopy, DTA-TG analyses and X-ray diffractometry for four compositions in the SiO₂Fe₂O₃ system (A: 5 wt% Fe₂O₃, B: 10 wt% Fe₂O₃, C: 20 wt% Fe₂O₃, D: 40 wt% Fe₂O₃).The gels were prepared by the hydrolysis of silicon tetraethoxide and iron triethoxide and successively dried and heated in oxygen in the temperature range 40–1000°C.Samples A and B gave typical amorphous X-ray patterns up to 700°C; heating at higher temperature yielded the precipitation of quartz, cristobalite and hematite in sample A, cristobalite and hematite in sample B. Crystallization was also detected by DTA in sample A for which X-ray diffraction exhibited a larger effect.In samples C and D crystallization took place starting from 300°C with the precipitation of hematite, which remained the only crystalline phase up to 1000°C.The presence of hematite was confirmed by the obtained Mössbauer spectra which showed the characteristic sextet. The apportion of iron ions in the Fe³⁺ and Fe²⁺ oxidation states was also determined, together with the attribution of the probable coordination states for Fe³⁺ ions.Complex magnetic structure appeared in samples treated above 800°C.     

BaO–B2O3–SiO2–Al2O3 sealing glass for intermediate temperature solid oxide fuel cell

Glasses in the formulation close to BaSiO₃–BaB₂O₄ eutectic compound are developed for sealing of intermediate-temperature (500–650 °C) solid oxide fuel cell (IT-SOFC). Thermal and microstructural analyses of the glasses with 0–10 mol% Al₂O₃ are also conducted. Detailed crystallization kinetics and interfacial stability of the glass in contact with yttria-stabilized zirconia (YSZ) and samaria-doped ceria (SDC) are investigated and compared. The results show that the formulation, 47BaO–21B₂O₃–27SiO₂–5Al₂O₃ (G1A5), performs the best on glass forming ability (GFA) among all tested formulations, and shows matched thermal expansion and working temperature to CeO₂-based electrolytes of IT-SOFC. Two major crystalline phases that precipitate from G1A5 above 750 °C are platy hexacelsian and BaSiO₃ grains.     

Preparation and characterization of indium doped tin oxide (ITO) via a non-aqueous sol-gel

ABSTRACT

Tin-doped indium oxide (ITO) nanoparticles (NPs) were conceived as promising materials using as noncarbon support for Pt NPs on the cathode side of Proton Exchange Membrane Fuel Cells (PEMFC). In this paper, ITO nanoparticles have been synthesized via a nonaqueous sol-gel process using indium acetylacetonate and tin bis(acetylacetonate)dichloride in oleyamine as starting materials. The ITO exhibits solid solution phase, relatively porous, good crystallinity with a uniform size of 15–20 nm, resulting in a high specific surface area and excellent conductivity. The effects of reaction temperature, calcination temperature on the specific surface area as well as the conductivity of ITO nanoparticles were studied in this paper. We found that the ITO nanoparticles synthesized at 235°C and calcination temperature at 500°C for 3 hours shows the excellent conductivity of 1.242 S/cm, was significantly ～8-fold higher than that of commercial ITO produced by Sigma-Aldrich (0.15 S/cm). The results of this research suggested that the ITO synthesized by non-aqueous sol-gel process exhibits relatively good properties as well as can apply this process to prepare the others nanomaterial support based on In₂O₃-materials by doping different oxide into indium oxide.     

Ionic conductivity of Bi12(V,Bi)O20 + δ single crystal (δ = 0.27) with a sillenite-type structure

The ionic conductivity of nonstoichiometric Bi₁₂(V_0.89Bi_0.03)O_20.27 single crystal with a sillenite-type structure has been investigated by impedance spectroscopy; its conductivity at 673 K is 2 × 10^?3 S/cm, which is about two orders of magnitude higher than the conductivity of oxide superionic conductor single crystal Zr_0.88Y_0.12O_1.94. As follows from crystallochemical analysis, ion transport in Bi₁₂(V_0.89Bi_0.03)O_20.27 is due to additional O^2? ions, which arise due to oxygen nonstoichiometry.     

Synthesis and properties of oxide ion conductor Pr2Mo2O9 with La2Mo2O9 structure

Polycrystalline Pr₂Mo₂O₉ samples have been prepared by solid-state synthesis and single crystals of this compound have been grown. Pr₂Mo₂O₉ is unstable in the temperature range 700–900°C and partially decomposes with the formation of Pr₂Mo₃O₁₂ at these temperatures, but upon further heating to 1000–1050°C, Pr₂Mo₂O₉ is recovered. At room temperature, the structure, polymorphism, and physical properties of Pr₂Mo₂O₉ are similar to those of the known oxide ion conductor La₂Mo₂O₉. Pr₂Mo₂O₉ exhibits a reversible first-order phase transition to the cubic phase in the temperature range 520–540°C. The electric conductivity of Pr₂Mo₂O₉ is close to that of La₂Mo₂O₉ and amounts to 3.5 × 10⁻² S/cm at 700°C. The conductivity of Pr₂Mo₂O₉ is described by the Arrhenius law in the low-temperature phase and by the Vogel-Fulcher-Tammann equation in the high-temperature phase.     

