(Invited) High Entropy Multication Oxide Battery Materials

High entropy oxides (HEOs), in which multication occupation of a single crystallographic site plays an important role in the properties, have become relevant in energy storage [1,2], catalysis [3.4], and many more areas. In a subset of these compounds the entropy, rather than enthalpy, plays a dominant role in stabilizing a single-phase structure at high temperatures. In other cases, the multication occupation merely contributes to stability and properties, but the entropy remains dominant in the stability. The field originated with high entropy metal alloys (HEAs)[5], and then expanded to oxides, borides, sulfides, and more. In the case of HEOs, the first example is the rock salt (Mg0.2Ni0.2Co0.2Cu0.2Zn0.2)O, which has generated a great deal of interest in this class of materials.[6,7] It has been shown that HEOs are of interest for high ionic conductivity and electrochemical energy storage. We have examined the electrochemical performance of new high entropy elecrolytes and found an effect of composition on the cycling performance. Samples were prepared through sol-gel routes and high energy milling of starting binary oxides. We have investigated the synthesis using high temperature in-situ X-ray diffraction on a Panalytical diffractometer equipped with an XRK900 stage. STEM/EDS studies on ex-situ samples will be presented that show elemental distribution, with Raman and EIS measurements providing information on ionic diffusion. The results of this study will be highly impactful for the growing community of researchers investigating the design and synthesis of the new class of materials, the high entropy oxides. [1] Q. Wang, et. al., Multi-anionic and -cationic compounds: new high entropy materials for advanced Li-ion batteries, Energy Environ. Sci., 2019, 12, 2433; [2] D. Berardan, et. al., Room temperature lithium superionic conductivity in high entropy oxides, J. Mater. Chem. A, 2016, 4, 9536.; [3] H. Chen, et al., Mechanochemical Synthesis of High Entropy Oxide Materials under Ambient Conditions: Dispersion of Catalysts via Entropy Maximization, ACS Materials Lett. 2019, 1, 1, 83–88; [4] H. Chen, et. al., Entropy-stabilized metal oxide solid solutions as CO oxidation catalysts with high-temperature stability, J. Mater. Chem. A 2018, 6, 11129-11133; [5] Y. Lu, et. al., Sci. Rep. 4, 6200 (2014); Y. F. Ye, et. al., Mater. Today 19 (6), 349 (2016); Zhang, Y., et. al., Nature Commun. 6, 8736 (2015); [6] C. M. Rost, et. al., Nature Commun. 6, 8485 (2015); [7] B. Jiang, et. al., Probing the Local Site Disorder and Distortion in Pyrochlore High-Entropy Oxides. Journal of the American Chemical Society 2021, 143, (11), 4193-4204