Fabrication of solid oxide fuel cell based on doped ceria electrolyte by one-step sintering at 800 °C

Ce_0.8Gd_0.05Y_0.15O_1.9 (GYDC) electrolyte was prepared by a carbonate co-precipitation method. Lithium nitrate at 1, 1.5, 2 and 3 mol% was added to GYDC as sintering additive. 96% relative density was achieved for GYDC at sintering temperature of 800 °C with addition of 1.5 mol% LiNO₃. The conductivities of GYDC with sintering aids LiNO₃ were measured by a.c. impedance spectroscopy and showed comparable values to that of pure GYDC sample sintered at 1400 °C. A single cell with 1.5 mol% LiNO₃ infiltrated GYDC electrolyte was fabricated by sintering at 800 °C for only 2 h. Lithiated NiO was synthesized by the glycine-nitrate combustion method and employed as cathode material. The cell was tested at temperatures from 500 to 575 °C and a maximum power density of 73 mW cm^− 2 was obtained at 575 °C. These preliminary results indicate that LiNO₃ is a very effective sintering additive for intermediate temperature solid oxide fuel cell fabrication.     

Synthesis and performance of Y-doped La0.7Sr0.3CrO3−δ as a potential anode material for solid oxygen fuel cells

Y-doped La_0.7Sr_0.3CrO_3−δ is a promising anode catalyst for solid oxygen fuel cell (SOFC). The performances of chemical and physical are measured by SEM, XRD and FT-IR. The conductivities of catalyst are measured by DC four-probe method in 20% H₂S-N₂, 3% H₂-N₂ and air from 573 K to 1173 K, respectively. The results show that Y-doped La_0.7Sr_0.3CrO_3−δ powders have perfect perovskite phase structure with no extra peaks and exhibit good chemical compatibility with Ce_0.8Sm_0.2O_1.9 (as electrolyte) in air. Through XRD and FT-IR analysis no sulfur-containing species is detected after exposure to the 20% H₂S at 1173 K for 5 h. Meanwhile, Y-doped La_0.7Sr_0.3CrO_3−δ shows that the highest conductivity is 0.21 S/cm at 1173 K in H₂S. The open circuit voltages are 0.85 V at 1173 K in H₂S and 1.04 V at 823 K in H₂. The maximal power densities are 12.4 mW/cm² in H₂S and 1.59 W/cm² in H₂ for cells comprising Y-doped La_0.7Sr_0.3CrO_3−δ-Sm_0.2Ce_0.8O_1.9/Sm_0.2Ce_0.8O_1.9/Ag.     

H2/Pt/Ce0.9Gd0.1O1.95/Pt/O2 fuel cell operated in the intermediate temperature range 500 – 700°C

Ce_0.9Gd_0.1O_1.95 (GCO), is one of the potential candidate electrolytes for intermediate temperature Solid Oxide Fuel Cells (ITSOFC). GCO has high oxide ion conductivity in the intermediate temperature range (500 – 700 °C) compared to other Ce_1−yGd_yO_2-2/y compositions and the Gd³⁺ ion is the most appropriate dopant material compared to other rare earth materials such as Sm³⁺, Y³⁺, Zr³⁺, etc. Our results show that the fuel cell H₂/Pt/Ce_0.9Gd_0.1O_1.95/Pt/O₂ operated in the temperature range 500 – 700°C gives the maximum power densities 0.0049 W/cm² at 500 °C and 0.0126 W/cm² at 650 °C for cell voltages 0.6275 V and 0.6278 V, respectively, where the electrolyte was kept in 5% H₂ (+ Argon) for 12 hours before use in the fuel cell. Maximum power densities are 0.0038 W/cm² at 500 °C and 0.0270 W/cm² at 650 °C for cell voltages 0.5986 and 0.5913 V, respectively, where the electrolyte was kept in 2 % O₂ (+ Argon) for 12 hours before use in the fuel cell. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

The size and strain effects on the Raman spectra of Ce1−xNdxO2−δ (0≤x≤0.25) nanopowders

Ultrafine Ce_1−xNd_xO_2−δ (x=0-0.25) powders were synthesized by self-propagating room temperature synthesis. Raman spectra were measured at room temperature in the 300-700 cm⁻¹ spectral range. The shift and asymmetric broadening of the Raman F_2g mode at about 454 cm⁻¹ in pure and doped ceria samples could be explained with combined size and inhomogenous strain effects. Increased concentration of O²⁻ vacancies with doping is followed by an appearance of new Raman feature at about 545 cm⁻¹.     

