Study on rare earth electrolyte of SDC-LSGM

Ce0.85Sm0.15O1.925 （SDC） and La0.9Sr0.1Ga0.5Mg0.2O2.85 （LSGM） were synthesized using Glycine-Nitrate Process （GNP）, and the composite electrolytes were prepared by mixing SDC and LSGM. An X-ray diffraction pattern indicated that the mixture of SDC and LSGM consisted of their original phases after heating at 1450 ℃ for 10 h. The electronic conductivity of SDC-LSGM composite electrolytes were measured by direct current polarization method using Hebb-Wagner ion blocking cell at 700-800 ℃ in the oxygen partial pressure range of 104-10-20 MPa and compared with the results of SDC. Typical polarization curves, which were theoretically predicted, were observed on all the samples. The slopes of lgσe-lgPo2 plot for all the composite electrolytes agreed with the theoretically predicted value of-1/4 at some intermediate oxygen partial pressures and -1/6 at low oxygen partial pressure. The electronic conductivity of SDC-LSGM composite electrolytes decreased with the increase in LSGM content, whereas the ionic transport number ti of all the samples increased with the increase in LSGM content.     

Structural and electrical properties of La2-xSrxMo2O9-δ

Sr-doped La2Mo2O9 were prepared by solid state reaction and characterized by XRD,impedance spectroscopy and HebbWagner polarization method.XRD patterns of the samples indicated that the solubility limit of Sr2+ in La2-xSrxMo2O9-δ was in the range of 7 mol.% to 7.5 mol.%,i.e.,the maximum stoichiometric coefficient x in La2-xSrxMo2O9-δ was larger than 0.14 and less than 0.15.The cubic lattice parameter of La2-xSrxMo2O9-δ(0相似文献   

Electrical Properties and Microwave Synthesis of Mixed Rare Earth Oxide Ln0.7Sr0.3-xCaxCo0.9Fe0.1O3-δ

In order to lower the raw materials cost and develop a novel cathode materials for intermediate temperature solid oxide fuel cell(ITSOFC), using mixed rare earth replacing the expensive pure La2O3 as the raw materials, the powders of Ln0.7Sr0.3-xCaxCo0.9Fe0.1O3-δ (Ln=the mixed rare earth, x=0.05, 0.10, 0.15) for the applications as the cathode materials were prepared by microwave sintering process. The crystal structure and the particles morphology of the obtained powders were characterized by XRD and SEM, the electrical conductivity of all samples sintered at 1200 ℃ for 3 h was also measured as the function of the temperature from 100 to 800 ℃ by DC four-probe method in air. The experimental results show that due to the influence of mixed rare earth the powders of Ln0.7Sr0.3-xCaxCo0.9Fe0.1O3-δ synthesized at 1200 ℃ for 0.5 h with the mean particle size of 1～20 μm was of perovskite and cubic fluorite phase as well a little SrO phase, the electrical conductivity of the samples decreases with the adding Ca2+ content, and are all higher than 100 S·cm-1 from 500 to 700 ℃ when x≤0.10. Ln0.7Sr0.3-xCaxCo0.9Fe0.1O3-δ. Can meet the demand of the electrical properties for the cathode materials in ITSOFC.     

Wet chemical synthesis of La9.83–xSrxSi6O26+δ（0≤x≤0.50） powders,characterization of intermediate and final products

