Co-synthesis of nano-sized LSM–YSZ composites with enhanced electrochemical property

Nano-sized LSM–YSZ composite was co-synthesized by a glycine–nitrate process (GNP). Transmission electron microscopy revealed that the as-prepared LSM–YSZ particles consist of nano-sized powders with a dominant YSZ phase. Backscatter electron image shows that LSM and YSZ phases were regularly dispersed within the composite. Alternating current impedance measurement revealed that the co-synthesized LSM–YSZ electrode shows lower polarization resistance and activation energy than the physically mixed LSM–YSZ electrode. This electrochemical improvement would be attributed to the increase in three-phase boundary and good dispersion of LSM and YSZ phases within the composite. This paper is dedicated to Professor Su-Il Pyun on the occasion of his 65th birthday.     

Formation of thin YSZ electrolyte films by electrophoretic deposition on porous cathodes

The structure, dispersity, stability, and electrophoretic deposition (EPD) of suspensions of spherical ZrO₂ stabilized Y₂O₃ (YSZ) nanoparticles with a mean size of 10.9 nm onto the porous surface of La_0.6Sr_0.4MnO₃ (LSM) with a pore size of 3–20 μm were studied by electron microscopy, photon correlation spectroscopy, and electroacoustical analysis. The optimum conditions of deposition were attained by using a mixed isopropanol-acetylacetone dispersion medium, which provided the aggregative stability of the suspension with 95% individual particles. The maximum pore size on the covered surface should be up to 0.5 μm if nanoparticles with a mean diameter of 10–20 nm are used. When the pores are larger, the EPD of YSZ will be effective if an additional intermediate LSM layer is formed by EPD to provide the required pore size.     

锰酸镧双层复合电极的制备和性能的研究

固体氧化物燃料电池（ Solid Oxide Fuel Cell, SOFC）是一种很有希望的新型能源转换系统 .它具有能量转换效率高、可利用燃料范围广、低排放等普通热机所无法比拟的优点,已倍受人们的关注 .　　锶掺杂的锰酸镧（ La1－ xSrxMnO3, LSM）由于具有高的电子导电性和对氧还原的良好的电催化活性,以及它和钇稳定的氧化锆（ YSZ）都有良好的热稳定性和化学稳定性,因此是目前广泛使用的阴极材料 .以 YSZ为固体电解质的固体氧化物燃料电池的一个主要缺点是操作温度太高（约为 1273 K）,如果把电池的操作温度降低到 873－ 1073 K,则…     

(La0.8Sr0.2)0.9MnO3–Gd0.2Ce0.8O1.9 composite cathodes prepared from (Gd, Ce)(NO3) x -modified (La0.8Sr0.2)0.9MnO3 for intermediate-temperature solid oxide fuel cells

Development of high performance cathodes with low polarization resistance is critical to the success of solid oxide fuel cell (SOFC) development and commercialization. In this paper, (La_0.8Sr_0.2)_0.9MnO₃ (LSM)–Gd_0.2Ce_0.8O_1.9(GDC) composite powder (LSM ~70 wt%, GDC ~30 wt%) was prepared through modification of LSM powder by Gd_0.2Ce_0.8(NO₃) _x solution impregnation, followed by calcination. The electrode polarization resistance of the LSM–GDC cathode prepared from the composite powder was ~0.60 Ω cm² at 750 °C, which is ~13 times lower than that of pure LSM cathode (~8.19 Ω cm² at 750 °C) on YSZ electrolyte substrates. The electrode polarization resistance of the LSM–GDC composite cathode at 700 °C under 500 mA/cm² was ~0.42 Ω cm², which is close to that of pure LSM cathode at 850 °C. Gd_0.2Ce_0.8(NO₃) _x solution impregnation modification not only inhibits the growth of LSM grains during sintering but also increases the triple-phase-boundary (TPB) area through introducing ionic conducting phase (Gd,Ce)O_2-δ, leading to the significant reduction of electrode polarization resistance of LSM cathode.     

