Abstract

Among the most challenging issues in electrochemical energy storage is developing insightful in situ probes of redox processes for a working cell. This is particularly true for cells that operate on the basis of chemical transformations such as Li–S and Li–O2, where the factors that govern capacity and cycling stability are difficult to access owing to the amorphous nature of the intermediate species. Here, we investigate cathodes for the Li–S cell comprised of sulfur-imbibed robust spherical carbon shells with tailored porosity that exhibit excellent cycling stability. Their highly regular nanoscale dimensions and thin carbon shells allow highly uniform electrochemical response and further enable direct monitoring of sulfur speciation within the cell over the entire redox range by operando X-ray absorption spectroscopy on the S K-edge. The results reveal the first detailed evidence of the mechanisms of sulfur redox chemistry on cycling, showing how sulfur fraction (under-utilization) and sulfide precipitation impact capacity. Such information is critical for promoting improvements in Li–S batteries.