Electrochemical Phase Evolution of Metal‐Based Pre‐Catalysts for High‐Rate Polysulfide Conversion

In situ evolution of electrocatalysts is of paramount importance in defining catalytic reactions. Catalysts for aprotic electrochemistry such as lithium-sulfur (Li-S) batteries are the cornerstone to enhance intrinsically sluggish reaction kinetics but the true active phases are often controversial. Herein, we reveal the electrochemical phase evolution of metal-based pre-catalysts (Co4 N) in working Li-S batteries that renders highly active electrocatalysts (CoSx ). Electrochemical cycling induces the transformation from single-crystalline Co4 N to polycrystalline CoSx that are rich in active sites. This transformation propels all-phase polysulfide-involving reactions. Consequently, Co4 N enables stable operation of high-rate (10 C, 16.7 mA cm-2 ) and electrolyte-starved (4.7 μL mgS-1 ) Li-S batteries. The general concept of electrochemically induced sulfurization is verified by thermodynamic energetics for most of low-valence metal compounds.