In this paper we reported the preparation and extensive characterization of La9.83–x Sr x Si6O26+δ(0≤x≤0.50) precursors, intermediate and final products. The sintering reactions, the phase formation, the structure as well as the powders’ morphology were studied by means of thermogravimetric analysis, X-ray diffraction(XRD), Fourier-transform infrared spectroscopy(FTIR) and scanning electron microscopy(SEM). Moreover, the effect of stoichiometry on precursor’s structure and morphology as well as on intermediate and final products was reported. As was concluded pure La9.83Si6O26+δ, La9.38Sr0.45Si6O26+δ and La9.33Sr0.50Si6O26+δ could be prepared after sintering at 1400 °C for 20 h while La9.68Sr0.15Si6O26+δ and La9.53Sr0.30Si6O26+δ compounds contained minor traces(<3.5%) of La2Si2O7 secondary phase. Concerning the synthesis, there have been no previous reports on the preparation of pure La9.83Si6O26+δ, La9.38Sr0.45Si6O26+δ and La9.33Sr0.50Si6O26+δ compounds. The final powders consisted of spherical particles and an increase of Sr content seemed to inhibit sintering phenomena. The existence of interstitial oxygen at intermediate crystallographic positions of apatite structure had great effect on Si O4 sub-structure distortion. The increase of Sr content led to a major reduction of interstitial oxygen quantity and the refutation of silicon tetrahedron distortion.     

Crystal structure,thermal expansion and electrical conductivity of Pr（Ga1-xCox）0.9Mg0.1O3-δ （x=0, 0.1, 0.2, 0.3）

Pr（Ga1-xCox）0.9Mg0.1O3-δ （x=0, 0.1, 0.2, 0.3） was synthesized using solid-state reaction technique to study the effects of Co doping on their structure and properties. Room and high temperature XRD, DSC and electrical conductivity measurement with D.C. four-probe technique were adopted in the study. The results indicated its orthorhombic-distorted perovskite structure at room temperature. PrGa0.9Mg0.1O3-δ maintained its orthorhombic-distorted structure between 298 and 1173 K. For Pr（Ga0.7Co0.3）0.9Mg0.1O3-δ, such structure existed below 873 K. From 873 to 1173 K, it possessed tetragonal structure. The transformation from orthorhombic to tetragonal structure at 873 K was of second order. The intrinsic volume thermal expansion of tetragonal structured Pr（Ga0.7Co0.3）0.9Mg0.1O3-δ Was about 50% higher than those of PrGa0.9Mg0.1O3-δ. The electrical conductivity increased with Co content. The activation energies of conduction for Pr（Ga1-xCox）0.9Mg0.1O3-δ are in range from 0.197 to 0.246 eV, much lower than 1.543 eV for PrGaO3.     

Crystal structure, thermal expansion and electrical conductivity of Pr(Ga1-xCox)0.9Mg0.1O3-δ(x=0,0.1,0.2,0.3)

Pr(Ga1-xCox)0.9Mg0.1O3-δ(x=0, 0.1, 0.2, 0.3) was synthesized using solid-state reaction technique to study the effects of Co doping on their structure and properties. Room and high temperature XRD, DSC and electrical conductivity measurement with D.C. four-probe technique were adopted in the study. The results indicated its orthorhombic-distorted perovskite structure at room temperature. PrGa0.9Mg0.1O3-δ maintained its orthorhombic-distorted structure between 298 and 1173 K. For Pr(Ga0.7Co0.3)0.9Mg0.1O3-δ, such structure existed below 873 K. From 873 to 1173 K, it possessed tetragonal structure. The transformation from orthorhombic to tetragonal structure at 873 K was of second order. The intrinsic volume thermal expansion of tetragonal structured Pr(Ga0.7Co0.3) 0.9Mg0.1O3-δ was about 50% higher than those of PrGa0.9Mg0.1O3-δ. The electrical conductivity increased with Co content. The activation energies of conduction for Pr(Ga1-xCox)0.9Mg0.1O3-δ are in range from 0.197 to 0.246 eV, much lower than 1.543 eV for PrGaO3.     