High performance solid oxide fuel cells with electrocatalytically enhanced (La,Sr)MnO3 cathodes

The conventionally mixed LSM–YSZ, LSM impregnated YSZ (LSM + YSZ) and Pd impregnated LSM–YSZ (Pd + LSM–YSZ) cathodes, were prepared and evaluated by electrochemical impedance spectroscopy and single cell testing. The electrochemical performance of the impregnated cathodes have been significantly boosted due to the formation of nano-sized LSM and Pd particles on the YSZ and LSM–YSZ substrates, respectively, and in turn, the increased area of the triple phase boundary (TPB) where the O₂ reduction reaction occurs, the power densities as high as 1.42 and 0.83 W cm^?2 at 750 °C were achieved from single cells with the Pd + LSM–YSZ and LSM + YSZ cathodes, respectively, in contrast to 0.20 W cm^?2 from the single cell with the conventional LSM–YSZ cathode. Suggesting the Pd + LSM–YSZ and LSM + YSZ cathodes can be well used for the intermediate temperature solid oxide fuel cells (IT-SOFCs).     

Mid-temperature solid oxide fuel cells with thin film ZrO<Subscript>2</Subscript>: Y<Subscript>2</Subscript>O<Subscript>3</Subscript> electrolyte

Data on the mid-temperature solid-oxide fuel cells (SOFC) with thin-film ZrO₂-Y₂O₃ (YSZ) electrolyte are shown. Such a fuel cell comprises a carrying Ni-YSZ anode, a YSZ electrolyte 3–5 μm thick formed by vacuum ion-plasma methods, and a LaSrMnO₃ cathode. It is shown that the use of a combined method of YSZ electrolyte deposition, which involves the magnetron deposition of a 0.5–1.5-μm thick sublayer and its pulse electron-beam processing allows a dense nanostructured electrolyte film to be formed and the SOFC working temperature to be lowered down as the result of a decrease in both the solid electrolyte Ohmic resistance and the Faradaic resistance to charge transfer. SOFC are studied by the methods of voltammentry and impedance spectroscopy. The maximum power density of the SOFC under study is 250 and 600 mW/cm⁻² at temperatures of 650 and 800°C, respectively.     

Effect of Calcination Temperature on the Properties of Mn–Zr–Ce Catalysts in the Oxidation of Carbon Monoxide

Kinetics and Catalysis - The effect of the calcination temperature of MnOх–ZrO2–CeO2 catalysts on their structural properties and activity in the reaction of CO oxidation has been...     

The Comparative Study of Reaction Mechanisms and Catalytic Performances of Cu–SSZ-13 and Fe–SSZ-13 for the NH3-SCR Reaction

Catalysis Surveys from Asia - The catalytic performances and mechanism differences of model catalysts Cu–SSZ-13 and Fe–SSZ-13 with similar metal content and Si/Al ratio were compared....     

Sintering studies on Ni–Cu–YSZ SOFC anode cermet processed by mechanical alloying

New 40 vol%[(Cu)–Ni]–YSZ cermet materials processed by mechanical alloying (MA) of the row powders are prepared. The powder compacts are sintered in air, hydrogen and inert (argon) atmospheres at a dilatometer and tubular furnace up to 1,350 °C. Sintering by activated surface concept (SAS) can anticipate and enhance the densification in such powders. Stepwise isothermal dilatometry (SID) sintering kinetics study is performed allowing determining kinetic parameters for Ni–YSZ and Ni–Cu–YSZ pellets. Two-steps sintering processes is indicated while Cu-bearing material features the smallest activation energy for sintering. The allied MA–SAS method is a promising route to prepare SOFC fuel cell anode materials.     

