Bulk ceria-zirconia solid solutions (Ce1−xZrxO2−δ, CZO) are highly suited for application as oxygen storage materials in automotive three-way catalytic converters (TWC) due to the high levels of achievable oxygen non-stoichiometry δ. In thin film CZO, the oxygen storage properties are expected to be further enhanced. The present study addresses this aspect. CZO thin films with 0 ≤ x ≤ 1 were investigated. A unique nano-thermogravimetric method for thin films that is based on the resonant nanobalance approach for high-temperature characterization of oxygen non-stoichiometry in CZO was implemented. The high-temperature electrical conductivity and the non-stoichiometry δ of CZO were measured under oxygen partial pressures pO2 in the range of 10−24–0.2 bar. Markedly enhanced reducibility and electronic conductivity of CeO2-ZrO2 as compared to CeO2−δ and ZrO2 were observed. A comparison of temperature- and pO2-dependences of the non-stoichiometry of thin films with literature data for bulk Ce1−xZrxO2−δ shows enhanced reducibility in the former. The maximum conductivity was found for Ce0.8Zr0.2O2−δ, whereas Ce0.5Zr0.5O2-δ showed the highest non-stoichiometry, yielding δ = 0.16 at 900 °C and pO2 of 10−14 bar. The defect interactions in Ce1−xZrxO2−δ are analyzed in the framework of defect models for ceria and zirconia.

Featuring high levels of achievable oxygen non-stoichiometry δ, Ce1−xZrxO2−δ solid solutions (CZO) are crucial for application as oxygen storage materials in, for example, automotive three-way catalytic converters (TWC). The use of CZO in form of films combined with simple manufacturing methods is beneficial in view of device miniaturization and reducing of TWC manufacturing costs. In this study, a comparative microstructural and electrochemical characterization of film and conventional bulk CZO is performed using X-ray diffractometry, scanning electron microscopy, and impedance spectroscopy. The films were composed of grains with dimensions of 100 nm or less, and the bulk samples had about 1 µm large grains. The electrical behavior of nanostructured films and coarse-grained bulk CZO (x > 0) was qualitatively similar at high temperatures and under reducing atmospheres. This is explained by dominating effect of Zr addition, which masks microstructural effects on electrical conductivity, enhances the reducibility, and favors strongly electronic conductivity of CZO at temperatures even 200 K lower than those for pure ceria. The nanostructured CeO2 films had much higher electrical conductivity with different trends in dependence on temperature and reducing atmospheres than their bulk counterparts. For the latter, the conductivity was dominantly electronic, and microstructural effects were significant at T < 700 °C. Nanostructural peculiarities of CeO2 films are assumed to induce their more pronounced ionic conduction at medium oxygen partial pressures and relatively low temperatures. The defect interactions in bulk and film CZO under reducing conditions are discussed in the framework of conventional defect models for ceria.

Recently, a laboratory setup for microwave-based characterization of powder samples at elevated temperatures and different gas atmospheres was presented. The setup is particularly interesting for operando investigations on typical materials for exhaust gas aftertreatment. By using the microwave cavity perturbation method, where the powder is placed inside a cavity resonator, the change of the resonant properties provides information about changes in the dielectric properties of the sample. However, determining the exact complex permittivity of the powder samples is not simple. Up to now, a simplified microwave cavity perturbation theory had been applied to estimate the bulk properties of the powders. In this study, an extended approach is presented which allows to determine the dielectric properties of the powder materials more correctly. It accounts for the electric field distribution in the resonator, the depolarization of the sample and the effect of the powder filling. The individual method combines findings from simulations and recognized analytical approaches and can be used for investigations on a wide range of materials and sample geometries. This work provides a more accurate evaluation of the dielectric powder properties and has the potential to enhance the understanding of the microwave behavior of storage materials for exhaust gas aftertreatment, especially with regard to the application of microwave-based catalyst state diagnosis.

No abstract

Thermoelectric generators (TEGs) offer a versatile solution to convert low‐grade heat into useful electrical power. While reducing the length of the active thermoelectric legs provides an efficient strategy to increase the maximum output power density pmax, both the high electrical contact resistances and thermomechanical stresses are two central issues that have so far prevented a strong reduction in the volume of thermoelectric materials integrated. Here, it is demonstrated that these barriers can be lifted by using a nonconventional architecture of the legs which involves inserting thick metallic layers. Using skutterudites as a proof‐of‐principle, several single‐couple and multi‐couple TEGs with skutterudite layers of only 1 mm are fabricated, yielding record pmax ranging from 3.4 up to 7.6 W cm−2 under temperature differences varying between 450 and 630 K. The highest pmax achieved corresponds to a 60‐fold increase per unit volume of skutterudites compared to 1 cm long legs. This work establishes thick metallic layers as a robust strategy through which high power density TEGs may be developed.