In Situ Formation of Copper‐Based Hosts Embedded within 3D N‐Doped Hierarchically Porous Carbon Networks for Ultralong Cycle Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries are promising energy storage systems due to their large theoretical energy density of 2600 Wh kg−1 and cost effectiveness. However, the severe shuttle effect of soluble lithium polysulfide intermediates (LiPSs) and sluggish redox kinetics during the cycling process cause low sulfur utilization, rapid capacity fading, and a low coulombic efficiency. Here, a 3D copper, nitrogen co‐doped hierarchically porous graphitic carbon network developed through a freeze‐drying method (denoted as 3D Cu@NC‐F) is prepared, and it possesses strong chemical absorption and electrocatalytic conversion activity for LiPSs as highly efficient sulfur host materials in Li–S batteries. The porous carbon network consisting of 2D cross‐linked ultrathin carbon nanosheets provides void space to accommodate volumetric expansion upon lithiation, while the Cu, N‐doping effect plays a critical role for the confinement of polysulfides through chemical bonding. In addition, after sulfuration of Cu@NC‐F network, the in situ grown copper sulfide (CuxS) embedded within CuxS@NC/S‐F composite catalyzes LiPSs conversion during reversible cycling, resulting in low polarization and fast redox reaction kinetics. At a current density of 0.1 C, the CuxS@NC/S‐F composites' electrode exhibits an initial capacity of 1432 mAh g−1 and maintains 1169 mAh g−1 after 120 cycles, with a coulombic efficiency of nearly 100%. An in situ grown copper sulfide (CuxS) embedded within a 3D CuxS@NC/S‐F composite not only dynamically promotes the electrochemical reaction kinetics of LiPSs and reduces the polarization inside Li‐S batteries, but also contributes to the capacity by the electrochemical reaction. The elaborate structure design and rational heteroatomic doping play crucial roles in achieving high capacity and long‐term cycling in Li–S batteries.