Metal‐sulfur batteries (MSBs) are considered up‐and‐coming future‐generation energy storage systems because of their prominent theoretical energy density. However, the practical applications of MSBs are still hampered by several critical challenges, i.e., the shuttle effects, sluggish redox kinetics, and low conductivity of sulfur species. Recently, benefiting from the high surface area, regulated networks, molecular/atomic‐level reactive sites, the metal‐organic frameworks (MOFs)‐derived nanostructures have emerged as efficient and durable multifaceted electrodes in MSBs. Herein, a timely review is presented on recent advancements in designing MOF‐derived electrodes, including fabricating strategies, composition management, topography control, and electrochemical performance assessment. Particularly, the inherent charge transfer, intrinsic polysulfide immobilization, and catalytic conversion on designing and engineering of MOF nanostructures for efficient MSBs are systematically discussed. In the end, the essence of how MOFs’ nanostructures influence their electrochemical properties in MSBs and conclude the future tendencies regarding the construction of MOF‐derived electrodes in MSBs is exposed. It is believed that this progress review will provide significant experimental/theoretical guidance in designing and understanding the MOF‐derived nanostructures as multifaceted electrodes, thus offering promising orientations for the future development of fast‐kinetic and robust MSBs in broad energy fields.

Benefiting from the merits of low cost, ultrahigh‐energy densities, and environmentally friendliness, metal–sulfur batteries (M–S batteries) have drawn massive attention recently. However, their practical utilization is impeded by the shuttle effect and slow redox process of polysulfide. To solve these problems, enormous creative approaches have been employed to engineer new electrocatalytic materials to relieve the shuttle effect and promote the catalytic kinetics of polysulfides. In this review, recent advances on designing principles and active centers for polysulfide catalytic materials are systematically summarized. At first, the currently reported chemistries and mechanisms for the catalytic conversion of polysulfides are presented in detail. Subsequently, the rational design of polysulfide catalytic materials from catalytic polymers and frameworks to active sites loaded carbons for polysulfide catalysis to accelerate the reaction kinetics is comprehensively discussed. Current breakthroughs are highlighted and directions to guide future primary challenges, perspectives, and innovations are identified. Computational methods serve an ever‐increasing part in pushing forward the active center design. In summary, a cutting‐edge understanding to engineer different polysulfide catalysts is provided, and both experimental and theoretical guidance for optimizing future M–S batteries and many related battery systems are offered.

Accelerating insoluble Li2S2−Li2S reduction catalysis to mitigate the shuttle effect has emerged as an innovative paradigm for high‐efficient lithium‐sulfur battery cathodes, such as single‐atom catalysts by offering high‐density active sites to realize in situ reaction with solid Li2S2. However, the profound origin of diverse single‐atom species on solid‐solid sulfur reduction catalysis and modulation principles remains ambiguous. Here we disclose the fundamental origin of Li2S2−Li2S reduction catalysis in ferromagnetic elements‐based single‐atom materials to be from their spin density and magnetic moments. The experimental and theoretical studies disclose that the Fe−N4‐based cathodes exhibit the fastest deposition kinetics of Li2S (226 mAh g−1) and the lowest thermodynamic energy barriers (0.56 eV). We believe that the accelerated Li2S2−Li2S reduction catalysis enabled via spin polarization of ferromagnetic atoms provides practical opportunities towards long‐life batteries.

Li−S batteries are considered to be the most promising nextgeneration advanced energy-storage systems. However, the sluggish reaction kinetics and the "shuttle effect" of lithium polysulfides (LiPSs) severely limit their battery performances. To overcome the complex and multiphase sulfur redox chemistry of LiPSs, in this study, we propose a new type of cobalt-based double catalytic sites (DCSs) codoped mesoporous carbon to immobilize and reversibly catalyze the LiPS intermediates in the cycling process, thus eliminating the shuttle effect and improving the charge−discharge kinetics. The theoretical calculation shows that the well-designed DCS configuration endows LiPSs with both strong and weak binding capabilities, which will facilitate the synergistic and reversible catalytic conversion. Furthermore, the experimental results also confirm that the DCS structure shows significantly enhanced catalytic kinetics than the single catalytic sites. The Li−S battery equipped with the DCS structure displays an extremely high discharge capacity of 918 mA h g −1 at a current density of 0.2 C and can reach a capacity of 867 mA h g −1 after 200 cycles with an ultralow capacity attenuation rate of 0.028% for each cycle. This study opens new avenues to address the catalytic requirements both in discharging and charging processes.

Multiphase sulfur redox reactions with advanced homogeneous and heterogeneous electrochemical processes in lithium–sulfur (Li–S) batteries possess sluggish kinetics. The slow kinetics leads to significant capacity decay during charge/discharge processes. Therefore, electrocatalysts with adequate sulfur‐redox properties are required to accelerate reversible polysulfide conversion in cathodes. In this study, we have fabricated an oxygen‐modulated metal nitride cluster (C‐MoNx‐O) that has a moderate binding ability to the insoluble Li2Sx for reversible polysulfide electrocatalysis. A Li–S battery equipped with C‐MoNx‐O electrocatalyst displayed a high discharge capacity of 875 mAh g−1 at 0.5 C. The capacity decay rate of each cycle was only 0.10% after 280 cycles, which is much lower than the control groups (C‐MoOx: 0.16%; C‐MoNx: 0.21%). Kinetic studies and theoretical calculations suggest that C‐MoNx‐O electrocatalyst presents a moderate binding ability to the insoluble Li2S2 and Li2S when compared to the C‐MoOx and C‐MoNx surfaces. Thus, the C‐MoNx‐O can effectively immobilize and reversibly catalyze the solid–solid conversion of Li2S2–Li2S during charge–discharge cycling, thus promoting reaction kinetics and eliminating the shuttle effect. This study to design oxygen‐doped metal nitrides provides innovative structures and reversible solid–solid conversions to overcome the sluggish redox chemistry of polysulfides.