Breaking Barriers to High‐Practical Li‐S Batteries with Isotropic Binary Sulfiphilic Electrocatalyst: Creating a Virtuous Cycle for Favorable Polysulfides Redox Environments

Investigations into lithium–sulfur batteries (LSBs) has focused primarily on the initial conversion of lithium polysulfides (LiPSs) to Li(2)S(2). However, the subsequent solid–solid reaction from Li(2)S(2) to Li(2)S and the Li(2)S decomposition process should be equally prioritized. Creating a virtuous cycle by balancing all three chemical reaction processes is crucial for realizing practical LSBs. Herein, amorphous Ni(3)B in synergy with carbon nanotubes (aNi(3)B@CNTs) is proposed to implement the consecutive catalysis of S(8(solid)) → LiPSs((liquid)) → Li(2)S((solid)) →LiPSs((liquid)). Systematic theoretical simulations and experimental analyses reveal that aNi(3)B@CNTs with an isotropic structure and abundant active sites can ensure rapid LiPSs adsorption‐catalysis as well as uniform Li(2)S precipitation. The uniform Li(2)S deposition in synergy with catalysis of aNi(3)B enables instant/complete oxidation of Li(2)S to LiPSs. The produced LiPSs are again rapidly and uniformly adsorbed for the next sulfur evolution process, thus creating a virtuous cycle for sulfur species conversion. Accordingly, the aNi(3)B@CNTs‐based cell presents remarkable rate capability, long‐term cycle life, and superior cyclic stability, even under high sulfur loading and extreme temperature environments. This study proposes the significance of creating a virtuous cycle for sulfur species conversion to realize practical LSBs.