A Ni/YSZ composite containing Ce0.9Ca0.1O2−δ particles as an anode for SOFCs

A composite material (hereafter referred to as NYC) containing Ni, Y₂O₃-stabilized ZrO₂ (YSZ) and Ce_0.9Ca_0.1O_2−δ (CC10) particles was prepared and used as the anode of solid oxide fuel cells (SOFCs). The performance of NYC was better than that of conventional Ni/YSZ anodes in terms of anodic overpotential and interface impedance. The additional CC10 particles improved the anode properties. XRD results suggest that a solid solution of YSZ and CC10 was produced. From impedance measurements, it is concluded that the solid solution exhibits substantial electronic conduction. Ni/YSZ/15 wt% Ce_0.9Ca_0.1O_2−δ anodes exhibited the best properties over the experimental temperature range. A SOFC with an anode of Ni/YSZ/15 wt% Ce_0.9Ca_0.1O_2−δ provided the maximum power density and current density. Addition of CC10 with an average particle size of 0.3 μm was more advantageous than that with an average size of 3 μm.     

Energy transfer in Y3Al5O12:Ce, Pr and CaMoO4:Sm, Eu phosphors

Non-radiative energy transfers (ET) from Ce³⁺ to Pr³⁺ in Y₃Al₅O₁₂:Ce³⁺, Pr³⁺ and from Sm³⁺ to Eu³⁺ in CaMoO₄:Sm³⁺, Eu³⁺ are studied based on photoluminescence spectroscopy and fluorescence decay patterns. The result indicates an electric dipole-dipole interaction that governs ET in the LED phosphors. For Ce³⁺ concentration of 0.01 in YAG:Ce³⁺, Pr³⁺, the rate constant and critical distance are evaluated to be 4.5×10⁻³⁶ cm⁶ s⁻¹ and 0.81 nm, respectively. An increase in the red emission line of Pr³⁺ relative to the yellow emission band of Ce³⁺, on increasing Ce³⁺ concentration is observed. This behavior is attributed to the increase of spectral overlap integrals between Ce³⁺ emission and Pr³⁺ excitation due to the fact that the yellow band shifts to the red spectral side with increasing Ce³⁺ concentration. In CaMoO₄:Sm³⁺, Eu³⁺, Sm³⁺-Eu³⁺ transfer occurs from ⁴G_5/2 of Sm³⁺ to ⁵D₀ of Eu³⁺. The rate constant of 8.5×10⁻⁴⁰ cm⁶ s⁻¹ and the critical transfer distance of 0.89 nm are evaluated.     

Partial electronic conductivity and electrolytic domain of bilayer electrolyte Zr0.84Y0.16O1.92/Ce0.9Gd0.1O1.95

Partial electronic conductivity and total conductivity have been determined by Hebb-Wagner polarization method and a.c. impedance spectroscopy, respectively, on bilayer electrolyte Zr_0.84Y_0.16O_1.92(YSZ)/Ce_0.9Gd_0.1O_1.95(GDC) with thickness ratios 10^− 3/1 and 10^− 4/1 at 800°, 900° and 1000 °C, respectively. While their ionic conductivities remain close to that of GDC, the electronic conductivities are suppressed the more from that of GDC towards that of YSZ the higher the thickness ratio, as expected. Even when the GDC-side is exposed to reducing atmosphere, the electronic conductivity is also suppressed, but to a less extent. It is suggested that oxygen activity distribution is discontinuous across the YSZ/GDC interface under ion-blocking condition, refuting the “continuity hypothesis” that has been usually adopted in calculating the oxygen activity distribution across a multilayer of mixed conductor oxides. The electrolytic domain widths of the bilayer electrolyte are reported depending on temperature, thickness ratio and direction of oxygen activity gradient imposed.     

