Bo, RenhengTaheri, MahdiarDi Bernardo, IolandaMotta, N.Chen, HongjunTsuzuki, TakuyaYu, GuihuaTricoli, Antonio2021-06-221530-6984http://hdl.handle.net/1885/237892The lithium−sulfur (Li−S) system is a promising material for the nextgeneration of high energy density batteries with application extending from electrical vehicles to portable devices and aeronautics. Despite progress, the energy density of current Li−S technologies is still below that of conventional intercalation-type cathode materials due to limited stability and utilization efficiency at high sulfur loading. Here, we present a conducting polymer hydrogel integrated highly performing free-standing three-dimensional (3D) monolithic electrode architecture for Li−S batteries with superior electrochemical stability and energy density. The electrode layout consists of a highly conductive three-dimensional network of N,P codoped carbon with welldispersed metal−organic framework nanodomains of ZIF-67 and HKUST-1. The hierarchical monolithic 3D carbon networks provide an excellent environment for charge and electrolyte transport as well as mechanical and chemical stability. The electrically integrated MOF nanodomains significantly enhance the sulfur loading and retention capabilities by inhibiting the release of lithium polysulfide specificities as well as improving the charge transfer efficiency at the electrolyte interface. Our optimal 3D carbon-HKUST-1 electrode architecture achieves a very high areal capacity of >16 mAh cm−2 and volumetric capacity (CV) of 1230.8 mAh cm−3 with capacity retention of 82% at 0.2C for over 300 cycles, providing an attractive candidate material for future high-energy density Li−S batteries.Prof. Antonio Tricoli acknowledges the support of Australian Research Council DP150101939, Australian Research Council DE160100569, and Westpac 2016 Research Fellowship.© 2019 American Chemical SocietyLi−S batterieshigh loadingthree-dimensional electrodesconducting polymer hydrogelmetal−organic frameworks2019-06-2510.1021/acs.nanolett.9b01033