Influence of the melting conditions of heavy metal oxide glasses containing bismuth oxide on their optical absorption

Glasses of the systems Bi₂O₃-SiO₂, Bi₂O₃-PbO-Ga₂O₃, Bi₂O₃-PbO-Ga₂O₃-GeO₂ and Bi₂O₃-GeO₂-Li₂O have been prepared and the interaction of their melts with crucibles of different materials has been analytically determined. Silica and porcelain crucibles were very strongly corroded and the glass composition was noticeably altered. Instead platinum crucibles are not affected if the Bi₂O₃ content is not too high. The color of the glasses changes in all cases from pale yellow to deep brown when the melting temperature reaches approximately 1000 °C. The higher the temperature and the Bi₂O₃ content the darker the brown color, independently of the nature of the employed crucible. The addition of oxidizing ions (Sb⁵⁺, As⁵⁺ or Ce⁴⁺) to the glass batch prevents darkening. Nanoparticles of elementary bismuth Bi⁰ are observed by transmission electron microscopy in the glasses melted above 1000 °C. The partial thermoreduction of the Bi₂O₃ during the heating of the glass melt is proposed as the mechanism responsible for the observed darkening.     

Crystallization of some semiconducting chalcogenide glasses in the AsSeBi system

Isothermal crystallization in vacuum and in air was studied in glassy As Se_1.5Bi_0.05 at 240 and 260°C. Electrical properties, density, and microhardness were measured. X-ray diffraction of the annealed samples was also examined.Unlike As Se_1.5, As Se_1.5Bi_0.05 easily crystallizes. The first process of devitrification has an induction period (characteristic parameters suffer little changes). As crystallization increases, the density of the alloys also increases and the microhardness decreases. The electrical conductivity increases at 20°C by 6–7 orders of magnitude and the activation energy of electrical conductivity decreases by about 1.7 eV.     

Electrical Conductivity and Thermoelectric Power of Silver Iododichromate Fast Ion Conducting Electrolytes

Fast ion conducting solid electrolytes are becoming increasingly important owing to their application in solid state ionic devices. The present work deals with the silver ion conducting x AgI – (1–x)Ag₂Cr₂O₇ electrolyte system. These electrolytes have been characterised by X-ray diffraction, electrical conductivity, electronic conductivity and thermoelectric power techniques. A high ionic conductivity of the order of 10⁻³ S/cm has been observed for the composition mol% 80 AgI–20 Ag₂Cr₂O₇, at room temperature. The electronic conductivity of this electrolyte is three orders of magnitude lower than the ionic conductivity.     

Relaxation of polaronic charge carriers in lithium manganese spinels

Lithium manganese spinels Li_1+xMn_2−xO₄, 0 ⩽ x ⩽ 0.33, were prepared by wet chemistry technique followed by heat-treatment at 750 °C or 800 °C. Differential scanning calorimetry was used to reveal phase transitions. Electrical properties were studied by impedance spectroscopy. LiMn₂O₄ exhibited phase transition below room temperature. The transition, seen as an exothermic event in DSC and a steep decrease of conductivity upon cooling, was sharp in sample sintered at 800 °C and broadened over a range of temperature in sample sintered at 750 °C. In the low temperature phase of LiMn₂O₄, two relaxations of similar strength were observed in the frequency dependent permittivity. The low frequency process was identified as relaxation of charge carriers since the relaxation frequency followed the same temperature dependence as the dc conductivity. The high frequency process exhibited milder temperature dependence and was attributed to dipolar relaxation in the charge-ordered structure. The dipolar relaxation was barely visible in Li substituted samples, x ⩾ 0.05, which did not undergo structural phases transition. Measurements extended to liquid nitrogen temperature showed gradual lowering of the activation energy of conductivity and relaxation frequencies, behavior typical for phonon-assisted hopping of small polarons.     