Preparation and Electrical Transport Properties of Perovskite Oxide Ln0.5Sr0.5CoO3

The superfine powders of Ln0.5 Sr0.5 CoO3 （Ln = La, Pr, Nd, Sm, Eu） were obtained by solid state reactions. The crystal structure and electrical transport properties of samples doped with different rare earth elements as well as the forming process of the Perovskite structure were studied. The result shows that when the temperature reaches 1200 ℃, the samples will become a steady and unitary Perovskite phase by solid state reactions. The conductive behavor at low temperature is consistent with small polaron mechanism （i. e., localized electronic carriers having a thermally activated mobility）. However, the maximum of conductivity appears at about 700 ℃, and the conductivity of La0.5Sr0.5CoO3 is the biggest in the intermediate-temperature （600 - 850 ℃ ）, so it is fit for cathode material of intermediate-temperature solid oxide fuel cells.     

Microwave assisted synthesis,sinterability and properties of Ca-Zn co-doped LaCrO_3 as interconnect material for IT-SOFCs

The interconnect materials La0.7Ca0.3Cr1-xZnxO3-δ(x=0,0.01,0.03,0.05,0.07) were prepared by a microwave assisted sol-gel auto-ignition process.The crystalline structures of the samples were characterized by X-ray diffraction(XRD) and the lattice parameters were evaluated with Rietveld method.For Ca-Zn co-doped LaCrO3 with x=0.03,the sintering activity was improved,and the relative density came up to 96.5% for the sample sintered at 1300 oC for 10 h.The electrical conductivity of the samples was increased from 21.1 S/cm to the maximum of 70.9 S/cm at 650 oC in air,with the x content increasing from 0.01 to 0.03.However,with x further increasing,the electrical conductivity was decreased.The average thermal expansion coefficient(TEC) of the samples at RT-1000 oC in air was ca.10.0×10-6 K-1.All data indicated that the La0.7Ca0.3Cr1-xZnxO3-δ series ceramics would be potential candidate to be used as an interconnect materials for IT-SOFCs.     

Structure and Electrical Conductivity of Compositely Doped Oxide Solid Electrolyte La0.8Sr0.2Ga0.8Mg0.12Co0.08O2.8

(La, Sr) (Ga, Mg) O3-δ, (LSGM) perovskite compositions doped with transition metal Co on the B-site were prepared by solid state reaction. The effect of partial substitution of Ga for Co, La0.8Sr0.2Ga0.8Mg0.12Co0.08O2.8 (LSGMC2008) on the electrical conductivity was discussed. The results showed the compacted samples sintered at 1350℃ possesses increased electrical conductivity at low temperatures. The XRD patterns of the title materials indicated that LSGMC2008 possessed orthorhombic perovskite-type structure. The grains distributed relatively uniform from SEM photo. The Arrhenius plots of ionic conductivity in air of the LSGMC2008 exhibited differing slopes in the low-and high-temperature regions, and the corresponding Ea values were much lower than that of LSGM2020. All of these suggested that even at low sintering temperature, proper amount Co doped was beneficial to improve ionic conductivity of LSGM.     

Magnetic Transition of La0.8Sr0.2Mn1-xCoxO3（x =0, 0.3, 0.5, 1.0）

A series of rare earth compound oxides with the formula of La0.8Sr0.2Mn1-xCoxO3（ were prepared by the method of citric acid. Structures, figures and magnetic properties of the x=0.0, 0.3, 0.5, 1.0） samples were analyzed by means of XRD, SEM and SQUID. Experiment results prove that all the samples are hexagonal, but their figures and magnetic properties are different. La0.8Sr0.2MnO3 is ferromagnetic. La0.8Sr0.2Mn0.7CO0.3O3 and La0.8Sr0.2Mn0.5Co0.5O3 are ferrimagnetic. La0.8Sr0.2CoO3 is antiferromagnetic. SEM results indicate that the structure of the first three are three-dimensional reticulations which are made up of some small ellipsoids which link up at the head and the end. The fourth sample looks like some dispersed small balls.     

