The kinetics of stoichiometry change of an oxide--a prototype of a simple solid-state reaction and a process of substantial technological relevance--is studied and analyzed in great detail. Oxygen incorporation into strontium titanate was chosen as a model process. The complete reaction can be phenomenologically and mechanistically understood beginning with the surface reaction and ending with the transport in the perovskite. Key elements are a detailed knowledge of the defect chemistry of the perovskite as well as the application of a variety of experimental and theoretical tools, many of them evolving from this study. The importance of the reaction and transport steps for (electro)chemical applications is emphasized.

Solid oxide fuel cells (SOFC) are under intensive investigation since the 1980's as these devices open the way for ecologically clean direct conversion of the chemical energy into electricity, avoiding the efficiency limitation by Carnot's cycle for thermochemical conversion. However, the practical development of SOFC faces a number of unresolved fundamental problems, in particular concerning the kinetics of the electrode reactions, especially oxygen reduction reaction. We review recent experimental and theoretical achievements in the current understanding of the cathode performance by exploring and comparing mostly three materials: (La,Sr)MnO3 (LSM), (La,Sr)(Co,Fe)O3 (LSCF) and (Ba,Sr)(Co,Fe)O3 (BSCF). Special attention is paid to a critical evaluation of advantages and disadvantages of BSCF, which shows the best cathode kinetics known so far for oxides. We demonstrate that it is the combined experimental and theoretical analysis of all major elementary steps of the oxygen reduction reaction which allows us to predict the rate determining steps for a given material under specific operational conditions and thus control and improve SOFC performance.

Bulk Li2O2 is shown to exhibit ionic conductivity via lithium vacancies and electronic conductivity via electron holes (localized as superoxide ions). This is the first systematic study on the charge carrier chemistry of peroxides with high relevance for the performance kinetics of Li-oxygen batteries.

Thermodynamics shows halide perovskites to be highly unstable against oxygen. Light accelerates O2 interaction kinetics. The materials stays metastable in the dark.

The proton uptake of 18 compositions in the perovskite family (Ba,Sr,La)(Fe,Co,Zn,Y)O 3-δ , perovskites, which are potential cathode materials for protonic ceramic fuel cells (PCFCs), is investigated by thermogravimetry. Hydration enthalpies and entropies are derived, and the doping trends are explored. The uptake is found to be largely determined by the basicity of the oxide ions. Partial substitution of Zn on the B-site strongly enhances proton uptake, while Co substitution has the opposite effect. The proton concentration in Ba 0.95 La 0.05 Fe 0.8 Zn 0.2 O 3-δ is found to be 10% per formula unit at 250 °C, 5.5% at 400 °C, and 2.3% at 500 °C, which are the highest values reported so far for a mixed-conducting perovskite exhibiting hole, proton, and oxygen vacancy transport. A comprehensive set of thermodynamic data for proton uptake in (Ba,Sr,La)(Fe,Co,Zn,Y)O 3-δ is determined. Defect interactions between protons and holes partially delocalized from the B-site transition metal to the adjacent oxide ions decrease the proton uptake. From these results, guidelines for the optimization of PCFC cathode materials are derived.

An extensive set of DFT calculations on LaMnO 3 slabs has been generated and used as a basis to identify the most probable reaction mechanism for oxygen incorporation into (La, Sr)MnO 3-δ cathode materials. MnO 2 [001] is found to be the most stable surface termination under fuel cell operation conditions (high temperature, high pO 2 , cubic unit cell). Chemisorption leading to the formation of O 2 -, O 2 2-, and O -atop Mn is exothermic, but due to the negative adsorption entropy and electrostatic repulsion the levels of coverage of molecular oxygen adsorbates are low (in the few percent range). Under typical solid oxide fuel cell conditions, a mechanism in which the encounter of O -with a surface oxygen vacancy at the surface is rate-determining exhibits the fastest rate. The variation of the reaction rate and preferred mechanism(s) with adsorbate and point defect concentrations is discussed.

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Conductivity measurements were performed on microcrystalline and nanocrystalline ceria (undoped and doped) in dry as well as wet atmosphere. Below 200-250 °C, the nanocrystalline samples exhibit an enhanced total conductivity under wet conditions, which increases with decreasing temperature. In addition, thermo-gravimetric analysis revealed a strong water uptake below 200 °C. DC-polarization measurements confirm the ionic character of conductivity in the nanocrystalline samples at low temperatures. The role of both grain boundaries and residual porosity on the enhanced conductivity below 200 °C is discussed.