Electrochemical open circuit voltage (OCV) characterization of SOFC materials

In this paper, we are reporting an extensive characterization, by means of open circuit voltage measurements, of Ce_0.8Gd_0.2O₂, La_0.9Sr_0.1Ga_0.8Mg_0.2O₃, and La₂Mo_0.6W_1.4O₉ oxide-ions and BaCe_0.8Y_0.2O₃ and BaCe_0.55Zr_0.3Y_0.15O₃ proton-conducting electrolyte materials for solid oxide fuel cell (SOFC) applications. This simple and common technique, well known for a long time in the electrochemical study of solid oxide fuel cells, has been here proposed for the electrical characterization of these ceramic materials, in order to define their ionic transport numbers, the maximum voltage performances, the thermal and chemical stability, and also to suggest the ideal temperature range for different applications, as in the electrochemical devices, sensors, and SOFC field. In the paper, controlled and reproducible working conditions have been applied in a wide range of temperature, by means of ultrapure gas (H₂ and O₂), under operational conditions found in real SOFC devices and, mainly, without the usual problems related to the chemical compatibility, the depolarization efficiency, and the high current density required to the electrode materials in the design of a more efficient SOFC device.     

Microstructures and electrical conductivity of nanocrystalline ceria-based thin films

Ceria-based thin films are potential materials for use as gas-sensing layers and electrolytes in micro-solid oxide fuel cells. Since the average grain sizes of these films are on the nanocrystalline scale (< 150 nm), it is of fundamental interest whether the electrical conductivity might differ from microcrystalline ceria-based ceramics. In this study, CeO₂ and Ce_0.8Gd_0.2O_1.9−x thin films have been fabrication by spray pyrolysis and pulsed laser deposition, and the influence of the ambient average grain size on the total DC conductivity is investigated. Dense and crack-free CeO₂ and Ce_0.8Gd_0.2O_1.9−x thin films were produced that withstand annealing up to temperatures of 1100 °C. The dopant concentration and annealing temperature affect highly the grain growth kinetics of ceria-based thin films. Large concentrations of dopant exert Zener drag on grain growth and result in retarded grain growth. An increased total DC conductivity and decreased activation energy was observed when the average grain size of a CeO₂ or Ce_0.8Gd_0.2O_1.9−x thin film was decreased.     

The chemical stability and conductivity improvement of protonic conductor BaCe0.8 − x Zr x Y0.2O3 − δ

A series of BaCe_0.8???x Zr _x Y_0.2O_3???δ (BCZYx) (x?=?0, 0.2, 0.4, 0.6, 0.8) powders were prepared by EDTA–citrate complexing sol–gel process in this paper. The electrical conducting behavior, as well as chemical stability, was investigated. X-ray diffraction (XRD) results reveal that all samples are homogenous perovskite phases. Observed from XRD patterns and thermogravimetric curves, the samples with x?≥?0.4 survive in the pure CO₂, while samples with various Zr contents all present structurally stable against steam at 800 °C. The Zr-free sample of BaCe_0.8Y_0.2O_3???δ possesses the maximum bulk conductivity, 4.25?×?10^?2 S/cm, but decomposes into Ba(OH)₂ and Ce_0.8Y_0.2O_3???δ in steam. A negative influence of increasing Zr content on the conductivity of BCZYx can be observed by impedance tests. Considering the effect of temperature on the bulk conductivity, BCZY0.4 is preferred to be applied in SOFC as a protonic conductor, ranging from 1.52?×?10^?4 to 1.51?×?10^?3 S/cm (500–850 °C) with E _a?=?0.859 eV, which is proved to be a good protonic conductor with t _H+?≥?0.9.     