Single‐crystal growth and characterization of mullite‐type orthorhombic Bi2M4O9 (M = Al3+, Ga3+, Fe3+)

Pure and homogeneous single crystals of orthorhombic mullite‐type Bi₂M₄O₉ (M = Al³⁺, Ga³⁺, Fe³⁺), and a mixed Bi₂Fe_1.7Ga_2.3O₉ crystal from an equimolar Ga/Fe composition were grown by the top seeded solution growth (TSSG) method. All these compounds melt incongruently in the range of about 800 and 1100 °C. In case of bismuth gallate and ferrate inclusion‐free crystals with dimensions up to several cubic centimeters can be grown. Limited solubility in Bi₂O₃ and the high steepness of the liquidus curve are the reasons for getting only small imperfect bismuth aluminate crystals. In contrast to ceramic materials preparation reported in literature, divalent calcium and strontium could not be incorporated into the mullite‐type structure during the melt growth process. Several fundamental physical properties like heat capacity, thermal expansion, heat conductivity, elastic constants, high‐pressure behavior and oxygen diffusivity were determined by different research groups using single‐crystalline samples from the as‐grown materials. Furthermore, the refractive indices of Bi₂Ga₄O₉ were measured in the range of 0.430 and 0.700 μm. Such as many other bismuth containing compounds the refractive indices of Bi₂Ga₄O₉ are larger than 2, and Bi₂Ga₄O₉ is an optic biaxial positive crystal. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electrochemical characterizations and the effect of glycerol in biopolymer electrolytes based on methylcellulose-potato starch blend

ABSTRACT

Polymer electrolytes have been prepared by blending methylcellulose (MC)-potato starch, doped with lithium perchlorate (LiClO₄) and plasticized with glycerol. The blend of 60 wt% MC-40 wt% starch was found to be the most suitable ratio to serve as polymer host. Fourier transform infrared (FTIR) spectroscopy analysis proved the interaction among the components. X-ray diffraction (XRD) analysis indicated that the conductivity enhancement is due to the increase in amorphous content. The highest ionic conductivity obtained at room temperature was (4.25 ± 0.82) × 10^?4 S cm^?1 for MC-starch-LiClO₄-20 wt% glycerol. The highest conducting samples in both systems were found to obey Arrhenius rule. Dielectric study further strengthens the conductivity result.     

Preparation and characterization of CuO doped Bi2O3–B2O3–BaO–ZnO glass system for transparent dielectric layer

The electrical, thermal, optical, and morphological properties of CUO doped Bi₂O₃–B₂O₃–BaO–ZnO glasses were studied as a PbO-free, low firing transparent dielectric layer for plasma display panels (PDP). CuO improved the transmittance of Bi₂O₃–B₂O₃–BaO–ZnO by up to 84% in the visible region, eliminating a yellowish color typical of Bi₂O₃–B₂O₃–BaO–ZnO. A slight absorption within the near infrared (NIR) region was also observed. The glass transition temperature (T_g), thermal coefficient of expansion (TCE), and root-mean square (rms) roughness of 0.005 wt% CuO doped Bi₂O₃–B₂O₃–BaO–ZnO were found to be 455 °C, 81.4 × 10⁻⁷/K, respectively, and 162 ± 14 Å, which satisfied the requirements for a transparent dielectric layer for PDP application.     

Synthesis and Electrical Properties of a Fluorite-Like Nd<Subscript>5</Subscript>Mo<Subscript>3</Subscript>O<Subscript>16</Subscript> Compound with Partial Substitution of Molybdenum by Tungsten,Niobium, or Vanadium

The phase formation of Nd₅Mo_{3 – x}W _x O_16.5, Nd₅Mo_{3 – x}Nb _x O_{16.5 – х/2}, and Nd₅Mo_{3 – x}V _x O_{16.5 – х/2} solid solutions based on a fluorite-like Nd₅Mo₃O_16.5 compound (mixed conductor with interstitial oxygen conductivity) has been studied. The electrical conductivity of doped compounds obeys the Arrhenius law and, at a low impurity content, is as high as 0.03–0.08 S/cm at 800°C. Substitution of Mo⁶⁺ cations by V⁵⁺ and Nb⁵⁺ cations reduces the interstitial oxygen content, which causes a decrease in the solid-solution electrical conductivity by 1–2 orders of magnitude and a decrease in the cubic unit-cell parameter. A wide diffuse anomaly with a maximum of about 1500–4000 has been observed in the temperature dependence of the permittivity for all single-crystal and polycrystalline samples in the range of 300–900°C.     

Synthesis on large area and uniform nanosheet morphology of polycrystalline cobalt oxide Co3O4 obtained from oxidation of Co films in a pure oxygen atmosphere

Large area and uniform nanosheets Co₃O₄ have been fabricated by thermal annealing of cobalt thin film under the DC magnetron sputtering method. The synthesis is based on controlling the simple thermal oxidative formation of precursor Co films. The Co films were heated at 300, 400, and 500 °C for two hours in a pure oxygen atmosphere. At 300 °C, CoO and Co₃O₄ phases appear to survive together. An amount of pure polycrystalline Co₃O₄ nanosheets were observed at 400 °C. The structural and morphological properties of the nanosheets Co₃O₄ were characterized by means of transmission electron microscopy (TEM) and Raman spectroscopy.     

