Revealing the Selective Bifunctional Electrocatalytic Sites via In Situ Irradiated X‐Ray Photoelectron Spectroscopy for Lithium–Sulfur Battery

The electrocatalysts are widely applied in lithium–sulfur (Li–S) batteries to selectively accelerate the redox kinetics behavior of Li(2)S, in which bifunctional active sites are established, thereby improving the electrochemical performance of the battery. Considering that the Li–S battery is a complex closed “black box” system, the internal redox reaction routes and active sites cannot be directly observed and monitored especially due to the distribution of potential active‐site structures and their dynamic reconstruction. Empirical evidence demonstrates that traditional electrochemical test methods and theoretical calculations only probe the net result of multi‐factors on an average and whole scale. Herein, based on the amorphous TiO(2‐) (x) @Ni selective bifunctional model catalyst, these limitations are overcome by developing a system that couples the light field and in situ irradiated X‐ray photoelectron spectroscopy to synergistically convert the “black box” battery into a “see‐through” battery for direct observation of the charge transportation, thus revealing that amorphous TiO(2‐) (x) and Ni nanoparticle as the oxidation and reduction sites selectively promote the decomposition and nucleation of Li(2)S, respectively. This work provides a universal method to achieve a deeper mechanistic understanding of bidirectional sulfur electrochemistry.