Low energy ion scattering (LEIS) applied to ionic materials

Surfaces and interfaces play a dominant role in the performance of devices like fuel cells and membranes based on ionic materials. The LEIS technique offers a unique possibility to determine the composition of the outermost atomic layer, which is often quite different from that of deeper layers. For instance impurities that are present in minute concentrations −1 ppb or even less- in the bulk may segregate to the surface and there become the dominant species. By carefully sputtering away the top layers also a compositional depth profile can be made of the first 10 to 20 layers. The basic principles of the LEIS technique will be explained, answering questions like: why is it so extremely surface sensitive; what does the instrumentation look like; what can you learn from the results. Its applicability to ionic materials will be demonstrated with results from measurements on various substrates used in fuel cells. The oxygen exchange across the surface of Sm_0.8Sr_0.2CoO₃ can be studied, because it is possible to differentiate between the¹⁸O and¹⁶O isotopes. One can determine which elements are on top in La_0.8Sr_0.2Ga_0.8Mg_0.2O_3±δ. The top layer of Ce_0.8Gd_0.2O_1.9 proves to be enriched in Gd oxide. The Y segregation in isotopically enriched YSZ is being studied. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Chemical and redox stabilities of a solid oxide fuel cell with BaCe0.8Y0.2O3−α functioning as an electrolyte and as an anode

The operation of a solid oxide fuel cell (SOFC) based on BaCe_0.8Y_0.2O_3−α (BCY20) at 800 °C was studied without using an anode material. A porous, Ce-rich phase with a fluorite structure was formed at a depth of approximately 10 μm from the BCY20 surface by heat treatment at 1700 °C. This was due to the vaporization of BaO from the BCY20 surface. This treatment improved the cell performance and chemical stability to CO₂ because the Ce-rich phase functioned as an electrically conducting and protective layer. The heat-treated BCY20 also had better chemical and redox stabilities over a Ni–Ce_0.8Sm_0.2O_1.9 (SDC) cermet anode attached to the SDC electrolyte. The cell with the heat-treated BCY20 operated well on unhumidified methane, ethane, propane, and butane without carbon deposition, while the cell with the Ni–SDC cermet anode degraded within a few hours. Moreover, the BCY20 showed higher tolerance to 10 ppm H₂S and stability over 20 times redox cycling in comparison to the Ni–SDC cermet anode.     

Gadolinium doped Ceria nanocrystals synthesized from mesoporous silica

Highly crystalline and thermally stable gadolinium doped ceria (GDC) particles have been synthesized by hard template route for the first time. This oxide is being recognized as an intermediate temperature (500–700 °C) electrolyte material for applications in solid-oxide fuel cells. The GDC particles show high crystallinity and nanometric size (2.83 ± 0.05 nm in diameter) and Raman analyses confirm the formation of the solid solution instead of a CeO₂ and Gd₂O₃ mixture. EDX and EELS studies indicate a stoichiometry coherent with the Gd_0.2Ce_0.8O_1.9 phase. The synthesized nanometric powder is expected to be used in solid oxide fuel cells as well as in the catalytic treatment of automobile exhaust fumes.

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Graphical abstract

     

Spray pyrolysis of electrolyte interlayers for vacuum plasma-sprayed SOFC

The effects of gadolinia-doped ceria (CGO, Ce_0.8Gd_0.2O_1.9−x) and yttria-doped zirconia (8YSZ, Zr_0.92Y_0.08O_2−x) interlayers prepared by spray pyrolysis between vacuum plasma-sprayed 8YSZ electrolytes (8YSZ–VPS) and screen-printed (La_0.8Sr_0.2)_0.98MnO₃ cathodes (LSM) on the power output of solid oxide fuel cells (SOFC) are investigated. Amorphous thin films are deposited and then converted to nanocrystalline electrolyte–cathode interlayers during the first heat-up cycle of a SOFC to the operating temperature. CGO thin films between the YSZ plasma-sprayed electrolyte and the LSM cathode increased the power output by more than 20% compared to cells without interlayers, whereas YSZ films degraded the power output of cells. It is assumed that CGO improves the charge transfer at the electrolyte–cathode interface and that the CGO layer prevents the formation of undesirable insulation of La-zirconate at the interface 8YSZ/LSM.     

