Synthesis, characterization and electrical properties of the new solid electrolyte materials Ce6-xErxMoO15-delta (0.0 < x < 1.5)

A new series of oxides, Ce6-xErxMoO15-delta (0.0 less than or equal to x less than or equal to 1.5), was synthesized using wet-chemistry techniques. The precursors and resultant oxide powders were characterized by differential thermal analysis/thermogravimetry, x-ray diffraction, and IR, Raman and x-ray photoelectron spectroscopy. The formation temperature of the powders was found to be as low as 350degreesC. Ce6-xErxMoO15-delta crystallized to a fluorite-related cubic structure. The electrical conductivity of the samples was investigated by using ac impedance spectroscopy. This showed that the presence of Er was related to the oxygen-ion conductivity, and that the highest oxygen-ion conductivity was found in Ce6-xErxMoO15-delta (x = 0.4), ranging from 5.9 x 10(-5) S cm(-1) at 300degreesC to 1.26 x 10(-2) S cm(-1) at 700degreesC, respectively. This kind of material shows a potential application in intermediate-temperature solid oxide fuel cells.

GAMMA-RADIATION INDUCED CROSS-LINKED PEO-LICLO4 SOLID-ELECTROLYTE SYSTEM

Aimed at raising the room temperature ionic conductivity of PEO-based solid polymer electrolyte and considered that the ionic conduction preferentially occurs in the amorphous phase, we lightly crosslinked the high MW PEO through gamma-irradiation and further suppressed the residual crystallinity by plasticizing with propylene carbonate. By incorporating LiClO4 salt to the above described polymer host, the ambient (25 degrees C) ionic conductivity of the electrolyte system could reach as high as 6.8 X 10(-4) S/cm. As the electrolyte was a crosslinked system, it was mechanically self-supportable. Based on the preliminary results of the electrochemical performance of the secondary lithium battery, assembled by using this kind of solid electrolyte and polyaniline as positive electrode, it is realized that the electrolyte thus prepared is of high expectancy.

Electrochemical H2S sensor with H2SO4 pre-treated Nafion membrane as solid polymer electrolyte

It is reported for the first time that the performance of the electrochemical H2S sensor with the Nation membrane pre-treated with the concentrated H2SO4 as the solid electrolyte is much more stable than that for the sensor with the Nation membrane without H2SO4 pretreatment. The sensitivity of the sensor is about 2.92 muA/ppm. The response time of the sensor is about 9 s. The detection limit is about 0.1 ppm. Therefore, this kind of the electrochemical H2S gas sensor may be desirable for the practical application.

Nitrate-citrate combustion synthesis and properties of Ce1-xSmxO2-x/2 solid solutions

A nitrate-citrate combustion route to synthesize nanocrystalline samarium-doped ceria powders for solid electrolyte ceramics is presented. This route is based on the gelling of nitrate solutions by the addition of citric acid and ammonium hydroxide, followed by an intense combustion process due to an exothermic redox reaction between nitrate and citrate ions. The influence of ignition temperature on the characteristics of the powders was studied. The change of the crystal structure with the content of doped Sm was investigated. High temperature X-ray, and Raman scattering were used to characterize the sample. The lattice constant and unit volume increase with doping level and increasing temperature. Dense ceramic samples prepared by uniaxial pressing and sintering in air were also studied.

Low temperature preparation of ceria solid solutions doubly doped with rare-earth and alkali-earth and their properties as solid oxide fuel cells

A series of solid electrolytes, (Ce(0.8)Ln(0.2))(1 - x)MxO2 - delta(Ln = La, Nd, Sm, Gd, M:Alkali-earth), were prepared by amorphous citrate gel method. XRD patterns indicate that a pure fluorite phase is formed at 800 degreesC. The electrical conductivity and the AC impedance spectra were measured. XPS spectra show that the oxygen vacancies increase owing to the MO doping, which results in the increase of the oxygen ionic transport number and conductivity. The performance of ceria-based solid electrolyte is improved. The effects of rare-earth and alkali-earth ions on the electricity were discussed. The open-circuit voltages and maximum power density of planar solid oxide fuel cell using (Ce0.8Sm0.2)(1 - 0.05)Ca0.05O2 - delta as electrolyte are 0.86 V and 33 mW . cm(-2), respectively.

