Bidirectional Tandem Electrocatalysis Manipulated Sulfur Speciation Pathway for High‐Capacity and Stable Na‐S Battery

Abstract The sluggish polysulfide redox kinetics and the uncontrollable sulfur speciation pathway, leading to serious shuttling effect and high activation barrier associated with sulfur cathode. We describe here the use of core–shell structured composite matrixes containing abundant catalytic sites for nearly fully reversible cycling of sulfur cathodes for Na‐S batteries. The bidirectional tandem electrocatalysis provide successive reversible conversion of both long‐ and short‐chain polysulfides, whereas Fe 2 O 3 accelerates Na 2 S 8 /Na 2 S 6 to Na 2 S 4 conversion and the redox‐active Fe(CN) 6 4− ‐doped polypyrrole shell catalyzes Na 2 S 4 reduction to Na 2 S. The electrochemically reactive Na 2 S can be readily charged back to sulfur with minimal overpotential. Simultaneously, stable cycling of Na‐S pouch cell with a high reversible capacity of 696 mAh g −1 is also demonstrated. The bidirectional confined tandem catalysis renders the manipulation of sulfur redox electrochemistry for practical Na‐S cells.