A Versatile Metal‐Organic‐Framework Pillared Interlayer Design for High‐Capacity and Long‐Life Lithium‐Sulfur Batteries

Abstract Developing high‐performance lithium‐sulfur batteries is a promising way to attain higher energy density at a lower cost beyond the state‐of‐the‐art lithium‐ion battery technology. However, the major issues impeding their practical applications are the sluggish kinetics and the parasitic shuttling reactions of sulfur and polysulfides. Here, pillaring the multilayer graphene membrane with a metal–organic framework (MOF) demonstrates the substantial impact of a versatile interlayer design in tackling these issues. Unlike regular composite separators reported so far, the participation of tri‐metallic Ni−Co−Mn MOF as pillars supports the construction of an ion‐channel interconnected interlayer structure, unexpectedly balancing the interfacial concentration polarization, spatially confining the soluble polysulfides, and vastly affording the lithiophilic sites for highly efficient polysulfide sieving/conversion. As a demonstration, we show that the MOF‐pillared interlayer structure enables outstanding capacity (1634 mAh g −1 at 0.1 C) and longevity (average capacity decay of 0.034 % per cycle in 2000 cycles) for lithium‐sulfur batteries. Besides, the multilayer separator can be readily integrated into the high‐nickel cathode (LiNi 0.91 Mn 0.03 Co 0.06 O 2 )‐based lithium‐ion batteries, which efficiently suppresses the undesired phase evolution upon cycling. These findings suggest the potential of “gap‐filling” materials in fabricating multi‐functional separators, bringing forward the pillared interlayer structure for energy‐storage applications.