In situ sulfur-doped graphene nanofiber network as efficient metal-free electrocatalyst for polysulfides redox reactions in lithium–sulfur batteries

The major challenge for realistic application of Li-S batteries lies in the great difficulty in breaking through the obstacles of the sluggish kinetics and polysulfides shuttle of the sulfur cathode at high sulfur loading for continuously high sulfur utilization during prolonged charge-discharge cycles.Here we demonstrate that large percentage of sulfur can be effectively incorporated within a three-dimensional(3D)nanofiber network of high quality graphene from chemical vapor deposition(CVD),through a simple ball-milling process.While high quality graphene network provided continuous and durable channels to enable efficient transport of lithium ions and electrons,the in-situ sulfur doping from the alloying effect of ball milling facilitated desirable affinity with entire sulfur species to prevent sulfur loss and highly active sites to propel sulfur redox reactions over cycling.This resulted in remarkable rate-performance and excellent cycling stability,together with large areal capacity at very high sulfur mass loading(Specific capacity over 666 mAh g-1after 300 cycles at 0.5 C,and areal capacity above 5.2 mAh cm-2at 0.2C at sulfur loading of 8.0 mg cm-2 and electrolyte/sulfur(E/S)ratio of 8μL mg-1;and high reversible areal capacities of 13.1 m Ah cm-2 at a sulfur load of 15 mg cm-2 and E/S of 5μL mg-1).

Confining sulfur in intact freestanding scaffold of yolk-shell nanofibers with high sulfur content for lithium-sulfur batteries

Nanostructure design holds great potential in fabricating sulfur electrodes that host a high sulfur loading and still attain high electrochemical utilization for the developing of high-energy-density lithium-sulfur(Li-S) batteries. In this contribution, we introduce the yolk-shell structure into a freestanding carbon nanofibers film and construct a complete hollow yolk-shell Ti O2/carbon nanofibers@void@TiN@carbon(TiO2-CNFs@void@Ti N@C) composite. With inherent double conductive network and strong adsorption capability for polysulfides, the Ti O2-CNFs@void@Ti N@C composite can not only provide sufficient electrical contact for the insulating sulfur, but also effectively entrap polysulfides for prolonged cycle life. As a result, an excellent capacity retention ratio of 60.9% after 1000 cycles at 1 C as well as a high capacity of688.5 mA h g^(-1) at 5 C rate is accomplished with the cells employing Ti O2-CNFs@void@TiN @C as a cathode substrate for sulfur. Moreover, the TiO2-CNFs@void@Ti N@C composite, with a high S mass loading of9.5 mg cm^(-2), delivers a superb areal capacity of 8.2 mAh cm^(-2).