Solid solution formation, densification and ionic conductivity of Gd- and Sm-doped ceria

The processes of solid solution formation, densification and electrical conductivity in samaria and gadolinia-doped ceria solid electrolytes were studied by Raman spectroscopy, density and impedance spectroscopy measurements. Bulk specimens of Ce_0.9Gd_0.1O_1.95 and Ce_0.8Sm_0.2O_1.9 were prepared by solid state reactions at several dwell temperatures and holding times. Hydrostatic density results show a fast increase in sintered density up to 1 h holding time. Raman spectra of specimens sintered for 1 h show a prominent band at 463 cm^− 1 assigned to the cubic fluorite-type lattice of cerium oxide, and low-intensity bands at 344 and 363 cm^− 1 attributed to free samarium and gadolinium sesquioxides, respectively. Solid solution completion was achieved only at temperatures above 1400 °C. Electrical conductivity measurements were used to study mass transport. Analysis of impedance data allowed for determining the activation energy for cation diffusion in Ce_0.9Gd_0.1O_1.95 and Ce_0.8Sm_0.2O_1.9 sintered specimens.     

Specifics of the Electrical Properties of Composite Solid Oxide Membranes Based on SrTi<Subscript>0.5</Subscript>Fe<Subscript>0.5</Subscript>O<Subscript>3–δ</Subscript>

The electrical properties of dual-phase fluorite-pervoskite oxide systems based on strontium titanate- ferrite (SrTi_0.5Fe_0.5O_3–δ) are studied. We find that the oxygen ionic and ambipolar conductivities of strontium titanate-ferrite can be considerably improved by introducing the fluorite phase Ce_0.8(Sm_0.8Sr_0.2)_0.2O_2–δ. This is advantageous considering the prospects of applying these types of composite materials in different electrochemical devices, e.g., as membrane materials in electrochemical converters for the production of hydrogen and syngas and anode materials in solid oxide fuel cells.     

Epitaxial growth of atomically flat gadolinia-doped ceria thin films by pulsed laser deposition

Epitaxial growth of Ce_0.8Gd_0.2O₂(CGO) films on (001) TiO₂-terminated SrTiO₃ substrates by pulsed laser deposition was investigated using in situ reflective high energy electron diffraction. The initial film growth shows a Stransky–Krastanov growth mode. However, this three-dimensional island formation is replaced by a two-dimensional island nucleation during further deposition, which results in atomically smooth CGO films. The obtained high-quality CGO films may be attractive for the electrolyte of solid-oxide fuel cells operating at low temperature.     

Magnetic dynamics of phase separation domains in GdMn<Subscript>2</Subscript>O<Subscript>5</Subscript> and Gd<Subscript>0.8</Subscript>Ce<Subscript>0.2</Subscript>Mn<Subscript>2</Subscript>O<Subscript>5</Subscript> multiferroics

Specific features of the magnetic properties and magnetic dynamics of isolated phase separation domains in GdMn₂O₅ and Gd_0.8Ce_0.2Mn₂O₅ have been investigated. These domains represent 1D superlattices consisting of dielectric and conducting layers with the ferromagnetic orientation of their spins. A set of ferromagnetic resonances of separate superlattice layers has been studied. The properties of the 1D superlattices in GdMn₂O₅ and Gd_0.8Ce_0.2Mn₂O₅ are compared with the properties of the previously investigated RMn₂O₅ (R = Eu, Tb, Er, and Bi) series. The similarity of the properties for all the RMn₂O₅ compounds with different R ion types is established. Based on the concepts of the magnetic dynamics of ferromagnetic multilayers and properties of semiconductor superlattices, a 1D model of the superlattices in RMn₂O₅ is built.     

Spontaneous stress-induced oxidation of Ce ions in Gd-doped ceria at room temperature

Cerium oxides are widely used within catalysis and fuel cells. The key parameters of interest, including catalytic activity, transport properties and defect structure are all fundamentally linked to the oxidation state of the cerium ions within the material which can adopt a 3+ or 4+ oxidation state. We use Raman spectroscopy, as well as scanning and optical microscopy to show that the oxidation state of cerium ions within Ce_0.8Gd_0.2O_2?x can be altered either through chemically induced strain (imparted during processing), mechanical indentation, fracture or applied mechanical load. This work shows that both the chemical environment and stress state will play a role in determining the oxidation state of the cerium ions within ceria containing materials. It has been shown that the rate of oxidation of Ce_0.8Gd_0.2O_2?x can be dramatically altered at room temperature via changing the local stress state of the material.     

