“Bowling Collision Effect” of CoMo6 Polyoxometalate Units Enables Wide Temperature Range from −20 to 60 °C and Dendrite Mitigation Li‐S Batteries

Abstract To improve the performance of Lithium‐Sulfur (Li‐S) batteries, the reaction catalysts of lithium polysulfides (LiPSs) reactions should have the characteristics of large surface area, efficient atomic utilization, high conductivity, small size, good stability, and strong adjustability. Herein, Anderson‐type polyoxometalate ([TMMo 6 O 24 ] n− , TM = Co, Ni, Fe, represented by TMMo 6 POMs) are used as the modified materials for Li‐S battery separator. By customizing the central metal atoms, this work gains insights into the layer‐by‐layer electron transfer mechanism between TMMo 6 units and LiPSs, similar to the collision effect of a bowling ball. Theoretical analysis and in situ experimental characterization show that the changes of CoMo 6 units with moderate binding energy and lowest Gibbs free energy result in the formation of robust polar bonds and prolonged S─S bonds after adsorption. Hence, the representative Li‐S battery with CoMo 6 and graphene composite modified separator has a high initial capacity of 1588.6 mA h g −1 at 0.2 C, excellent cycle performance of more than 3000 cycles at 5 C, and uniform Li + transport over 1900 h. More importantly, this work has revealed the inherent contradiction between the kinetics and thermodynamics, achieving a stable cycle in the temperature range of −20 to 60 °C.