Structural,magnetic and electrical characterization of the La0.7Ca0.3Co1–xMnxO3（x=0,0.7 and 1） compounds prepared by a simple method

Structural, magnetic and electrical properties of the La0.7Ca0.3Co1–xMnxO3（x=0, 0.7 and 1） samples prepared by a simple method were systematically studied and it was found that the crystal structure was transformed from rhombohedral for La0.7Ca0.3CoO3（LCCO） and La0.7Ca0.3Co0.3Mn0.7O3（LCCMO） samples to orthorhombic for La0.7Ca0.3MnO3（LCMO） sample. The AC magnetic susceptibility measurements showed that LCCO sample underwent a transition from paramagnetic（PM） to ferromagnetic（FM） phase at Curie temperature, TC~155 K and below Curie temperature, the glassy ferromagnetism nature was observed. In LCCMO sample,clear evidence of spin glass（SG） state was observed at low temperature. PM-FM phase transition at about TC~260 K and long range FM order at low temperatures were observed in LCMO sample. Both the LCCO and LCCMO samples exhibited insulating behavior in the whole range of measuring temperature whereas the LCMO sample underwent a clear metal-insulator（MI） transition at about TMI~263 K, corresponding to Curie temperature. Metallic region of ρ（T） curve of the LCMO sample was fitted to the model of electron-electron and electron-magnon scattering. The charge carrier transport behavior in all the samples was compared based on polaronic models.     

Synthesis and characterization of calcium and manganese-doped rare earth oxide La_(1-x)Ca_xFe_(0.9)Mn_(0.1)O_(3-δ) for cathode material in IT-SOFC

In order to develop novel cathode materials with high performance for intermediate temperature SOFC(IT-SOFC),Ca and Mn doped rare earth oxides La1-xCaxFe0.9Mn0.1O3-δ(x=0.1,0.3 and 0.5,denoted as LCFM9191,LCFM7391 and LCFM5591) were synthesized by solid state reaction(SSR) method.The formation process,phase structure and microstructure of the synthesized samples were characterized using thermogravimetry/differential scanning calorimetry(TG/DSC),X-ray diffraction(XRD) and scanning electron microscopy(SEM).The thermal expansion coefficients(TEC) of the samples were analyzed at 100-900 oC by thermal dilatometry.The electrical conductivities of the samples were measured with direct current(DC) four-terminal method from 300 to 850 oC.The results indicated that the samples(x=0.1 and 0.3) exhibited a single phase with orthorhombic and cubic perovskite structure,respectively after being sintered at 1200 oC for 3 h.The electrical conductivity of the samples increased with temperature up to a maximum value,and then decreased.The small polaron hopping was regarded as the conducting mechanism for synthesized samples at T≤600 oC.The negative temperature dependence occurring at higher temperature was due to the creation of oxygen vacancies for charge balance.LCFM7391 had higher mixed conductivity(>100 S/cm) at intermediate temperature and could meet the demand of cathode material for IT-SOFC.In addition,the average TECs of LCFM9191 and LCFM7391 were 11.9×10-6 and 13.1×10-6 K-1,respectively,which had good thermal match to the common electrolytes.     

Influence of oxygen non-stoichiometry on physical properties of NdSr2Mn2O7±δ

Nd Sr2Mn2O7+δ compounds were synthesized by ceramic method under three different cooling conditions. The Nd Sr2Mn2O7+δ samples were characterized by powder X-ray diffraction(XRD). Oxygen non-stoichiometry data for the studied powders were determined by using gravimetric and X-ray photoelectron spectroscopy(XPS) methods. The correlation of cooling method and oxygen as non-stoichiometry was established. The electroconductivity in samples was studied by using four-point probe method, and the strong correlation with non-stoichiometry was found out. Magnetization measurements were carried out. It was found that the magnetic and transport properties of the samples were also influenced by oxygen non-stoichiometry. The evolution of the magnetic properties could be explained by the formation of magnetic clusters in the vicinity of oxygen vacancies(OV) and strong competition between the superexchange and double exchange interactions.     