Sol-gel synthesis and properties of Ce1-xGdxO2-x/2 solid solutions

A series of solid electrolytes Ce1-xGdxO2-x/2(x=0 similar to0.6) was prepared by sol-gel method. The structure, thermal expansion coefficient and electrical properties of the solid solutions were systematically studied. XRD data showed that a complete cubic fluorite structure was formed at 160 degreesC. The purity of the product prepared by the sol-gel method is higher, the grain size is uniformly smaller. They were easily sintered into highly dense ceramic pellets at 1 300 degreesC. The sintering temperature was significantly lower than that by traditionally high temperature solid phase reaction method. The thermal expansion coefficient of Ce0.8Gd0.2O1.9, determined from high- temperature XRD data, is 8. 125 X 10(-6) K-1. Impedance spectra analyses showed that the grain-boundary resistance of the solid electrolyte prepared by sol-gel method was reduced or even eliminated. The conductivity of Ce0.8Gd0.2O1.9 is 5.26 X 10(-3) S/cm at 600 degreesC. The activation energy (E-a) is 0.82 eV.

Low temperature preparation and fuel cell properties of rare earth doped barium cerate solid electrolytes

The solid electrolytes, BaCe(0.8)Ln(0.2)O(2.9) (Ln: Gd, Sm, Eu), were prepared by the sol-gel method. XRD indicated that a pure orthorhombic phase was formed at 900 degrees C. The synthesis temperature by the sol-gel method was about 600 degrees C: lower than the high temperature solid phase reaction method. The electrical conductivity and impedance spectra were measured and the conduction mechanism was studied. The grain-boundary resistance of the solid electrolyte could be reduced or eliminated by the sol-gel method. The conductivity of BaCe0.8Gd0.2O2.9 is 7.87 x 10(-2) S.cm(-1) at 800 degrees C. The open-circuit voltage of hydrogen-oxygen fuel cell using BaCe0.8Gd0.2O2.9 as electrolyte was near to 1 V and its maximum power density was 30 mW.cm(-2).

Sol-gel synthesis and electrical properties of ceria-based solid electrolytes

A series of solid electrolytes (Ce0.8RE0.2)(1-x)MxO2-delta(RE: Rare earth, M: Alkali earth) were prepared by sol-gel methods. XRD indicated that a pure fluorite phase was formed at 800 degrees C. The synthesis temperature by the sol-gel methods was about 700 degrees C lower than by the traditional ceramic method. The electrical conductivity and impedance spectra were measured. XPS showed that the oxygen vacancy increased obviously by doping MO, thus, resulting in the increase of the oxygen ionic transport number and conductivity. The performance of ceria-based solid electrolyte was improved. The effects of RE2O3 and MO on the electrical properties were discussed. The conductivity and the oxygen ionic transport number of (Ce0.8Sm0.2)(1-0.05)Ca0.05O2-delta is 0.126 S.cm(-1) and 0.99 at 800 degrees C, respectively.

Effects of Pr dopant on grain boundary and electrical properties of Ce5.2Sm0.8MoO15-delta

Material formulated as Ce5.2Sm0.8-xPrxMo15-(delta) (x=0.08) was prepared by adding small amounts of Pr dopant in oxide Ce5.2SM0.8-xPrxMoO15-delta. Structural and electrical properties were investigated by means of X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM) and AC impedance spectroscopy. The effect of small amounts of Pr on microstructure and electrical conductivity was discussed. It was showed that the material doped with Pr has a lot of dents and small openings, which provide channels for oxygen ions, resulting in lower grain boundary and total conductivity activation energy. Thus the corresponding grain boundary conductivity and total conductivity of the material were improved notably. The grain boundary conductivity of the material doped with Pr is 6.79 X 10(-3) S center dot cm(-1) at 500 degrees C, which is twice as large as that without Pr (5.61 X 10(-5) S center dot cm(-1)).

Application of modified Nafion membrane to the sulfur dioxide gas electrochemical sensor

The electrochemical SO2 sensor worked at the fixed potential and prepared with Nafion membrane as the solid electrolyte was studied. It v as observed that after Nafion membrane, was treated with H2SO4, the water-preserving ability of the membrane was increased. In turn, the performance of the sensor became stable. After lifetime test for 4 months, the performance of the sensor deceased slightly, Thus this kind of sensor may become a gas sensor for the practical application.

A novel electrochemical method for simultaneously measuring diffusion coefficient and ion transference number

This paper introduces a new method to estimate the diffusion coefficient and transference number of a salt or an electroactive ion in a solution with little or no supporting electrolyte. The above two parameters can be obtained from a single potential step experiment without previous knowledge of either one. It would appear that the method could also be used in the study of ion transport in a high viscosity solvent or a solid electrolyte. (C) 1998 Elsevier Science S.A.