Electrochemical synthesis of ammonia based on doped-ceria-carbonate composite electrolyte and perovskite cathode

Electrochemical synthesis of ammonia was investigated using a cobalt-free La_0.6Sr_0.4Fe_0.8Cu_0.2O_3-δ-Ce_0.8Sm_0.2O_2-δ (LSFCu-SDC) composite cathode and SDC-ternary carbonate composite electrolyte. La_0.6Sr_0.4Fe_0.8Cu_0.2O_3-δ and Ce_0.8Sm_0.2O_2-δ were prepared via combined EDTA-citrate complexing sol-gel and glycine nitrate processes, respectively, and characterised by X-ray diffraction (XRD). Ammonia was successfully synthesised from wet hydrogen and dry nitrogen under atmospheric pressure using Ni-SDC, SDC-carbonate and LSFCu-SDC composites as anode, electrolyte and cathode respectively. Ammonia formation was observed at 400, 425, 450 and 475 °C and the maximum rate of ammonia production was found to be 5.39 × 10⁻⁹ mol s⁻¹ cm⁻² at 450 °C and 0.8 V. The AC impedance measurements were recorded before and after the ammonia synthesis in the range of temperature 400-475 °C. The formation of ammonia at the N₂ side together with stable current at 450 °C under constant voltage demonstrates that SDC-(Li/Na/K)₂CO₃ composite electrolyte exhibits significant proton conduction at a temperature around 450 °C.     

Raman spectra of Ba6−3xSm8+2xTi18O54 solid solution

Raman spectra of Ba_6−3xSm_8+2xTi₁₈O₅₄ solid solution were investigated as the function of x and sintering time. Reasonable explanations were provided about the Raman shifts and their intensities at 1013, 590, 751, 280, 232 cm⁻¹. 1013 cm⁻¹ demonstrates the existence of BaCO₃ phase in solid solution, 590 cm⁻¹ is the symmetric stretching mode of the basal oxygens of the octahedral; 280 and 232 cm⁻¹ are the symmetric stretching modes resulted from the tilt of octahedral when large cation sites are Sm³⁺ and Ba²⁺. The shoulder peak appearing around 302 cm⁻¹ is related to the vacancy produced by the unequal valence of Sm³⁺ and Ba²⁺.     

Preparation, structure and oxide ion conductivity in Ce6−xYxMoO15−δ (x=0.1-1.4) solid solutions

The Ce_6−xY_xMoO_15−δ solid solution with fluorite-related structure have been characterized by differential thermal analysis/thermogravimetry (DTA/TG), X-ray diffraction (XRD), IR, Raman, scanning electric microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) methods. The electric conductivity of samples is investigated by Ac impedance spectroscopy. An essentially pure oxide-ion conductivity of the oxygen-deficiency was observed in pure argon, oxygen and air. The highest oxygen-ion conductivity was found in Ce_5.5Y_0.5MoO_15−δ ranging from 5.9×10⁻⁵ (S cm⁻¹) at 300 °C to 1.3×10⁻² (S cm⁻¹) at 650 °C, respectively. The oxide-ion conductivities remained stable over 80 h-long test at 800 °C. These properties suggested that significant oxide-ionic conductivity exists in these materials at moderately elevated temperatures.     

Microstructural studies of bulk and thin film GDC

Ceria rare earth solid solutions are known as solid electrolyte with potential application in oxygen sensors and solid oxide fuel cells. We report the preparation of gadolinia-doped ceria, Ce_0.90Gd_0.10O_1.95, by the conventional solid-state reaction method and the preparation of thin films from a sintered pellet of gadolinia-doped ceria by the pulsed laser deposition technique. The effect of process conditions, such as substrate temperature, oxygen partial pressure, and laser energy on microstructural properties of these films are examined using powder X-ray diffraction, scanning electron microscopy, atomic force microscopy, and Raman spectroscopy.     