Post-test analysis of electrode-supported solid oxide electrolyser cells

Three solid oxide cells have been investigated after long-term high temperature electrolysis to explain the phenomena of accelerated degradation. These cells contain a Ni-YSZ cermet (Ni-yttria-stabilised-zirconia) as hydrogen electrode (cathode), yttria-stabilised-zirconia (YSZ) as electrolyte, Ce_0.8Gd_0.2O_1.9 (CGO) as diffusion barrier layer and La_0.58Sr_0.4Co_0.2Fe_0.8O₃ (LSCF) as oxygen electrode (anode). Cell 1, cell 2 and cell 3 were tested continuously at about 770 °C, with a current density of ?1 A cm^?2 and 80 % H₂O of absolute humidity for 9000, 1770 and 1460 h, respectively. It was found that in cell 1, the degradation rate was about 2.2 % per 1000 h, in cell 2 the degradation rate increased to 3.4 % per 1000 h and in cell 3 the degradation rate was 2.6 % per 1000 h. The mode of cell degradation was also investigated as a function of the cell fabrication in the four layers system (anode/diffusion barrier layer/electrolyte/cathode). An intergranular fractured surface along the grain boundaries of the electrolyte, and the formation of porous structures throughout the thickness of the electrolyte were observed in cell 1. LSCF, as the oxygen electrode, showed compositional fluctuations with a changed perovskite composition and formation of cobalt oxide. This phenomenon reduces the electrical conductivity and, probably, also the catalytic properties. The hydrogen electrode did not show major changes in all the three cells tested. Cells 2 and 3 showed similar features as observed for cell 1, except the fact that they retained the electrolyte structure without intergranular fracture and formation of porosity after continuous testing for long duration.     

Stable and high conductivity ceria/bismuth oxide bilayer electrolytes for lower temperature solid oxide fuel cells

A highly conductive bismuth oxide/ceria bilayer electrolyte was developed to reduce solid oxide fuel cell (SOFC) operating temperatures. Bilayer electrolytes were fabricated by depositing a layer of Er_0.2Bi_0.8O_1.5 (ESB) of varying thickness via pulsed laser deposition and dip-coating on a Sm_0.2Ce_0.8O_1.9 (SDC) substrate. The open-circuit potential (OCP) and ionic transference number (t _i) of ESB/SDC electrolytes were tested in a fuel cell arrangement as a function of relative thickness, temperature, and with H₂/H₂O and CO/CO₂ on the anode side and air on the cathode side. These EMF measurements showed a significant increase in OCP and t _i with the bilayer structure, as compared to the cells with a single SDC electrolyte layer. Furthermore, improvement in the OCP and t _i of bilayer SOFCs was observed with increasing relative thickness of the ESB layers. Hence, the bilayer structure overcomes the limited thermodynamic stability of bismuth oxides and prevents electronic conductivity of ceria-based oxides in reducing atmosphere.     

Structural,thermal and electrical properties of Bi and Y co-doped barium zirconium cerates

Bismuth- and yttrium-co-doped barium cerates were successfully synthesised by solid-state reactions followed by sintering between 1,400 and 1,500 °C for 1 to 6 h allowing densification above 98 % to be obtained. All samples were found to retain their original orthorhombic structure after treatment in either oxidising or reducing atmospheres (dry and wet). Mechanical strength was affected by structure upon reduction due in part to strains and stresses induced by bismuth ionic size variations. Conductivity values as high as 0.055 S/cm were obtained for sample BaCe_0.6Zr_0.1Y_0.1Bi_0.2O_3?δ and of 0.0094 S/cm for the Zr-free compound BaCe_0.7Y_0.2Bi_0.1O_3?δ at 700 °C in air. In all the investigated materials, sample BaCe_0.6Zr_0.1Y_0.1Bi_0.2O_3?δ exhibits the highest conductivity in both air and wet 5 % H₂/Ar with good mechanical strength. BaCe_0.6Zr_0.1Y_0.1Bi_0.2O_3?δ is a promising mixed H⁺/e^? conductor, a potential component of composite anode for solid oxide fuel cells.     

