A Covalent Organic Framework with Extended π‑Conjugated Building Units as a Highly Efficient Recipient for Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries have recently become a research hotspot because of their tempting theoretical capacity and energy density. Nevertheless, the notorious shuttle of polysulfides hinders the advancement of Li–S batteries. Herein, a two-dimensional covalent organic framework (COF) with extended π-conjugated units has been designed, synthesized, and used as sulfur recipients with 88.4 wt % in loading. The COF offers an elaborate platform for sufficient Li–S redox reactions with almost theoretical capacity release (1617 mA h g^–1 at 0.1 C), satisfactory rate capability, and intensively traps polysulfides for a decent Coulombic efficiency (ca. 98.0%) and extremely low capacity decay (0.077% per cycle after 528 cycles at 0.5 C). The structural factors of the COF on the high-performance batteries are revealed by density functional theory calculations to be the high degrees of conjugation and proper interlayer space. This work not only demonstrates the great potential of COFs as highly efficient sulfur recipients but also provides a viable guidance for further design of COF materials to tackle shuttling issues toward active materials in electrochemical energy storage.