Crafting La0.2Sr0.8MnO3-δ membrane with dense surface from porous YSZ tube

This work reports a new design of asymmetric tubular oxygen-permeable ceramic membrane (OPCM) consisting of a porous Y₂O₃ stabilized ZrO₂ (YSZ) tube (with ∼1 μm of pore diameters and 31% porosity) as the support and a gas-tight mixed conductive membrane. The membrane has an interlocking structure composed of a host matrix, Ag(Pd) alloy (9:1 by wt) doped perovskite-type (LSM80, 90wt%), and the embedded constituent, pristine LSM80. The Ag(Pd) alloy component promotes not only electronic conductivity and mechanical strength but also reduction of both porosity and pore sizes in the layer (∼10-μm-thick) where it dopes. The porous structure in this layer could then be closed through a solution coating procedure by which ingress of an aqueous solution containing stoichiometric nitrate salts of La³⁺, Mn³⁺, and Sr²⁺ to the pore channels takes place first and the mixture of nitrate salts left after drying is subjected to pyrolysis to generate tri-metal oxides in situ. This is followed by calcinations at l,300 °C to consolidate the embedded trioxide and to cohere them with the Ag(Pd)-LSM80 host matrix. The structure formed is dubbed LSM80(S)-Ag(Pd)-LSM80, which was confirmed gas-tight by electron micrograph and N₂ permeation test. Finally, we assess the chemical compatibility between LSM80 and YSZ at the sintering temperature by X-ray diffraction and electrochemical impedance analysis. The oxygen permeation of the fabricated LSM80(S)-Ag(Pd)-LSM80-YSZ membrane is within the temperature range of 600 to 900 °C. The tests reveal good compatibility between the LSM80 and YSZ and a reasonably high oxygen permeation flux in association with this OPCM assembly.     

Electrocatalytic properties of La0.9Sr0.1MnO3-based electrodes for oxygen reduction

Electrochemical reduction of oxygen at the interface between a La_0.9Sr_0.1MnO₃ (LSM)-based electrode and an electrolyte, either yttria-stabilized-zirconia (YSZ) or La_0.8Sr_0.2Ga_0.9Mg_0.1O₃ (LSGM), has been investigated using DC polarization, impedance spectroscopy, and potential step methods at temperatures from 1053 to 1173 K. Results show that the mechanism of oxygen reduction at an LSM/electrolyte interface changes with the type of electrolyte. At an LSM/YSZ interface, the apparent cathodic charge transfer coefficient is about 1 at high temperatures, implying that the rate-determining step (r.d.s.) is the diffusion of partially reduced oxygen species, while at an LSM/LSGM interface the cathodic charge transfer coefficient is about 0.5, implying that the r.d.s. is the donation of electrons to atomic oxygen. The relaxation behavior of the LSM/electrolyte interfaces displays an even more dramatic dependence on the type of electrolyte. Under cathodic polarization, the current passing through an LSM/YSZ interface increases with time whereas that through an LSM/LSGM interface decreases with time, further confirming that it is the triple phase boundaries (TPBs), rather than the surface of the LSM or the LSM/gas interface, that dominate the electrode kinetics when LSM is used as an electrode. Electronic Publication     

Volumetric and Viscosimetric Measurements for Methanol + CH 3 –O–(CH 2 CH 2 O) n –CH 3 ( n = 2, 3, 4) Mixtures at (293.15–303.15) K and Atmospheric Pressure: Application of the ERAS Model

Densities, $$\rho$$, and kinematic viscosities, $$\nu$$, have been determined at atmospheric pressure and at 293.15–303.15 K for binary mixtures formed by methanol and one linear polyether of the type CH3–O–(CH2CH2O)n–CH3 (n = 2, 3, 4). Measurements on $$\rho$$ and $$\nu$$ were carried out, respectively, using an Anton Paar DMA 602 vibrating-tube densimeter and an Ubbelohde viscosimeter. The $$\rho$$ values were used to compute excess molar volumes, $$V_{{\text{m}}}^{{\text{E}}}$$, and, together with the $$\nu$$ results, dynamic viscosities ($$\eta$$). Deviations from linear dependence on mole fraction for viscosity, $$\Delta \eta$$, are also provided. Different semi-empirical equations have been employed to correlate viscosity data. Particularly, the equations used are the: Grunberg–Nissan, Hind, Frenkel, Katti–Chaudhri, McAllister and Heric. Calculations show that better results are obtained from the Hind equation. The $$V_{{\text{m}}}^{{\text{E}}}$$ values are large and negative and contrast with the positive excess molar enthalpies, $$H_{{\text{m}}}^{{\text{E}}}$$, available in the literature, for these systems. This indicates that structural effects are dominant. The $$\Delta \eta$$ results are positive and correlate well with the difference in volumes of the mixture compounds, confirming the importance of structural effects. The temperature dependences of $$\eta$$ and of the molar volume have been used to calculate enthalpies, entropies and Gibbs energies, $$\Delta G^{*}$$, of viscous flow. It is demonstrated that $$\Delta G^{*}$$ is essentially determined by enthalpic effects. Methanol + CH3–O–(CH2CH2O)n–CH3 mixtures have been treated in the framework of the ERAS model. Results for $$H_{{\text{m}}}^{{\text{E}}}$$ are acceptable, while the composition dependence of the $$V_{{\text{m}}}^{{\text{E}}}$$ curves is poorly represented. This has been ascribed to the existence of strong dipolar and structural effects in the present solutions.     

