Facile preparation of ZrO2 whiskers by LiF-KCl molten salts synthesis

Monoclinic zirconia (ZrO2) whiskers were made via the molten salt method using zirconyl chloride octahydrate (ZrOCl2 ? 8H2O) as zirconium source, potassium chloride (KCl) as molten salt and lithium fluoride (LiF) as a mineraliser. DSC-TG, XRD, FE-SEM, Raman and TEM were performed to study the effects of heat treatment temperature, holding time and heating rate on the synthesis of zirconia whiskers. The results indicate that zirconia whiskers with diameters of 50-80 nm and aspect ratios of 10-30 can be obtained by heating the precursor at slow rate (3?C/min) to 718?C for 1 h and then at faster rate (7?C/min) to 950?C for 3 h. The whiskers have a smooth surface and grow in [001] direction. The key to the ZrO2 whiskers growth is the controlled dissolution and precipitation of the ZrO2 in a LiF-KCl molten salt solution environment.

The Detection of Monoclinic Zirconia and Non-Uniform 3D Crystallographic Strain in a Re-Oxidized Ni-YSZ Solid Oxide Fuel Cell Anode

The solid oxide fuel cell (SOFC) anode is often composed of nickel (Ni) and yttria-stabilized zirconia (YSZ). The yttria is added in small quantities (e.g., 8 mol %) to maintain the crystallographic structure throughout the operating temperatures (e.g., room-temperature to >800 °C). The YSZ skeleton provides a constraining structural support that inhibits degradation mechanisms such as Ni agglomeration and thermal expansion miss-match between the anode and electrolyte layers. Within this structure, the Ni is deposited in the oxide form and then reduced during start-up; however, exposure to oxygen (e.g., during gasket failure) readily re-oxidizes the Ni back to NiO, impeding electrochemical performance and introducing complex structural stresses. In this work, we correlate lab-based X-ray computed tomography using zone plate focusing optics, with X-ray synchrotron diffraction computed tomography to explore the crystal structure of a partially re-oxidized Ni/NiO-YSZ electrode. These state-of-the-art techniques expose several novel findings: non-isotropic YSZ lattice distributions; the presence of monoclinic zirconia around the oxidation boundary; and metallic strain complications in the presence of variable yttria content. This work provides evidence that the reduction–oxidation processes may destabilize the YSZ structure, producing monoclinic zirconia and microscopic YSZ strain, which has implications upon the electrode’s mechanical integrity and thus lifetime of the SOFC.