New Insight into the Working Mechanism of Lithium-Sulfur Batteries under a Wide Temperature Range

Sweet potato-derived carbon with a unique solid core/porous layer core/shell structure is used as a conductive substrate for gradually immobilizing sulfur to construct a cathode for Li-S batteries. The first discharge specific capacity of the Li-S batteries with the C-10K@2S composite cathode at 0.1C is around 1645 mAh g^-1, which is very close to the theoretical specific capacity of active sulfur. Especially, after 175 cycles at 0.5C, the maintained specific discharge capacities of the C-10K@2S cathode at -20, 0, 25, and 40 °C are about 184.9, 687.2, 795.5, and 758.3 mAh g^-1, respectively, and the cathode is superior to most of the classical carbon form matrices. Working mechanisms of the cathodes under different temperatures are confirmed based on X-ray photoelectron spectroscopy (XPS) and in situ X-ray diffraction (XRD) characterizations. Distinctively, during the discharge stage, the widely proposed two-step cathodic reactions occur simultaneously rather than sequentially. In addition, the largely accelerated phase conversion efficiency of the cathode at a higher temperature (from room temperature to 40 °C) contributes to its enhanced charge/discharge specific capacity, while the byproduct Li₂S₂O₇ or Li₃N irreversibly formed during the cycles limits its application performance at 0 °C. These conclusions would be very significant and useful for designing cathodes for Li-S batteries with excellent wide working temperature performance.