Chemomechanical properties and microstructural stability of nanocrystalline Pr-doped ceria: An in situ X-ray diffraction investigation

The chemomechanical properties and microstructural stability of nanocrystalline Pr_xCe_1 − xO_2 − δ solid solutions are studied as a function of temperature by in situ X-ray diffraction measurements under oxidizing conditions at P(O₂) ~ 200 mbar. The chemical expansion coefficient of nanocrystalline powder specimens, operative at intermediate temperatures during which Pr⁴⁺ is reduced to Pr³⁺, is found to be similar to that obtained for coarse-grained Pr_xCe_1 − xO_2 − δ. This is contrary to reports regarding variation of physical and chemical properties with crystallite size. The thermal expansion coefficient, measured under conditions for which Pr_xCe_1 − xO_2 − δ is highly oxygen deficient, was found to be greater than that measured for fully oxidized Pr_xCe_1 − xO_2 − δ, with potential sources of these changes discussed. Moreover, the microstructure of nanocrystalline Pr_xCe_1 − xO_2 − δ is observed to have excellent stability at working temperatures below 800 °C, enabled by the inherent microstrain in the structure, highlighting the potential application of this material for solid state electrochemical devices.     

Metal-supported solid oxide fuel cells with barium-containing in-situ cathodes

Materials containing barium (Ba), such as SmBa_0.5Sr_0.5Co₂O_5-d/Ce_0.9Gd_0.1O_1.9 (SBSC50) and Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-d (BSCF), are considered for use as an in-situ cathode in metal-supported solid oxide fuel cells (SOFCs). The electrochemical properties and sintering behavior of these materials are investigated in terms of area specific resistances (ASRs), I-V-P characteristics and microstructure. The properties of in-situ cathodes comprised of SBSC50 and BSCF are compared with those of conventional cathodes, such as La_0.8Sr_0.2MnO_3-d (LSM), La_0.8Sr_0.2FeO_3-d (LSF), La_0.6Sr_0.4Co_0.2Fe_0.8O_3-d (LSCF) and Sm_0.5Sr_0.5CoO_3-d/Ce_0.8Sm_0.2O_1.9 (SSC40). Impedance spectroscopy analysis using Nyquist and Bode plots and microstructure analysis is conducted to understand the reason behind electrochemical performance differences between in-situ cathodes and sintered cathodes. From this analysis, we are also able to verify the electrochemical behavior of well-defined in-situ cathodes. SBSC50 and BSCF are the incorporated in our metal-supported cells without the use of any additional sintering process. The metal-supported cells are successfully fabricated using a high temperature sinter-joining process and we fail to detect any defects or deformation after fabrication. At an operating temperature of 800 °C, metal-supported cells with SBSC50 and BSCF cathodes exhibit maximum power densities of 0.50 Wcm^-2 and 0.65 Wcm^-2, respectively.     

The application of Raman and anti-stokes Raman spectroscopy for in situ monitoring of structural changes in laser irradiated titanium dioxide materials

The use of Raman and anti-stokes Raman spectroscopy to investigate the effect of exposure to high power laser radiation on the crystalline phases of TiO₂ has been investigated. Measurement of the changes, over several time integrals, in the Raman and anti-stokes Raman of TiO₂ spectra with exposure to laser radiation is reported. Raman and anti-stokes Raman provide detail on both the structure and the kinetic process of changes in crystalline phases in the titania material. The effect of laser exposure resulted in the generation of increasing amounts of the rutile crystalline phase from the anatase crystalline phase during exposure. The Raman spectra displayed bands at 144 cm⁻¹ (A1g), 197 cm⁻¹ (Eg), 398 cm⁻¹ (B1g), 515 cm⁻¹ (A1g), and 640 cm⁻¹ (Eg) assigned to anatase which were replaced by bands at 143 cm⁻¹ (B1g), 235 cm⁻¹ (2 phonon process), 448 cm⁻¹ (Eg) and 612 cm⁻¹ (A1g) which were assigned to rutile. This indicated that laser irradiation of TiO₂ changes the crystalline phase from anatase to rutile. Raman and anti-stokes Raman are highly sensitive to the crystalline forms of TiO₂ and allow characterisation of the effect of laser irradiation upon TiO₂. This technique would also be applicable as an in situ method for monitoring changes during the laser irradiation process.     

