Unexpected Effect of Electrode Architecture on High-Performance Lithium–Sulfur Batteries

In the past years, considerable efforts have been devoted to the deliberate synthesis of nanosulfur in various hosts with sophisticated structures to improve the performance of lithium–sulfur batteries (LSBs) and reveal the structure–property relationship. It is taken for granted that these elaborate sulfur nanostructures are well maintained in the ultimate electrode after the traditional mixing and coating method. Herein, we, for the first time, reveal the unexpected sulfur structure deterioration in nanosulfur/graphene composites during the electrode preparation using the traditional method because of the long-term neglected dissolution–recrystallization effect of sulfur in solvents. Consequently, compared with binder-free three-dimensional graphene/sulfur electrodes, the milled graphene/sulfur electrodes exhibit much worse electrochemical performance. On the basis of this, we further propose a facile and universal graphene oxide-assisted assembly method to avoid the dissolution–recrystallization of sulfur, by which binder-free three-dimensional ethylenediamine-functionalized graphene/sulfur (3DEFGS) electrodes have been successfully prepared. The 3DEFGS electrodes with a high areal sulfur loading of ∼6 mg cm–2 exhibit an ultrahigh initial capacity of 1394 mA h g–1 at 0.1 C, an excellent rate performance with a capacity of 796 mA h g–1 at 4 C, and superior long-term cycling stability (885 mA h g–1 after 500 cycles at 1 C), which are among the best performances achieved by all reported LSB cathodes with high areal sulfur loadings.