Structural, catalytic and electrical investigation on La1-xSrxCr1-yFeyO3- δ as anodes for IT-SOFCs

Ceria-based electrolytes prepared by solution combustion synthesis: The role of fuel on the materials properties

Ce0.8Sm0.2O2 − xpowders were synthesized by solution combustion synthesis using citric acid, cellulose and sucrose as single, or intimately mixed, fuels. The powders were characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, N2sorption at −196 °C, H2-temperature programmed reduction and thermogravimetric analyses. Textural properties of the powders were shaped by the peculiar employed fuel. The study of reducibility revealed that oxygen vacancies formation is mainly influenced by both parameters, specific surface area and total pore volume. The different tendency toward reduction played a key role in sintering under reducing atmosphe…

New synthetic strategies for the enhancement of the ionic conductivity in Ce0.8Sm0.2O2-x

Introduction Samarium-doped ceria has been widely investigat-ed for electrochemistry applications as full density elec-trolyte for intermediate temperature solid oxide fuel cells (IT-SOFC), between 500°C and 800°C [1]. One of the main challenges for the ceria-based electrolytes is to decrease the resistivity at the grain boundary zone, especially in this low temperature range. Microstructure and morphology of the powder play a fundamental role on the densification behaviour and grain boundary properties, thus affecting the overall conductivity of electrolytes [2]. In this light, solution combustion syn-thesis (SCS) represents a flexible method to produce ultra fine powders with suitable mic…

Studio di materiali avanzati per celle a combustibile ad ossidi solidi: influenza dei droganti e delle tecniche di sintesi sulle proprietà di anodi ed elettroliti

Today fuel cell (FC) technology is envisaged as a strategic alternative for providing clean energy through the exploitation of renewable sources; FC research is substantially funded by governments as a mean to meet the global market demand of zero environmental impact. Due to the high level of efficiency, FC devices are already able to compete with the existing power generation technologies and, in particular, solid oxide fuel cells (SOFCs) plants for stationary application constitute one the most efficient way to produce electric power and heat. Nowadays, the main challenges for SOFC research activity are: i) improving costs and durability, by reducing the operating temperature from ∼1000°…

Ionic conductivity of nanocrystalline heavily acceptor doped ceria: The role of the local atomic order

Acceptor doped ceria (CeO2) is a material that over the years has attracted much interest for applications in solid oxide fuel cells and oxygen membranes. This study aims at systematically investigating how the local atomic order and the dopant distribution affect the ionic transport of nanocrystalline CeO2 ceramics doped with samarium, erbium and ytterbium, with concentrations ranging between 10 and 30 at.%. For this purpose, a.c. electrochemical impedance spectroscopy together with Raman and fluorescence spectroscopy as well as XRD and EXAFS analysis have been carried out. In order to have detailed information on the bulk properties of these compositions also microcrystalline samples have…

Structure and oxide ion conductivity: local order, defect interactions and grain boundary effects in acceptor-doped ceria

The long-range and short-range structure of nanocrystalline and microcrystalline acceptor-doped ceria is investigated by a combined approach using EXAFS, XANES, Raman, and XRD, and correlated with the oxide-ion conductivity in the bulk and in grain boundaries. Compared to Yb3+ and Er3+, the positive influence of Sm3+ is attributed to the ability to repel oxygen vacancies, and to keep a localized disorder around the dopant. The long-range structural analysis shows lattice contraction for Yb- and Er-doping and lattice expansion for Sm-doping. The short-range analysis around the dopants and cerium highlights that a more complex structural rearrangement has to be assumed to explain the compleme…

Manganese iron oxide superparamagnetic powder by mechanochemical processing. Nanoparticles functionalization and dispersion in a nanofluid

Manganese ferrite nanoparticles were synthesized using a High-Energy Ball-Milling mechanochemical method. After 1 h of milling, the process produces a material consisting of single crystalline domain nanoparticles having a diameter of about 8 nm. Chemical properties of the synthesized powders allow an easy functionalization with citric acid. Both as-obtained and functionalized samples show superparamagnetic behaviour at room temperature, and the functionalized powder is stably dispersible in aqueous media at physiological pH. The average hydrodynamic diameter is equal to similar to 60 nm. Nanoparticles obtained by the reported High-Energy Ball-Milling method can be synthesized with high yie…

Direct Methane Oxidation on La1-xSrxCr1-yFeyO3-δ perovskite-type oxides as Potential Anode for Intermediate Temperature Solid Oxide Fuel Cells

Abstract La1−xSrxCr1−yFeyO3−δ (x = 0, 0.1, 0.15, 0.2; y = 0, 0.3, 0.5) perovskite-type oxide powders were synthesized by solution combustion synthesis and characterized by X-ray diffraction, X-ray photoelectron spectroscopy and H2-temperature programmed reduction. Selected compositions were studied by CH4-temperature programmed reduction in the absence and in the presence of H2S. Temperature programmed oxidation and structural characterizations were performed in order to discriminate the nature of residual deposits on the catalyst surface. The study about reduction in different methane-based mixture revealed that total and partial methane oxidation occurred in the range ∼450–1000 °C indepen…

FROM INTERCONNECTORS TO ANODE MATERIALS FOR IT-SOFCs:THE ROLE OF IRON IN La1-xSrxCr1-yFeyO3-δ

Solid–Solid Interfaces in Protonic Ceramic Devices: A Critical Review

The literature concerning protonic ceramic devices is critically reviewed focusing the reader's attention on the structure, composition, and phenomena taking place at solid-solid interfaces. These interfaces play a crucial role in the overall device performance, and the relevance of understanding the phenomena taking place at the interfaces for the further improvement of electrochemical protonic ceramic devices is therefore stressed. The grain boundaries and heterostructures in electrolytic membranes, the electrode-electrolyte contacts, and the interfaces within composite anode and cathode materials are all considered, with specific concern to advanced techniques of characterization and to …

The Role of the Local Atomic Order and Boundary Effects on the Electrical Transport of Ceria

Heavily acceptor doped ceria is a material of great relevance for applications in solid oxide fuel cells and oxygen membranes. Depending on the operation temperature, dopant concentration and microstructure (e.g. nanocrystalline vs. microcrystalline), the ionic transport properties of ceria can be mostly hindered by (i) grain boundaries or (ii) local atomic disorder in the bulk. Here, we present a selection of examples (ranging from thin films to ceramics) of how and to which extent these effects can affect the electrical transport properties. Emphasis will be given to the case of heavily doped nanocrystalline and microcrystalline ceria doped with samarium, erbium and ytterbium (dopant conc…

Catalytic and Electrical Properties of La1-xSrxCr1-yFeyO3-d as anodes for IT-SOFCs

Cation Diffusion and Segregation at the Interface between Samarium-Doped Ceria and LSCF or LSFCu Cathodes Investigated with X-ray Microspectroscopy

The chemical compatibility between electrolytes and electrodes is an extremely important aspect governing the overall impedance of solid-oxide cells. Because these devices work at elevated temperatures, they are especially prone to cation interdiffusion between the cell components, possibly resulting in secondary insulating phases. In this work, we applied X-ray microspectroscopy to study the interface between a samarium-doped ceria (SDC) electrolyte and lanthanum ferrite cathodes (La0.4Sr0.6Fe0.8Cu0.2O3(LSFCu); La0.9Sr0.1Fe0.85Co0.15O3(LSCF)), at a submicrometric level. This technique allows to combine the information about the diffusion profiles of cations on the scale of several micromet…