Sustaining vacancy catalysis via conformal graphene overlays boosts practical Li–S batteries

Sluggish reaction kinetics and uncontrollable dendrite growth are deemed as the main bottlenecks for practical Li–S batteries. Notwithstanding fruitful advances in designing dual-functional mediators for both electrodes, cooperative efforts on protecting catalytic active sites and optimizing solid electrolyte interphase (SEI) with the employment of industrial catalysts are still lacking. Herein, an oxygen vacancy (V_O)-sustained prototype mediator with layer-number controllable graphene modification (Al₂O₃@mG) is developed for concurrently accelerating redox kinetics at the S cathode and harvesting inorganic-rich SEI at the Li anode. Theoretical and experimental analysis reveals V_O enhances the electrocatalytic activity while the graphene overlay serving as a catalysis sustainer enables the vacancy protection. Meanwhile, Al₂O₃@mG is conductive to homogenizing Li-ion flux and boosting preferential decomposition of anions, thereby stabilizing Li metal anode. Benefiting from such dual-functional reformulation, Li–S batteries with Al₂O₃@mG modified separators achieve a relieved capacity decay of 0.032% per cycle over 1600 cycles at 1.0 C. The assembled pouch cell delivers high areal capacity and stable cyclic operation. Such a vacancy-sustained graphene maneuver showcases promising universality to be applied on various oxide candidates, offering a meaningful guidance in mediator design toward pragmatic Li–S batteries.