Investigations of Mechanisms Leading to Capacity Differences in Li/Na/K‐Ion Batteries with Conversion‐Type Transition‐Metal Sulfides Anodes

Abstract Conversion‐type transition‐metal sulfides (CT‐TMSs) have been extensively studied as the anode of Li/Na/K‐ion batteries due to their high theoretical capacity. An issue with the use of the material in the battery is that a large capacity difference is commonly observed. However, the underlying mechanism leading to the problem is still unknown. Here, the large capacity difference mechanisms of CT‐TMSs anodes in the Li/Na/K‐ion storage are elucidated, which arises from the difference in conversion degree and size of conversion products. Specifically, the increase in ionic radius will cause the increase in insertion‐reaction ion diffuse energy barrier and conversion‐reaction Gibbs free energies of phase transformation to decrease reaction kinetics, which causes a decrease in conversion degree and an increase in size of conversion products, thus leading to reduction in capacity. The increase in size and the decrease in the amount of conversion products inevitably reduce the amount of spin‐polarized electrons injection into Fe and corresponding ions storage amount into sulfides during the ion‐electron decoupling storage, thus reducing the capacity. The research clarifies the capacity difference mechanisms of CT‐TMSs anodes in Li/Na/K storage, providing valuable insights for designing Li/Na/K storage high‐capacity anodes.