Synergy of cations in high entropy oxide lithium ion battery anode.

High entropy oxides (HEOs) with chemically disordered multi-cation structure attract intensive interest as negative electrode materials for battery applications. The outstanding electrochemical performance has been attributed to the high-entropy stabilization and the so-called 'cocktail effect'. However, the configurational entropy of the HEO, which is thermodynamically only metastable at room-temperature, is insufficient to drive the structural reversibility during conversion-type battery reaction, and the 'cocktail effect' has not been explained thus far. This work unveils the multi-cations synergy of the HEO Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O at atomic and nanoscale during electrochemical reaction and explains the 'cocktail effect'. The more electronegative elements form an electrochemically inert 3-dimensional metallic nano-network enabling electron transport. The electrochemical inactive cation stabilizes an oxide nanophase, which is semi-coherent with the metallic phase and accommodates Li+ ions. This self-assembled nanostructure enables stable cycling of micron-sized particles, which bypasses the need for nanoscale pre-modification required for conventional metal oxides in battery applications. This demonstrates elemental diversity is the key for optimizing multi-cation electrode materials.

Sol-Gel Synthesis of Ceria-Zirconia-Based High-Entropy Oxides as High-Promotion Catalysts for the Synthesis of 1,2-Diketones from Aldehyde.

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.

High Entropy and Low Symmetry: Triclinic High-Entropy Molybdates.

Metal molybdates constitute a promising class of materials with a wide application range. Here, we report, to our knowledge for the first time, on the preparation and characterization of medium-entropy and high-entropy metal molybdates, synthesized by an oxalate-based coprecipitation approach. The high-entropy molybdate crystallizes in a triclinic structure, thus rendering it as high-entropy material with the lowest symmetry reported so far. This is noteworthy because high-entropy materials usually tend to crystallize into highly symmetrical structures. It is expected that application of the high-entropy concept to metal molybdates alters the material's characteristics and adds the features of high-entropy systems, that is, tailorable composition and properties. The phase purity and solid solution nature of the molybdates were confirmed by XRD, Raman spectroscopy, TEM, XPS, and ICP-OES.

Lithium containing layered high entropy oxide structures.

Layered Delafossite-type Lix(M1M2M3M4M5…Mn)O2 materials, a new class of high-entropy oxides, were synthesized by nebulized spray pyrolysis and subsequent high-temperature annealing. Various metal species (M = Ni, Co, Mn, Al, Fe, Zn, Cr, Ti, Zr, Cu) could be incorporated into this structure type, and in most cases, single-phase oxides were obtained. Delafossite structures are well known and the related materials are used in different fields of application, especially in electrochemical energy storage (e.g., LiNixCoyMnzO2 [NCM]). The transfer of the high-entropy concept to this type of materials and the successful structural replication enabled the preparation of novel compounds with unprecedented properties. Here, we report on the characterization of a series of Delafossite-type high-entropy oxides by means of TEM, SEM, XPS, ICP-OES, Mössbauer spectroscopy, XRD including Rietveld refinement analysis, SAED and STEM mapping and discuss about the role of entropy stabilization. Our experimental data indicate the formation of uniform solid-solution structures with some Li/M mixing.