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Advanced mixed ionic electronic conducting (MIEC) perovskites play an important role in many electrochemical systems for advanced energy technologies. They are major components in such devices as solid oxide fuel cells (SOFCs), oxygen separation membranes, chemical sensors and catalysts. In addition to energy technology, the development of these multifunctional materials is of crucial importance for transportation, aerospace engineering, and electronics. The use of these materials as chemical sensors is also important for anti-terrorism initiatives. The present book discusses progress and problems in the development of ionic, electronic, and MIEC materials as active materials in advanced energy systems; the development and design of solid-oxide fuel cells (SOFCs) for next-generation vehicles, chemical sensors and oxygen separation membranes; and identifies directions for future research, such as conducting mechanisms, stability and reliability of devices, degradation problems, crystal structure, classification of phase transitions exhibited by the materials.
This comprehensive handbook and ready reference details all the main achievements in the field of perovskite-based and related mixed-oxide materials. The authors discuss, in an unbiased manner, the potentials as well as the challenges related to their use, thus offering new perspectives for research and development on both an academic and industrial level. The first volume begins by summarizing the different synthesis routes from molten salts at high temperatures to colloidal crystal template methods, before going on to focus on the physical properties of the resulting materials and their related applications in the fields of electronics, energy harvesting, and storage as well as electromechanics and superconductivity. The second volume is dedicated to the catalytic applications of perovskites and related mixed oxides, including, but not limited to total oxidation of hydrocarbons, dry reforming of methane and denitrogenation. The concluding section deals with the development of chemical reactors and novel perovskite-based applications, such as fuel cells and high-performance ceramic membranes. Throughout, the contributions clearly point out the intimate links between structure, properties and applications of these materials, making this an invaluable tool for materials scientists and for catalytic and physical chemists.
Fuel cell technology is quite promising for conversion of chemical energy of hydrocarbon fuels into electricity without forming air pollutants. There are several types of fuel cells: polymer electrolyte fuel cell (PEFC), phosphoric acid fuel cell (PAFC), molten carbonate fuel cell (MCFC), solid oxide fuel cell (SOFC), and alkaline fuel cell (AFC). Among these, SOFCs are the most efficient and have various advantages such as flexibility in fuel, high reliability, simple balance of plant (BOP), and a long history. Therefore, SOFC technology is attracting much attention as a power plant and is now close to marketing as a combined heat and power generation system. From the beginning of SOFC development, many perovskite oxides have been used for SOFC components; for example, LaMnO -based oxide for the cathode and 3 LaCrO for the interconnect are the most well known materials for SOFCs. The 3 current SOFCs operate at temperatures higher than 1073 K. However, lowering the operating temperature of SOFCs is an important goal for further SOFC development. Reliability, durability, and stability of the SOFCs could be greatly improved by decreasing their operating temperature. In addition, a lower operating temperature is also beneficial for shortening the startup time and decreasing energy loss from heat radiation. For this purpose, faster oxide ion conductors are required to replace the conventional Y O -stabilized ZrO 2 3 2 electrolyte. A new class of electrolytes such as LaGaO is considered to be 3 highly useful for intermediate-temperature SOFCs.
The book summarizes the current state of the know-how in the field of perovskite materials: synthesis, characterization, properties, and applications. Most chapters include a review on the actual knowledge and cutting-edge research results. Thus, this book is an essential source of reference for scientists with research fields in energy, physics, chemistry and materials. It is also a suitable reading material for graduate students.
Surface exchange kinetics are a key indicator of performance for electrochemical devices including solid oxide fuel cells. Due to broad flexibility in dopant selection and concentration, mixed ionic-electronic conducting (MIEC) ABO3 perovskite oxides have been extensively explored as model systems to understand oxygen surface exchange kinetics for solid oxide fuel cell (SOFC) electrodes. Traditionally, transport properties are examined as functions of type and concentration of aliovalent cations, requiring multiple samples, resulting in changes in multiple characteristics and properties, often unintended. Moreover, the perovskite oxides generally accommodate only oxygen vacancies and not interstitials. In this study, the type and concentration of ionic defects (oxygen vacancies vs interstitials) in MIEC layered cuprates (La1.85Ce0.15CuO4) are systematically controlled, without change in cation doping or electronic conductivity, by electrochemical pumping of oxygen with and are analyzed through chemical capacitance, defect chemical modelling, and electrical conductivity. Oxygen surface exchange kinetics derived from electrochemical impedance spectra show a strong correlation with oxygen defect concentration increase, for both vacancies and interstitials. Key thermodynamic parameters, such as band gap energy (0.54±0.10 eV) and anion Frenkel enthalpy (0.618±0.074 eV) are derived. Evidence of oxygen vacancy ordering is observed from chemical capacitance analysis. Layered cuprates have multiple crystalline structure types – namely T, T*, and T’ – which share similar chemistry, but are known to have different properties, such as oxygen diffusivities. Control of structure is systematically studied by using different substrates and seed layers, and by electrochemical pumping of oxygen. A dynamic and reversible structural change in layered cuprate thin films is discovered, for the first time, by oxygen nonstoichiometry control. Oxygen diffusivities of T and T’ structures with the same cation chemistry (La2CuO4) are measured, for the first time, by oxygen isotope exchange experiment. The T-structured layered cuprate shows faster oxygen diffusion, but with higher activation compared to the T’ variant. On the other hand, faster oxygen surface exchange kinetics exhibited by the T’- as compared to the T- type structured cuprate, as measured by thin film conductivity relaxation, is attributed to a lower enthalpy of oxygen interstitial formation.
Ceramic Engineering and Science Proceedings Volume 34, Issue 4 - Advances in Solid Oxide Fuel Cells IX A collection of 13 papers from The American Ceramic Society's 37th International Conference on Advanced Ceramics and Composites, held in Daytona Beach, Florida, January 27-February 1, 2013. This issue includes papers presented in Symposium 3 - 10th International Symposium on Solid Oxide Fuel Cells: Materials, Science, and Technology.