Determination of The Oxygen Chemical Diffusion Coefficient in Perovskites by a Thermogravimetric Method

A thermogravimetric method has been used for the determination of the oxygen chemical diffusion coefficients in La_1–xSr_xMnO_3+δ; x=0; 0.05; 0.10; 0.15 (LSM). A temperature range of 700–1000°C was studied. The chemical diffusion coefficient varies between 1.6⋅10^–13 and 1.8⋅10^–10cm²s^–1 for the samples in the temperature range studied. The activation energy for oxygen chemical diffusion was determined to be 190–280 kJ mol^–1 for the LSM samples. The magnitude of the chemical diffusion coefficients of the LSM samples does not depend on the strontium site occupation factor. This revised version was published online in July 2006 with corrections to the Cover Date.     

Influence of YSZ buffer layer on the electric properties of compositionally graded (Ba,Sr)TiO<Subscript>3</Subscript> thin film

Compositionally graded Ba_1−x Sr _x TiO₃ (BST) (0 ≤ x ≤ 0.4) thin films were fabricated on Pt/Ti/SiO₂/Si and YSZ/Pt/Ti/SiO₂/Si substrates by a modified sol–gel technique. The YSZ buffer layer was prepared by RF magnetron sputtering. The microstructure of the graded BST films was investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The results showed that all the films have uniform and crack-free surface with a perovskite structure. The graded BST film with an YSZ buffer layer has larger dielectric constant and lower dielectric loss. The leakage current density of the graded BST film with an YSZ buffer layer lowers two orders than the film without buffer layer. The improved electric properties of the graded films with an YSZ buffer layer was attributed to the YSZ buffer layer act as an excellent seeding layer to enhance the graded BST film growth.     

Options for adjustment of microstructure and conductivity of cathodic substrates of La(Sr)MnO<Subscript>3</Subscript>

The electrodes of solid-oxide fuel cells (SOFCs) must be characterized by high conductivity to decrease ohmic losses and sufficient porosity to provide high gas diffusion rate. In the cases, when the SOFC electrodes are substrates, they must be synthesized at the temperature above the temperature of formation of their solid-electrolyte coating. Herewith, manufacturing of supporting electrodes with the required micro-structure is rather complicated. The present paper studies the effect of the method of manufacturing of the initial La_0.6Sr_0.4MnO₃ (LSM) powders, their degree of dispersion, introduction of sintering additives and pore agents on their microstructure, conductivity, and possibility of adjusting the temperature of SOFC cathodic substrate formation at which the required characteristics are reached. It is shown that sintering of cathodic substrates to the relative density of 65–70% can be carried out at the temperatures from 1050 to 1350–1400°C, which would allow obtaining electrolyte films of powders with different sintering ability on such substrates. The average pore size in cathodic substrates can be varied in the range of 0.4 to 2.5 μm by using the initial LSM powder with different dispersion degree and by employing graphite as a pore agent. At 900°C, conductivity of cathodic substrates of LSM grows at an increase in their relative density from 50% to 70% approximately from 50 to 100 S/cm and weakly depends on the dispersion degree of the initial powders.     

Electrical conductivities and microstructures of LSM,LSM-YSZ and LSM-YSZ/LSM cathodes fabricated on YSZ electrolyte hollow fibres by dip-coating