Comb polymer electrolytes - Ionic conductivity and cation-polymer interaction

Three comb polymers(CP) with oligo-oxyethylene side chains of the type -O(CH2CH2O)(n)CH3 were prepared from methyl vinyl ether/maleic anhydride alternating copolymer. Homogeneous amorphous polymer electrolytes were made from CP and LiCF3SO3 or LiClO4 by solvent-casting method, and their conductivities were measured as a function of temperature and salt concentration. The conductivity which displayed non-Arrhenius behaviour was analyzed using the Vogel-Tammann-Fulcher equation. The conductivity maximum appears at lower salt concentration when CP has longer side chains. XPS was used to study the cation-polymer interaction.

注浆法制备YSZ固体电解质及其性能研究

以多孔石膏模具为成型载体，以8mol%钇稳定氧化锆(YSZ)粉体为原料，采用注浆法制备出具一定体积和形状的全稳定YSZ固体电解质。对注浆成型工艺中制备素坯的各个环节的主要影响因素(粘结剂种类及用量的选择、固相含量、球磨时间等)与浆料稳定性、流动性及素坯密度之间进行优化实验，确定了制备悬浮稳定、流动性好的浆料的实验参数。 将利用上述浆料于多孔石膏模中成型后的素坯进行等静压操作，进一步提高其致密度，为制备致密化高的电解质材料奠定了条件。结果表明：注浆成型后的素坯在进一步等静压处理后相对密度可达53%左右，可以说注浆成型法是一种成型具一定体积素坯的简单可行的方法。 继而将成型后的素坯于不同的烧结条件下进行常压烧结，并对烧结后YSZ固体电解质的致密化程度、微观形貌(SEM)及导电性能进行测量和表征，借助于交流阻抗谱测量其导电性，采用氧浓差电池法测定其离子迁移数(能斯特响应)。通过对烧结体的性能分析，建立其致密程度、导电性与烧结条件之间的关系，并以此为依据来优化烧结工艺。 结果表明：样品的致密度随烧结温度和烧结时间的增加而提高，电导率随着致密度的提高而不断增加，其中在1550℃烧结3h的电解质制品500℃时的阻抗测试结果表明其离子导电率已超过投入实际使用的最小限定值；结合样品的微观形貌分析，在较高的烧结温度下晶粒增长显著，平均粒径可以达到微米级，而低温下增长不显著。 立足于砖层模型和多晶电解质晶界空间电荷层导电特性，对不同粒径的YSZ多晶固体电解质材料的晶界电导进行分析，结果表明随平均粒径的减小，YSZ多晶固体电解质材料晶界空间电荷层电势减小，而其中氧空位浓度增加，因此可以说，对高纯物质而言，晶粒的减小有助于提高其整体电导性。因而就优化烧结工艺而言，要制备高性能YSZ固体电解质可以以达到高致密度、抑制晶粒显著生长为原则来进行探讨。

Synthesis and Electrical Properties of New Solid State Electrolyte Materials Ce6-xHoxMoO15-delta(0.0 <= x <= 1.2)

Ce6-xHoxMoO15-delta(0.0 <= x <= 1.2) was synthesized by modified sol-gel method and characterized by differential X-ray diffraction(XRD), Raman, and X-ray photoelectron spectroscopy(XPS) methods. The oxide ionic conductivity of the samples was investigated by AC impedance spectroscopy. It shows that all the samples are single phase with a cubic fluorite structure. The solid solution Ce6-xHoxMoO15-delta(x=0.6) was detected to be the best conducting phase with the highest conductivity(sigma(t)=1.05x10(-2) S/cm) at 800 degrees C and the lowest activation energy(E-a=1.09 eV). These properties suggest that this kind of material has a potential application in intermediate-low temperature solid oxide fuel cells.

Synthesis and electrical properties of new solid state. Electrolyte materials Ce5.2RE0.8MoO15-delta

A series of solid state electrolytes, Ce-5.2 RE0.8 MoO15-delta (RE = Y, La, Sm, Gd, Dy, Ho, Er), were synthesized by sol-gel method. Their structures and electrical conductivities were characterized by X-ray Diffraction (XRD), Raman and X-ray Photoelectron Spectroscopy (XPS) and AC impedance spectroscopy, respectively. The results show that the concentrations of oxygen vacancy increased with increasing x and their conductivity were improved. And the cell parameters increase as the radius of RE3+ increases. Because the ionic radius of doped Dy3+ (0.0908 nm) is closed to that of Ce4+ (0.0920 nm), their oxide has minimal cell elastic straining between RE3+ and oxygen vacancy, and the system has the least association enthalpy, thus the oxide Ce-5.2 Dy-0.8 MoO15-delta exhibits a higher conductivity (7.02 x 10(-3) S/cm) and lower activation energy (1.056 eV) compared to the other doped compounds.