Differences in Electrochemistry between Fibrous SPAN and Fibrous S/C Cathodes Relevant to Cycle Stability and Capacity

Two different Li/S cathodes are compared in terms of capacity (mA . h . g sulfur −1 ) and intermediates during discharge and charge. One cathode material is based on fibrous SPAN, a sulfur-containing material obtained via the thermal conversion of poly(acrylonitrile), PAN, in the presence of sulfur. In this material, sulfur is covalently bound to the polymeric backbone. The second cathode material is based on porous activated carbon fibers (ACFs) with elemental sulfur embedded inside the ACFs' micropores. Cyclic voltammetry clearly indicates different discharge and charge chemistry of the two materials. While S-containing ACFs show the expected redox-chemistry of sulfur, SPAN does not form long-chain polysulfides during discharge; instead, sulfide is chopped off the polymer-bound sulfur chains to directly form Li 2 S. The high reversibility of this process accounts for both the high cycle stability and capacity of SPAN-based cathode materials.