Bimetallic Sulfide Hollow Nanocubes Heterostructure Promotes Dual Coupling of Conversion and Alloying/Dealloying Reactions to Achieve Durable Potassium-Ion Battery Anode.

Conversion and alloying-type transitional metal sulfides have attracted significant interests as anodes for Potassium-ion batteries (PIBs) and Sodium-ion batteries (SIBs) due to their high theoretical capacities and low cost. However, the poor conductivity, structural pulverization, and high-volume expansions greatly limit the performance. Herein, Co1-xS/ZnS hollow nanocube-like heterostructure decorated on reduced graphene oxide (Co1-xS/ZnS@rGO) composite is fabricated through convenient hydrothermal and post-heat vulcanization techniques. This unique composite can provide a more stable conductive network and shorten the diffusion length of ions, which exhibits a remarkable initial charge capacity of 638.5 mA h g-1 at 0.1 A g-1 for SIBs and 606 mA h g-1 at 0.1 A g-1 for PIBs, respectively; It is worth noting that the composite presents remarkable long stable cycle performance in PIBs, which initially delivered 274 mA h g-1 and sustained the charge capacity up to 245 mA h g-1 at high current density of 1 A g-1 after 2000 cycles. A series of in situ/ex situ detections and first principle calculations further validate the high potassium ions adsorption ability of Co1-xS/ZnS anode materials with high diffusion kinetics. This work will accelerate the fundamental construction of bimetallic sulfide hollow nanocubes heterostructure electrodes for energy storage applications.

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.