Ab Initio Simulation of Raman Fingerprints of Sulfur/Carbon Copolymer Cathodes During Discharge of Li‐S Batteries

Abstract Sulfur/carbon copolymers have emerged as promising alternatives for conventional crystalline sulfur cathodes for lithium‐sulfur batteries. Among these, sulfur‐ n ‐1,3‐diisopropenylbenzene (S/DIB) copolymers, which present a 3D network of DIB molecules interconnected via sulfur chains, have particularly shown a good performance and, therefore, have been under intensive experimental and theoretical investigations. However, their structural complexity and flexibility have hindered a clear understanding of their structural evolution during redox reactions at an atomistic level. Here, by performing state‐of‐the‐art ab initio molecular dynamics‐based Raman spectroscopy simulations, we investigate the spectral fingerprints of S/DIB copolymers arising from local structures during consecutive reactions with lithium. We discuss in detail Raman spectral changes in particular frequency ranges which are common in S/DIB copolymers having short sulfur chains and those consisting of longer ones. We also highlight those distinctive spectroscopic fingerprints specific to local S/DIB structures containing only short or long sulfur chains. This distinction could serve to help distinguish between them experimentally during discharge. Our theoretically predicted results are in a good agreement with experimental Raman measurements on coin cells at different discharge stages. This work represents, for the first time, an attempt to compute Raman fingerprints of sulfur/carbon copolymer cathodes during battery operation including quantum‐chemical and finite‐temperature effects, and provides a guideline for Raman spectral changes of arbitrary electrodes during discharge.