A facile mechanochemical reaction at ambient temperature was successfully applied to synthesize novel single-phase rock-salt-structured high-entropy oxides, containing five, six and seven metal elements in equiatomic amounts. This synthesis approach overcomes the limitations of the commonly known synthesis procedures, which would result in multiple-phase compounds. Redox-sensitive elements, such as Fe2+ and Mn2+, can now be considered. The corresponding single-phase Li-containing high-entropy oxyfluorides were obtained by introducing LiF into the lattice using the same strategy. All materials show single-phase rock-salt structures with lattice parameters depending on the incorporated ion sizes. Solid solution states result in high configurational entropies, and all elements appear homogenously distributed over the whole cationic and anionic sublattice. The straightforward synthesis technique, combined with utilized simple binary oxide precursors, paves the way for a multitude of novel high-entropy oxide and oxyfluoride compounds. The compounds were studied by means of X-ray diffraction, transmission electron microscopy, energy-dispersive X-ray spectroscopy and Mössbauer spectroscopy.
High entropy oxides (HEOs) constitute a promising class of materials with possibly new and largely unexplored properties. The virtually infinite variety of compositions (multi-element approach) for a single-phase structure allows the tailoring of their physical properties and enables unprecedented materials design. Nevertheless, this level of versatility renders their characterization as well as the study of specific processes or reaction mechanisms challenging. In the present work, we report the structural and electrochemical behavior of different multi-cationic HEOs. Phase transformation from spinel to rock-salt was observed upon incorporation of monovalent Li+ ions, accompanied by partial oxidation of certain elements in the lattice. This transition was studied by X-ray diffraction, inductively coupled plasma-optical emission spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, and attenuated total reflection infrared spectroscopy. In addition, the redox behavior was probed using cyclic voltammetry. Especially, the lithiated rock-salt structure HEOs were found to exhibit potential for usage as negative and positive electrode materials in rechargeable lithium-ion batteries.
Efficient Lewis-acid-catalyzed direct conversion of aldehydes to 1,2-diketones in the liquid phase was enabled by using newly designed and developed ceria–zirconia-based high-entropy oxides (HEOs) as the actual catalysts. The synergistic effect of various cations incorporated in the same oxide structure (framework) was partially responsible for the efficiency of multicationic materials compared to the corresponding single-cation oxide forms. Furthermore, a clear, linear relationship between the Lewis acidity and the catalytic activity of the HEOs was observed. Due to the developed strategy, exclusively diketone-selective, recyclable, versatile heterogeneous catalytic transformation of aldehydes can be realized under mild reaction conditions.
In this fundamental work, a series of experiments were performed to define the optimal amount of dispersant and solid content for feedstock with and without ceramic fibers (Nextel 610). Based on these fixed conditions, investigations were carried out to discover the effects of binder system, fiber sizing, and increasing fiber content on mixing and viscosity. In addition, the effects of kneading temperature and time, fiber sizing, and different binder systems on fiber length were investigated using a measuring mixer, high-pressure capillary rheometer, and microscopy. Stearic acid, as a dispersant, modified the particle surface and improved the rheological properties. Moreover, increasing the solid content in the feedstocks led to an exponential growth of final torque and relative viscosity, because of the increasing friction between particles. Paraffin wax (PW)- and polyethylene glycol (PEG)-based feedstocks showed different mixing behaviors and rheological results with increasing fiber, whereas PEG-based feedstocks had higher final torques and kneading energies without fibers, whilst PEG feedstocks displayed lower viscosities. Consequently, during kneading, the amount of fiber has been predominating over fiber length, and the effect of the binder, the kneading temperature, and time did not cause significant changes.
Configurational entropy stabilizes P2-type Na x MO 2 layered cathodes by suppressing TM migration and P2–O2 gliding. High-entropy compositions distribute redox activity, improving structural reversibility and cycling stability in Na-ion batteries.