Lanthanum strontium manganite – La_0.80Sr_0.20MnO₃ (LSM), LSM-Yttria stabilised zirconia (LSM-YSZ) composite and LSM-YSZ/LSM double-layer cathodes were separately fabricated on Yttria stabilised zirconia (YSZ) electrolyte hollow fibres by dip coating; their electrical conductivities and microstructures were then determined by the direct current four-probe method and scanning electron microscopy (SEM), respectively. Excellent cathode-electrolyte and cathode-cathode adhesion without delamination were achieved by the dip-coating fabrication method. The apparent electrical conductivities of porous LSM, LSM-YSZ and LSM-YSZ/LSM cathodes manufactured on YSZ hollow fibre by dip-coating and sintered at various temperatures in the range 1273–1473 K for 3 h, were 1.8 × 10³–5.5 × 10³ S/m, 0.32–209 S/m and 1.3 × 10³–5.5 × 10³ S/m, respectively, at measurement temperatures of 673–1073 K. The operating temperature dependence of the apparent electrical conductivity of the LSM, LSM-YSZ and LSM-YSZ/LSM cathodes was defined by the Arrhenius equation for electrical conductivity. The activation energies for electrical conductivity were derived as 0.106–0.147 eV, 0.83–0.94 eV, and 0.104–0.146 eV for the LSM, LSM-YSZ and LSM-YSZ/LSM cathodes, respectively. The LSM-YSZ and LSM-YSZ/LSM cathodes were strongly influenced by the YSZ and LSM phases, respectively.     

Oxygen isotope exchange between the gas-phase and the electrochemical cell O<Subscript>2</Subscript>, Pt | YSZ | Pt,O<Subscript>2</Subscript> under conditions of applied potential difference

The kinetics of oxygen isotope exchange between gas-phase oxygen and the electrochemical cell O₂, Pt | ZrO₂ + 10 mol % Y₂O₃ (YSZ) | Pt, O₂ with applied potential difference (ΔU = ±1.2 V) is studied in the temperature range of 600–800°С and the oxygen pressure interval of 3–13 kPa. An original design of a vacuum electrochemical cell with the separated gas space is put forward for studying how the potential difference on the electrochemical cell influences the kinetics of interaction of gas-phase oxygen with the gas electrode O₂, Pt | YSZ in the electrochemical cell. It is shown that the oxygen interphase exchange rate is the higher the more negative the charge on the electrode studied; moreover, the mechanism of gas-phase oxygen exchange with the gas electrode O₂, Pt | YSZ in the electrochemical cell depends fundamentally on the electrode charge sign. The possible reasons for the revealed differences are discussed; the corresponding models are proposed.     

Ion Implantation in Diazoquinone–Novolac Photoresist

High Energy Chemistry - The processes of modifying the structural and optical properties of FP9120 and S1813 diazoquinone–novolac photoresist films on single-crystal silicon wafers beyond the...     

O_2存在下NO在固体电解质电池上分解机理

研究了在O_2存在条件下,NO在Pd |YSZ| Pd固体电解质电池和RuO_2 |Pd|YSZ| Pd固体电解质电池上的分解性质,在O_2存在条件下650 ～ 700 ℃之间 ,在0 ～ 4.4 V直流电压作用下,NO在Pd |YSZ| Pd电池和RuO_2|Pd|YSZ| Pd电池 上的分解不以电解机制进行,而以电催化机理进行的。即在直流电压下,阴极催化 剂上的O~(2-)被直流电压通过YSZ固体电解质转移到阳极,以O_2的形式放出,以此 保持催化剂的活性状态。在Pd|YSZ|Pd 固体电解质电池上,Pd金属表面是催化NO分 解的主要活性位。RuO_2 |Pd|YSZ| Pd固体电解质电池上,某特定还原态的RuO_x (0 < x < 2)是NO分解的主要活性位。在O_2存在下,该电池在1 ～ 4 V间合适的电 压下,在650 ～ 700 ℃能选择性地对NO进行电催化分解。     

在RuO2|Pd|YSZ|PddeNOx电解池中O2-传导的速控步骤

研究了500～750℃富氧条件下RuO₂|M|YSZ|Pd(M=Ag,Pd,Pt,Au)固体电解质电解池在0～4V直流电压下对NO的分解性质.600℃下,O^2-在Pd|YSZ阴极界面处的传导是O^2-在RuO₂|Pd|YSZ|Pd固体电解质电解池中传导过程的速控步骤.反应温度越低,RuO₂|Pd|YSZ|Pd电解池上NO电催化分解相对于氧分解的选择性因子α越大.600℃下O^2-在M|YSZ阴极界面处的传导阻力按Ag2|Ag|YSZ|Pd电解池上分解率为15.3%,NO选择性因子达到13.4.