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, 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, 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 LiSO or LiN 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.