A wet-chemical route for the preparation of Ni–BaCe0.9Y0.1O3 − δ cermet anodes for IT-SOFCs

Nano-sized BaCe_0.9Y_0.1O_3 ? δ (BCY10) protonic conductor powders were used to prepare Ni-BCY10 cermets for anode-supported intermediate temperature solid oxide fuel cells. A new wet-chemical route was developed starting from Ni nitrates as precursors for NiO. BCY10 powders were suspended in a Ni nitrate aqueous solution that was evaporated to allow NiO precipitation on the BCY grains, obtaining NiO-BCY10 cermets. To obtain the final Ni-BCY10 anodes, pellets were reduced in dry H₂ at 700 °C. The structural and microstructural properties of the pellets were investigated using X-ray diffraction analysis and field emission scanning electron microscopy. A homogeneous dispersion of perovskite and nickel phases was observed. The chemical stability of the anodes was evaluated under wet H₂ and CO₂ atmosphere at 700 °C. The electrical properties of the Ni-BCY10 pellets were evaluated using electrochemical impedance spectroscopy measurements. The Ni-BCY10 cermet electrodes showed large electronic conductivity, demonstrating percolation through the Ni particles, and low area specific resistance at the BCY10 interface. These characteristics make the cermet suitable for application in BCY-based protonic fuel cells. The developed chemical route offers a simple and low-cost procedure to obtain promising high performance anodes.     

Anomalous conductivity and microstructure in gadolinium doped ceria prepared from nano-sized powder

The temperature and the oxygen partial pressure dependences of the electron and hole conductivities were measured by the dc polarization method using a Hebb–Wagner's ion blocking cell for Gd_0.2Ce_0.8O_1.9 polycrystalline bodies with grain size of 0.5 μm prepared by sintering of nano-sized powder. A significant enrichment of gadolinium was observed in the vicinity of the grain boundary by TEM/EDS analyses. The electron conductivity were comparable with those of conventional Gd_0.2Ce_0.8O_1.9 polycrystalline body with grain size of 2 μm, and it followed p(O₂)^− 1/4 dependence at temperatures T = 973–1273 K. However, the observed hole conductivity was higher than that of conventional Gd_0.2Ce_0.8O_1.9, and it did not follow p(O₂)^1/4 dependence. This anomalous p(O₂) dependence disappeared after the sample was treated at T = 1773 K for 38 h and grain size was enlarged to 2–10 μm.     

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.     

In situ RHEED analysis of epitaxial Gd2O3 thin films grown on Si (001)

Epitaxial Gd₂O₃ thin films were successfully grown on Si (001) substrates using a two-step approach by laser molecular-beam epitaxy. At the first step, a ～0.8 nm thin layer was deposited at the temperature of 200 ^°C as the buffer layer. Then the substrate temperature was increased to 650 ^°C and in situ annealing for 5 min, and a second Gd₂O₃ layer with a desired thickness was deposited. The whole growth process is monitored by in situ reflection high-energy electron diffraction (RHEED). In situ RHEED analysis of the growing film has revealed that the first Gd₂O₃ layer deposition and in situ annealing are the critical processes for the epitaxial growth of Gd₂O₃ film. The Gd₂O₃ film has a monoclinic phase characterized by X-ray diffraction. The high-resolution transmission electron microscopy image showed all the Gd₂O₃ layers have a little bending because of the stress. In addition, a 5–6 nm amorphous interfacial layer between the Gd₂O₃ film and Si substrate is due to the in situ high temperature annealing for a long time. The successful Gd₂O₃/Si epitaxial growth predicted a possibility to develop the new functional microelectronics devices.     

Sol-gel preparation of selected high temperature proton conductors

The sol-gel preparation of the compounds BaCe_0.8Y_0.2O_2.9 (BCY20), BaCe_0.8Gd_0.2O_2.9 (BCG20), BaTiO₃, BaTi_0.9Y_0.1O_2.95 and BaTi_0.9Er_0.1O_2.95 using the acrylamide route is described. The advantages lie in the short reaction time leading to the gels and the large batch sizes possible. In the case of the titanates there was the additional advantage that one of the starting compounds was metallic Ti powder which was dissolved in H₂O₂ and NH₃. Basically, all 5 compounds could be synthesized phase pure. The cerates were well described by PDF 35-1318 and absorb large quantities of water vapor in TG experiments. The doped titanates were cubic and were well characterized by PDF 31-0174. They only absorb relatively small amounts of water vapor but still may be termed proton conductors.