Integrated Design of Homogeneous/Heterogeneous Copper Complex Catalysts to Enable Synergistic Effects on Sulfur and Lithium Evolution Reactions

Fatal polysulfide shuttling, sluggish sulfur redox kinetics and detrimental lithium dendrites have curtailed the real discharge capacity, working lifespan and safety of lithium–sulfur (Li–S) batteries. Organic small molecule promotors as one type of emerging active catalysts can fulfil the management of the electrochemical species evolution behaviors. Herein, an integrated engineering is organized by synthesizing dual chlorine‐bridge enabled binuclear copper complex (Cu2(phen)2Cl2) and its derivative generated in electrolyte (Cu‐ETL) as the heterogeneous and homogeneous catalyst, respectively. The well‐designed Cu‐ETL with a optimized concentration of 0.25 wt.% as a homogeneous enabler offers highly utilized Cu centers and the sufficient interface contact for guiding the Li2S nucleation/decomposition reactions. The Cu2(phen)2Cl2 loaded on carbon spheres as an interlayer (Cu‐INT) can break through the catalytic limitation resulting from the saturated concentration of Cu‐ETL and thus offers an extended manipulation effect. Benefiting from the synergistic effect, the Li–S battery shows stable cycling at 3 C upon 500 cycles with a capacity degradation rate as low as 0.029% per cycle. Of specific note, an actual cell energy density of 372.1 Wh kg−1 is harvested by a 1.2 Ah‐level soft‐packaged pouch cell, implying a chance for requiring the demand of high‐energy batteries.