High-Entropy Sn0.8(Co0.2Mg0.2Mn0.2Ni0.2Zn0.2)2.2O4 Conversion-Alloying Anode Material for Li-Ion Cells: Altered Lithium Storage Mechanism, Activation of Mg, and Origins of the Improved Cycling Stability

Benefits emerging from applying high-entropy ceramics in Li-ion technology are already well-documented in a growing number of papers. However, an intriguing question may be formulated: how can the multicomponent solid solution-type material ensure stable electrochemical performance? Utilizing an example of nonequimolar Sn-based Sn0.8(Co0.2Mg0.2Mn0.2Ni0.2Zn0.2)2.2O4 high-entropy spinel oxide, we provide a comprehensive model explaining the observed very good cyclability. The material exhibits a high specific capacity above 600 mAh g-1 under a specific current of 50 mA g-1 and excellent capacity retention near 100% after 500 cycles under 200 mA g-1. The stability originates from the conversion-alloying reversible reactivity of the amorphous matrix, which forms during the first lithiation from the initial high-entropy structure, and preserves the high level of cation disorder at the atomic scale. In the altered Li-storage mechanism in relation to the simple oxides, the unwanted aggregated metallic grains are not exsolved from the anode and therefore do not form highly lithiated phases characterized by large volumetric changes. Also, the electrochemical activity of Mg from the oxide matrix can be clearly observed. Because the studied compound was prepared by a conventional solid-state route, implementation of the presented approach is facile and appears usable for any oxide anode material containing a high-entropy mixture of elements.