Functional Differentiation of Three Pores for Effective Sulfur Confinement in Li–S Battery

Abstract Shuttle effect of the dissolved intermediates is regarded as the primary cause that leads to fast capacity degradation of Li–S battery. Herein, a microporous carbon‐coated sulfur composite with novel rambutan shape (R‐S@MPC) is synthesized from microporous carbon‐coated rambutan‐like zinc sulfide (R‐ZnS@MPC), via an in situ oxidation process. The R‐ZnS is employed as both template and sulfur precursor. The carbon frame of R‐S@MPC composite possesses three kinds of pores that are distinctly separated from each other in space and are endowed with the exclusive functions. The central macropore serves as buffer pool to accommodate the dissolved lithium polysulfides (LPSs) and volumetric variation during cycling. The marginal straight‐through mesoporous, connected with the central macropore, takes the responsibility of sulfur storage. The micropores, evenly distributed in the outer carbon shell of the as‐synthesized R‐S@MPC, enable the blockage of LPSs. These pores are expected to perform their respective single function, and collaborate synergistically to suppress the sulfur loss. Therefore, it delivers an outstanding cycling stability, decay rate of 0.013% cycle⁻¹ after 500 cycles at 1 C, when the sulfur loading is kept at 4 mg cm⁻².