Synthesis of a Macroporous Conjugated Polymer Framework: Iron Doping for Highly Stable, Highly Efficient Lithium–Sulfur Batteries

Porous conjugated polymers offer enormous potential for energy storage because of the combined features of pores and extended π-conjugated structures. However, the drawbacks such as low pore volumes and insolubilities of micro- and mesoporous conjugated polymers restrict the loading of electroactive materials and thus energy storage performance. Herein, we report the synthesis of iron-doped macroporous conjugated polymers for hosting sulfur as the cathode of high-performance lithium–sulfur (Li–S) batteries. The macroporous conjugated polymers are synthesized via in situ growth of poly(3-hexylthiophene) (P3HT) from reduced graphene oxide (RGO) sheets, followed by gelation of the composite (RGO-g-P3HT) in p-xylene and freeze-drying. The network structures of the macroporous materials can be readily tuned by controlling the chain length of P3HT grafted to RGO sheets. The large pore volumes of the macroporous RGO-g-P3HT materials (ca. 34 cm3 g–1) make them excellent frameworks for hosting sulfur as cathodes of Li–S batteries. Furthermore, incorporation of Fe into the macroporous RGO-g-P3HT cathode results in reduced polarization, enhanced specific capacity (1,288, 1,103, and 907 mA h g–1 at 0.05, 0.1, and 0.2 C, respectively), and improved cycling stability (765 mA h g–1 after 100 cycles at 0.2 C). Density functional theory calculations and in situ characterizations suggest that incorporation of Fe enhances the interactions between lithium polysulfides and the P3HT framework.