Insights into Cyclable Lithium Loss as a Key Factor in Accelerated Capacity Fade of Lithiated Silicon-Sulfur Full Cells.

To evade the hurdles of dendrite growth and low Coulombic efficiency resulting from lithium metal anodes, integrating lithiated silicon anodes with sulfur cathodes to configure a lithiated silicon-sulfur (Si-S) full cell is a promising strategy to develop high-energy and high-safety rechargeable lithium batteries. Nevertheless, Si-S full cells always suffer accelerated capacity decay, even when excellent electrochemical performance of Li-S and Li-Si half cells is achieved. Herein, we report a comprehensive investigation of the capacity fade mechanism of Si-S full cells. It is revealed that cyclable lithium loss plays a key role in the accelerated capacity fade of Si-S full cells. In addition, cyclable lithium loss in Si-S full cells is mainly divided into irreversible lithium loss by forming inactive lithium compounds due to polysulfide shuttling and other side reactions, and restricted lithium because the Si/C anode cannot be fully delithiated when the Si-S full cell reaches the discharge cutoff voltage. From the 1st cycle to the 100th cycle, the irreversible lithium loss is determined to have increased from 21.7 to 54.5%, whereas the restricted lithium decreased from 24.6 to 16.7%, respectively. The high specific surface area of a Si/C anode leads to a remarkable irreversible lithium loss due to serious polysulfide shuttling in Si-S full cells. This work will help advance the practical application of Li-S batteries.