Fabrication of Al2O3 Coatings on Metal Substrates by Electrophoretic Deposition by the Addition of Polydimethylsiloxane-Based Organic-Inorganic Hybrid Materials as Binders

Polydimethylsiloxane (PDMS)-based organic-inorganic hybrids have been studied because of their high dielectric strength, heat resistivity, and flexibility. In this study, we fabricated Al₂O₃ coatings on metal substrates with sufficient electrical insulation, heat conductivity, and thermal stability by electrophoretic deposition (EPD) using PDMS-based hybrid binders. The scratch hardness, thermal conductivity, and electrical breakdown strength of the Al₂O₃ coating before and after heat treatment at 300 °C for 500 h were 2.0 N, 3.1 W/mK, and 60 kV/mm, respectively. These results demonstrate the usefulness of EPD using PDMS-based hybrid binders for fabricating flexible heat dissipative substrates used in high-temperature environments.     

Ce0.8Sm0.2O1.9-BaCe0.8Sm0.2O2.9复合电解质的成分对其电化学性能的影响

采用一步溶胶凝胶法制备摩尔比分别为9∶1、7∶3、5∶5和3∶7的复合电解质Ce0.8Sm0.2O1.9(SDC)-BaCe0.8Sm0.2O2.9(BCS)粉末,研究复合电解质SDC-BCS的相成分对电导率及其电化学性能的影响.结果表明:随着SDC含量的增加,复合电解质SDC-BCS的晶粒尺寸增大、电导率提高;复合电解质的晶界电导率均高于单相SDC的晶界电导率.不同成分的复合电解质制备的NiO-SDC-BCS|SDC-BCS|LSCF-SDC-BCS单电池的功率密度随着SDC含量的增加而提高.当SDC∶BCS的摩尔比为9∶1时,其单电池700 ℃的最大功率密度为550 mW/cm2,是单电池NiO-SDC|SDC|LSCF-SDC最大功率密度的3倍.     

Characterisation and mesomorphic behaviour of liquid crystals with dispersed PdCl2 nanoparticles

The synthesis and characterisation are carried on liquid crystalline (LC) p-dodecyloxy benzoic acid (12OBA) with 1 and 2 wt% for PdCl₂ nanoparticles dispersion. Further, characterizations are carried out by different spectroscopic techniques like X-ray diffraction spectrometric studies, scanning electron microscopy, Fourier transform infrared and differential scanning calorimetry (DSC). Textural determinations of the synthesised compounds are recorded by using polarising optical microscope (POM) attached with a hot stage and camera. The results show that the dispersion of PdCl₂ nanoparticles in 12OBA exhibits Nematic phases as same as the pure 12OBA with reduced clearing temperature as expected. Further, the nematic thermal ranges are quenched and the smectic C thermal range has been increased while performing both DSC and POM with the dispersion of 1 wt% PdCl₂ nanoparticles. Size dependence on bonding nature with LC compounds is established.     

The Effect of Plasticization on Conductivity and Other Properties of Starch/Chitosan Blend Biopolymer Electrolyte Incorporated with Ammonium Iodide

This work focuses on polymer electrolytes composed of a starch-chitosan blend host, ammonium iodide (NH₄I) and glycerol. Fourier transform infrared (FTIR) analysis confirms the interaction of starch-chitosan-NH₄I-glycerol. The highest room temperature conductivity is (1.28 ± 0.07) × 10^?3 S cm^?1, obtained by a sample containing 30 wt% glycerol. Dielectric studies showed that the electrolytes obeyed non-Debye behavior. The total ionic transference number for the 30 wt% glycerol sample was 0.991, and the conduction mechanism for this sample followed the quantum mechanical tunneling (QMT) model. Linear sweep voltammetry (LSV) showed that this sample was electrochemically stable up to 1.90 V. The highest conducting sample was used in the fabrication of an electrical double layer capacitor (EDLC) cell.     

On the existence of a pyrochlore-type phase in the system Bi2O3–TiO2

The existence of a bismuth titanate in the range between Bi₂Ti₄O₁₁ (Bi₂O₃ · 4 TiO₂) and Bi₄Ti₃O₁₂ (2 Bi₂O₃ 3TiO₂) has been investigated by X-ray diffraction of samples prepared by solid state reactions. For reaction temperatures above 1100 °C and a starting composition Bi₂O₃ · 2 TiO₂ there appeared additional lines which could be attributed to a cubic face-centred cell with a = 10.354 Å. A multiphase Rietveld analysis based on X-ray powder diffraction data confirmed the structural model of a pyrochlore for this compound. There is evidence that this phase belongs to the group of defect pyrochlores with a Bi³⁺-deficiency resulting in a composition of Bi_1.833Ti₂O_6.75.