Preparation and characterization of La0.9Sr0.1Ga0.8Mg0.2O3–δ thin film deposited by radio frequency magnetic sputtering

La0.9Sr0.1Ga0.8Mg0.2O3-δ (LSGM) electrolyte materials were synthesized by the solid state reaction method.The conductivity of LSGM materials was detected by four probe method,and it was 0.08 S/cm at 850 ℃.Dense and uniform films of LSGM materials were deposited by the magnetic sputtering on substrates of Si and La0.7Sr0.3Cr0.5Mn0.5O3-δ (LSCM).The experimental results showed that the deposition rates dropped and the average grain sizes of the films enlarged with increase in the substrate temperatures.In the sputtering process,the LSGM film was deposited with preferred growth direction.After annealing,the preferred growth direction disappeared and the film surface became smoother and denser.Through observing the deposition process,deposition mechanism was proposed,which was consistent with a model of island growth.     

Characterization of A-site excessive perovskite La0.7-xSmx＋0.02Ca0.3CrO3-δ

La0.7-xSmx+0.02Ca0.3CrO3-δ(0≤x≤0.4) powders with A-site excessive perovskite structure were synthesized by auto-ignition process and characterized. X-ray diffraction (XRD) patterns of samples after sintering at 1400℃ for 4 h were indexed as tetragonal structure. The relative densities were all above 96% although decreased slightly with the increasing content of samarium, indicating that the excessive A-site element was helpful to enhance their sinterability. Conductivities of the specimens in air increased with increasing content of samar-ium. The conductivity of La0.6Sm0.12Ca0.3CrO3-δ was 33.6 S/cm in air at 700 ℃ which was about 1.7 times as high as that of La0.7Ca0.3CrO3-δ (20.1 S/cm). Average thermal expansion coefficients (TECS) of the specimens increased from 11.06×10-6 to 12.72×10-6 K-1 when x in-creased from 0 to 0.4, and they were close to that of Y doped ZrO2 (YSZ). La0.7-xSmx+0.02Ca0.3CrO<3-δ>(0.1≤x≤0.3) were good choices for in-termediate temperature solid oxide fuel cells (IT-SOFCs) interconnect materials.     

Synthesis and Electrical Properties of La0.6M0.4FeO3-δ(M=Ca, Sr, Ba) as Cathodes for SOFCs

A series samples of La0.6M0.4FeO3-δ (M=Ca, Sr, Ba) perovskite-type oxides were prepared by glycine nitrate process (GNP). FTIR, TG-DSC, XRD and TEM techniques were used to characterize the chemical constitution, thermal stability and phase structure. The electrical conductivity of the samples was investigated by four-probe technique. With the increase of substituted-ionic radius, the temperature of phase formation increases, and the solid solubility decreases gradually, respectively. The La0.6Ca0.4FeO3-δ(LCF)powder is pure cubic perovskite-type crystalline after fired at 850 ℃ for 2 h. The XRD patterns of La0.6Sr0.4FeO3-δ(LSF) powder shows a small quantity of SrO peaks sintered at 1050 ℃ for 2 h. The electrical conductivity of LCF and LSF at 500～800 ℃ is over 100 S·cm-1, and the value of LCF is 1170 S·cm-1 at 800 ℃, which indicate that LCF and LSF may be used as a profitable cathode for IT-SOFCs. The characteristic of La0.6Ba0.4FeO3-δ(LBF) is poor, and the electrical conductivity at intermediate temperatures is 1/20 less than that of LSF.     

Preparation and characterization of Ce_(0.8)La_(0.2–x)Y_xO_(1.9) as electrolyte for solid oxide fuel cells

