Degradation Mechanisms of a Li–S Cell using Commercial Activated Carbon

Abstract

In lithium–sulfur (Li–S) batteries, encapsulation of sulfur in activated carbon (AC) materials is a promising strategy for preventing the dissolution of lithium polysulfide into electrolytes and enhancing cycle life, because instead of solid–liquid– solid reactions, quasi-solid-state (QSS) reactions occur in the AC micropores. While a high weight fraction of sulfur in S/ AC composites is essential for achieving a high energy density of Li–S cells, the deterioration mechanisms under such conditions are still unclear. In this study, we report the deterioration mechanisms during charge–discharge cycling when the discharge products overflow from the AC. Analysis using scanning electron microscopy and energy-dispersive X-ray spectrometry confirms that the sulfur in the S/AC composites migrates outside the AC as cycling progresses, and it is barely present in the AC after 20 cycles, which corresponds to the capacity decay of the cell. Impedance analysis clearly shows that the electrical resistance of the S/AC composite and the charge-transfer resistance of QSS reactions significantly increase as a result of sulfur migration. On the other hand, the charge–discharge cycling performance under limited-capacity conditions, where the discharge products are encapsulated inside the AC, is extremely stable. These results reveal the degradation mechanism of a Li–S cell with micro-porous carbon and provide crucial insights into the design of a S/AC composite cathode and its operating conditions needed to achieve stable cycling performance.