No abstract

Mayenite (12CaO·7AlO, C12A7) electride with an anti-zeolite nanoporous structure has attracted intense attention due to its versatile promising application potentials. However, the synthesis difficulty because of extremely harsh conditions (e.g., reduction in sealed calcium or titanium vapor) significantly obstructs its realistic applications. In this work, we employed a simple, efficient, and cost-effective route for synthesizing mayenite electrides (C12A7:e) in both powder and dense ceramic. C12A7:e powders with efficient electron doping (3.5 × 10 cm) were obtained via simple graphite reduction of a novel mixture precursor of CaAlO (CA) and CaAlO (C3A) derived from a modified Pechini method. The structural evolution during the electride formation was investigated, and it was found that reduction below 1300 °C induced the formation of CaAlO (C5A3), while reduction above 1400 °C helped retain the mayenite structure. Fully dense C12A7:e ceramics were also fabricated via graphite reduction of presintered pellets with a relative density of 97.9% starting from the CA+C3A mixture. Careful studies improved the mechanism cognition of graphite treatment that the electrons injection was probably initiated by surface reduction with involatile C species (e.g., C) rather than previously proposed CO, during which the mixed conduction of oxygen ions and electrons played an important role. Furthermore, the stability of C12A7:e in water as well as in the presence of moisture was discussed. These results not only suggest a novel precursor for fabricating high-quality mayenite electrides but also provide in-depth insights into the stability of the mayenite structure toward practical applications.

No abstract

No abstract

Protonic ceramics (PCs) with high proton conductivity at intermediate temperatures (300–600 °C) have attracted many applications in energy conversion and storage devices such as PC fuel/electrolysis cells, PC membrane reactors, hydrogen pump, hydrogen or water-permeable membranes, and gas sensors. One of the essential steps for fulfilling the practical utilization of these intermediate-temperature PC energy devices is the successful development of advanced manufacturing methods for cost-effectively and rapidly fabricating them with high energy density and efficiency in a customized demand. In this work, we developed a new laser 3D printing (L3DP) technique by integrating digital microextrusion-based 3D printing and precise and rapid laser processing (sintering, drying, cutting, and polishing), which showed the capability of manufacturing PCs with desired complex geometries, crystal structures, and microstructures. The L3DP method allowed the fabrication of PC parts such as pellets, cylinders, cones, films, straight/lobed tubes with sealed endings, microchannel membranes, and half cells for assembling PC energy devices. The preliminary measurement of the L3DP electrolyte film showed a high proton conductivity of ≈7 × 10−3 S/cm. This L3DP technique not only demonstrated the potential to bring the PCs into practical use but also made it possible for the rapid direct digital manufacturing of ceramic-based devices.