In this study, ultrafine Ce0.8La0.2–x Y x O1.9（for x=0, 0.05, 0.10, 0.15, 0.20） powders were successfully prepared by the sol-gel method.The samples were characterized by fourier transform infrared（FTIR）, thermogravimetric and differential scanning calorimetry（TG-DSC）, X-ray diffraction（XRD）, scanning electron microscopy（SEM）, AC impedance and thermal expansion measurements.Experimental results indicated that highly phase-pure cubic fluorite electrolyte Ce0.8La0.2–x Y x O1.9 powders were obtained after calcining at 600 °C.The as-synthesized powders exhibited high sintering activity, the Ce0.8La0.2–x Y x O1.9 series electrolytes which have higher relative densities over 96% could be obtained after sintered at 1400 °C for 4 h.Ce0.8La0.15Y0.05O1.9 electrolyte sintered at 1400 °C for 4 h exhibited higher oxide ionic conductivity（σ800 oC=0.057 S/cm）, lower electrical activation energy（E a=0.87 e V） and moderate thermal expansion coefficient（TEC=15.5×10-6 K-1, temperature range 25–800 °C）.     

Preparation and Characterization of Component Materials for Intermediate Temperature Solid Oxide Fuel Cell by Glycine-Nitrate Process

La1-xSrxGa1-yMgyO3-δ (LSGM) electrolyte, La1-xSrxCr1-yMnyO3-δ (LSCM) anode and La1-xSrxFe1-yMnyO3-δ (LSFM) cathode materials were all synthesized by glycine-nitrate process (GNP). The microstructure and characteristics of LSGM, LSCM and LSFM were tested via X-ray diffraction(XRD), scanning electron microcopy (SEM), A C impedance and four-probe direct current techniques. XRD shows that pure perovskite phase LSGM electrolyte and electrode (LSCM anode and LSFM cathode) materials were prepared after being sintered at 1400 ℃ for 20 h and at 1000 ℃ for 5 h, respectively. The max conductivities of LSGM (ionic conductivity), LSCM (total conductivity) and LSFM (total conductivity) materials are 0.02, 10, 16 S·cm-1 in the air below 850 ℃, respectively. The conductivity of LSCM becomes smaller when the atmosphere changes from air to pure hydrogen at the same temperature and it decreases with the temperature like metal. The porous and LSGM-based LSCM anode and LSFM cathode films were prepared by screen printing method, and the sintering temperatures for them were 1300 and 1250 ℃, respectively. LSGM and electrode (LSCM and LSFM) materials have good thermal and chemical compatibility.     

Clarification of the oxygen adsorption properties of YBaCo_4O_7 at high temperature by thermogravimetry

The oxygen adsorption/desorption properties of YBaCo4O7 at high temperature were investigated by thermogravimetry(TG) method,in which two types of oxygen adsorption were combined.The first type adsorbed oxygen at about 700 °C and released the adsorbed oxygen at 880 °C.After the first type oxygen desorption,even the temperature and oxygen flow were kept the same,a second type oxygen adsorption at about 880 °C occurred and the adsorbed oxygen were released at above 980 °C.The combination of these two types of oxygen adsorption/desorption was responsible for the difference in TG curves obtained by different heating programs.     

Preparation and performance of Pr-doped Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ) cathode for IT-SOFCs

(Ba0.5Sr0.5)1-xPrxCo0.8Fe0.2O3-δ(BSPCFx;x=0.00-0.30) oxides were synthesized by a sol-gel thermolysis process using combination of PVA and urea,and were also investigated as cathode material for intermediate temperature solid oxide fuel cells(IT-SOFCs).X-ray diffraction(XRD) results showed that all the samples formed a single phase cubic pervoskite-type structure after being calcined at 950 oC for 5 h and the lattice constant decreased with the Pr content increasing.The electrical conductivity of Ba0.5Sr0.5Co0.8Fe0.2O3-δ(BSCF) was greatly enhanced by Pr-doping.The thermal expansion coefficient(TEC) of BSPCFx was increased with the content of Pr increasing,and all the thermal expansion curves had an inflection at about 250-400 oC due to the thermal-induced lattice oxygen loss and the reaction of Co and Fe ion.Ac impedance analysis indicated that BSPCFx possessed better electrochemical performance.The polarization resistance of the sample with x=0.2 was only ～0.948 Ω cm2 at 500 oC,significantly lower than that of BSCF(～2.488 Ω cm2).