Crystallization of 21.25Gd2O3-63.75MoO3-15B2O3 glass induced by femtosecond laser at the repetition rate of 250 kHz

We report the formation of β′-Gd₂(MoO₄)₃ (GMO) crystal on the surface of the 21.25Gd₂O₃-63.75MoO₃-15B₂O₃ glass, induced by 250 kHz, 800 nm femtosecond laser irradiation. The morphology of the modified region in the glass was clearly examined by scanning electron microscopy (SEM). By micro-Raman spectra, the laser-induced crystals were confirmed to be GMO phases and it is found that these crystals have a strong dependence on the number and power of the femtosecond laser pulses. When the irradiation laser power was 900 mW, not only the Raman peaks of GMO crystals but also some new peaks at 214 cm⁻¹, 240 cm⁻¹, 466 cm⁻¹, 664 cm⁻¹ and 994 cm⁻¹which belong to the MoO₃ crystals were observed. The possible mechanisms are proposed to explain these phenomena.     

Hydrothermal synthesis, characterization and Raman studies of Eu activated Gd2O3 nanorods

Eu³⁺ (8 mol%) activated gadolinium oxide nanorods have been prepared by hydrothermal method without and with surfactant, cityl trimethyl ammonium bromide (CTAB). Powder X-ray diffraction (PXRD) studies reveal that the as-formed product is in hexagonal Gd(OH)₃:Eu phase and subsequent heat treatment at 350 and 600 °C transforms the sample to monoclinic GdOOH:Eu and cubic Gd₂O₃:Eu phases, respectively. The structural data and refinement parameters for cubic Gd₂O₃:Eu nanorods were calculated by the Rietveld refinement. SEM and TEM micrographs show that as-obtained Gd(OH)₃:Eu consists of uniform nanorods in high yield with uniform diameters of about 15 nm and lengths of about 50-150 nm. The temperature dependent morphological evolution of Gd₂O₃:Eu without and with CTAB surfactant was studied. FTIR studies reveal that CTAB surfactant plays an important role in converting cubic Gd₂O₃:Eu to hexagonal Gd(OH)₃:Eu. The strong and intense Raman peak at 489 cm⁻¹ has been assigned to A_g mode, which is attributed to the hexagonal phase of Gd₂O₃. The peak at ∼360 cm⁻¹ has been assigned to the combination of F_g and E_g modes, which is mainly attributed to the cubic Gd₂O₃ phase. The shift in frequency and broadening of the Raman modes have been attributed to the decrease in crystallite dimension to the nanometer scale as a result of phonon confinement.     

Effects of cobalt metal addition on sintering and ionic conductivity of Sm(Y)-doped ceria solid electrolyte for SOFC

The effects of cobalt addition (0.5 and 1 wt.%) on densification and ionic conductivity of Ce_0.9Sm_0.1O_1.95 (10SDC) and Ce_0.9Sm_0.075Y_0.025O_1.95 (2.5Y-SDC) have been studied. X-ray diffraction (XRD) showed that Co had changed to Co₃O₄ and Co₃O₄ + CoO after firing at 900 °C and 1300 °C respectively. The addition of Co promoted densification to occur at lower temperatures with a more uniform grain growth and greatly improved both grain boundary and bulk conductivity for 10SDC. Significant improvement of grain boundary for the 2.5Y-SDC samples was obtained, even at 1300 °C sintering, while bulk conductivity was slightly improved. Rapid grain growth along with improvement of ionic conductivity was observed when the samples were sintered further at higher temperature. Superior ionic conductivity of the 2.5Y-SDC samples with Co addition to that of the bare 10SDC suggested the potential use of Co as the co-dopant in this system to reduce the content of costly rare earth usage.     

