Binary Atomic Sites Enable a Confined Bidirectional Tandem Electrocatalytic Sulfur Conversion for Low‐Temperature All‐Solid‐State Na−S Batteries

Abstract

AbstractThe broader implementation of current all‐solid‐state Na−S batteries is still plagued by high operation temperature and inefficient sulfur utilization. And the uncontrollable sulfur speciation pathway along with the sluggish polysulfide redox kinetics further compromise the theoretical potentials of Na−S chemistry. Herein, we report a confined bidirectional tandem electrocatalysis effect to tune polysulfide electrochemistry in a novel low‐temperature (80 °C) all‐solid‐state Na−S battery that utilizes Na3Zr2Si2PO12 ceramic membrane as a platform. The bifunctional hollow sulfur matrix consisting binary atomically dispersed MnN4 and CoN4 hotspots was fabricated using a sacrificial template process. Upon discharge, CoN4 sites activate sulfur species and catalyze long‐chain to short‐chain polysulfides reduction, while MnN4 centers substantially accelerate the low‐kinetic Na2S4 to Na2S directly conversion, manipulating the uniform deposition of electroactive Na2S and avoiding the formation of irreversible products (e.g., Na2S2). The intrinsic synergy of two catalytic centers benefits the Na2S decomposition and minimizes its activation barrier during battery recharging and then efficiently mitigate the cathodic passivation. As a result, the stable cycling of all‐solid‐state Na−S cell delivers an attractive reversible capacity of 1060 mAh g−1 with a high CE of 98.5 % and a high energy of 1008 Wh kgcathode−1, comparable to the liquid electrolyte cells.