Rare Earth Single‐Atom Catalysis for High‐Performance Li−S Full Battery with Ultrahigh Capacity.

Lithium‐sulfur (Li−S) batteries have many advantages but still face problems such as retarded polysulfides redox kinetics and Li dendrite growth. Most reported single atom catalysts (SACs) for Li−S batteries are based on <italic>d</italic>‐band transition metals whose <italic>d</italic> orbital constitutes active valence band, which is inclined to occur catalyst passivation. SACs based on 4<italic>f</italic> inner valence orbital of rare earth metals are challenging for their great difficulty to be activated. In this work, we design and synthesize the first rare earth metal Sm SACs which has electron‐rich 4<italic>f</italic> inner orbital to promote catalytic conversion of polysulfides and uniform deposition of Li. Sm SACs enhance the catalysis by the activated 4<italic>f</italic> orbital through an <italic>f‐d‐p</italic> orbital hybridization. Using Sm‐N3C3 modified separators, the half cells deliver a high capacity over 600 mAh g−1 and a retention rate of 84.3 % after 2000 cycles. The fabricated Sm‐N3C3‐Li|Sm‐N3C3@PP|S/CNTs full batteries can provide an ultra‐stable cycling performance of a retention rate of 80.6 % at 0.2 C after 100 cycles, one of the best full Li−S batteries. This work provides a new perspective for the development of rare earth metal single atom catalysis in electrochemical reactions of Li−S batteries and other electrochemical systems for next‐generation energy storage. [ABSTRACT FROM AUTHOR]