Effects of O ions beam irradiation on crystal structure of rare earth sesquioxides

We report the results of ion irradiation influence on rare earth sesquioxides structure, which are materials of practical importance as a radiation resistant ceramics in nuclear applications. Y₂O₃, Gd₂O₃ and Er₂O₃ sesquioxides in the pellet form were irradiated by oxygen ions (O²⁺) beam with the energy of 30 keV and implantation fluence of 5 × 10²⁰ m⁻². Samples are characterized by Grazing Incidence X-ray Diffraction (GIXRD), Raman spectroscopy and atomic force microscopy (AFM). By GIXRD it was found partial transformation from cubic (C) to monoclinic (B) phase only in Gd₂O₃, induced by O²⁺ irradiation. This was confirmed by Raman spectroscopy. Although full phase transition from C to B phase in Y₂O₃ was not observed, the splitting and broadening of the main intensity Raman band for C phase could be explained by the stress and the disorder induced by the quenching. Analysis done by AFM showed changes in surface topology, i.e. values of average roughness (Ra) and root mean squared roughness (RMS) were significantly changed after irradiation for all samples. RMSs in Y₂O₃ before and after irradiation were 35 nm and 26 nm, respectively.     

Intralamellar structural modifications related to the proton exchanging in K4Nb6O17 layered phase

Basic structural aspects about the layered hexaniobate of K₄Nb₆O₁₇ composition and its proton-exchanged form were investigated mainly by spectroscopic techniques. Raman spectra of hydrous K₄Nb₆O₁₇ and H₂K₂Nb₆O₁₇·H₂O show significant modifications in the 950-800 cm⁻¹ region (Nb-O stretching mode of highly distorted NbO₆ octahedra). The band at 900 cm⁻¹ shifts to 940 cm⁻¹ after the replacement of K⁺ ion by proton. Raman spectra of the original materials and the related deuterated samples are similar suggesting that no isotopic effect occurs. Major modifications were observed when H₂K₂Nb₆O₁₇ was dehydrated: the relative intensity of the band at 940 cm⁻¹ decreases and new bands seems to be present at about 860-890 cm⁻¹. The H⁺ ions should be shielded by the hydration sphere what preclude the interaction with the layers. Removing the water molecules, H⁺ ions can establish a strong interaction with oxygen atoms, decreasing the bond order of Nb-O linkage. X-ray absorption near edge structure studies performed at Nb K-edge indicate that the niobium coordination number and oxidation state remain identical after the replacement of potassium by proton. From the refinement of the fine structure, it appears that the Nb-Nb coordination shell is divided into two main contributions of about 0.33 and 0.39 nm, and interestingly the population, i.e., the number of backscattering atoms is inversed between the two hexaniobate materials.     

Enhanced hydrogen production by doping Pr into Ce0.9Hf0.1O2 for thermochemical two-step water-splitting cycle

We synthesized (Ce_0.9Hf_0.1)_1−xPr_xO_2−δ (x=0, 0.05 and 0.1) using the polymerized complex method. The synthesized samples, as well as the samples after thermochemical two-step water-splitting cycles have a fluorite structure and Pr exists in the solid solutions with both trivalent and tetravalent states, as suggested by powder X-ray Diffraction (XRD) Patterns. The reduction fraction of Ce⁴⁺ in redox cycles (oxidation step in air) and two-step water-splitting cycles (oxidation step in steam) indicates that the addition of Pr into Ce–Hf oxide solid solution cannot improve the reduction fraction of Ce⁴⁺ during the redox cycles but both the reduction fraction of Ce⁴⁺ and H₂ yield are significantly enhanced during two-step water-splitting cycles. The chemical composition of 10 mol% Pr doped Ce_0.9Hf_0.1O₂ exhibits the highest reactivity for hydrogen production in H₂-generation step by yielding an average amount of 5.72 ml g⁻¹ hydrogen gas, which is much higher than that evolved by Ce_0.9Hf_0.1O₂ (4.50 ml g⁻¹). The enhancement effect of doping Pr on the performance during two-step water-splitting cycles is because of the multivalent properties of Pr, which can: (1) reduce the amount of Ce³⁺ oxidized by contamination air (contamination air eliminated by partial oxidation of Pr³⁺ to Pr⁴⁺) in H₂-generation step; (2) enhance the reaction rate in H₂-generation step by improving the ionic conductivity (extrinsic oxygen vacancies created by the substitution of Ce⁴⁺ by Pr³⁺).