Bi‐Co Based Bimetallic Catalysts for Synergistic Construction of Advanced Lithium‐Sulfur Batteries With High‐Safety and Wide Temperature Range Stability

ABSTRACT The limited number of active sites and rapid saturation of single‐metal catalysts hinder the sustained adsorption and efficient conversion of lithium polysulfides (LiPSs) in lithium‐sulfur batteries (LSBs). Here, we report a bimetallic catalyst (Bi‐CoP@G) with a core‐shell adsorptive‐conductive‐catalytic network to address the above challenges. In this structure, Bi sites strongly adsorb LiPSs via Bi‐S bonds, effectively immobilizing LiPSs and suppressing the shuttle effect. Complementarily, Co sites accelerate the redox kinetics of solid Li 2 S nucleation and dissolution. Interfacial charge redistribution and orbital coupling between the metals enhance electron transfer, establishing a synergistic “adsorption‐catalysis” cycle. Using Bi‐CoP@G/PP separators, the LSBs exhibit 82.9% capacity retention after 500 cycles at 1 C and an ultra‐low decay rate of 0.02% per cycle over 1000 cycles at 2 C. Moreover, the LSBs demonstrate stable cycling at a wide temperature range (‐20 to 50°C) and at the pouch‐LSB scale with a capacity of 124 mA h. Additionally, Bi‐CoP@G significantly enhances the fire safety of LBSs by simultaneously scavenging gas‐phase free radicals and promoting condensed‐phase carbonization during combustion. In summary, this work demonstrates a strategy for highly active bimetallic synergistic catalysts, offering a novel approach for the large‐scale production of advanced safe, and stable LSBs.