Understanding the role of different conductive polymers in improving the nanostructured sulfur cathode performance.

Lithium sulfur batteries have brought significant advancement to the current state-of-art battery technologies because of their high theoretical specific energy, but their wide-scale implementation has been impeded by a series of challenges, especially the dissolution of intermediate polysulfides species into the electrolyte. Conductive polymers in combination with nanostructured sulfur have attracted great interest as promising matrices for the confinement of lithium polysulfides. However, the roles of different conductive polymers on the electrochemical performances of sulfur electrode remain elusive and poorly understood due to the vastly different structural configurations of conductive polymer-sulfur composites employed in previous studies. In this work, we systematically investigate the influence of different conductive polymers on the sulfur cathode based on conductive polymer-coated hollow sulfur nanospheres with high uniformity. Three of the most well-known conductive polymers, polyaniline (PANI), polypyrrole (PPY), and poly(3,4-ethylenedioxythiophene) (PEDOT), were coated, respectively, onto monodisperse hollow sulfur nanopsheres through a facile, versatile, and scalable polymerization process. The sulfur cathodes made from these well-defined sulfur nanoparticles act as ideal platforms to study and compare how coating thickness, chemical bonding, and the conductivity of the polymers affected the sulfur cathode performances from both experimental observations and theoretical simulations. We found that the capability of these three polymers in improving long-term cycling stability and high-rate performance of the sulfur cathode decreased in the order of PEDOT > PPY > PANI. High specific capacities and excellent cycle life were demonstrated for sulfur cathodes made from these conductive polymer-coated hollow sulfur nanospheres.