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.
Highlights
We showed that the laser 3D printing (L3DP) method is capable of manufacturing Protonic ceramics (PCs) with desired complex geometries, crystal structures, and microstructures
We further demonstrated the success of manufacturing PC parts such as pellets, cylinders, cones, films, straight/lobed tubes with sealed endings, microchannel membranes, and half cells for assembling protonic ceramic energy devices (PCEDs)
The ceramic powder to water (C/W) ratio and the amount of binder both can adjust the viscosity of the paste to the desired range, in this work, we fixed the C/W ratio at 1:1 to prevent cracking during drying and varied the amount of the binder to optimize the paste viscosity
Summary
Along with the development of new materials for achieving high proton conductivity [1,2,3], protonic ceramics (PCs) have achieved significant progress on intermediate-temperature (300–600 ◦ C) protonic ceramic energy devices (PCEDs) such as PC fuel cells [4,5,6,7,8], PC electrolysis cells [9], reversible PC electrochemical cells [10,11,12,13], PC membrane reactors [14,15,16], hydrogen-permeable membranes [17,18], water-permeable membranes, and solid-state ammonia synthesis cells [19,20,21,22,23]. The 3D printing of ceramics has caught significant attention too, the common challenges for ceramic processing such as the difficulty for achieving high accuracy due to the significant shrinkage, the difficulty for fulfilling crack-free rapid sintering due to the intrinsic brittleness, the difficulty for depositing precise layers due to the heavy involvement of additive materials (e.g., polymer binders and solvents) are the significant obstacles for the 3D printing-based advanced manufacturing. We further demonstrated the success of manufacturing PC parts such as pellets, cylinders, cones, films, straight/lobed tubes with sealed endings, microchannel membranes, and half cells for assembling PCEDs. The preliminary characterization of the L3DP-derived PC electrolyte films showed a high proton conductivity, which provided a substantial prerequisite for the successful PCEDs
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