Accelerated Multi-step Sulfur Redox Reactions in Lithium-Sulfur Batteries Enabled by Dual Defects in Metal-Organic Framework-based Catalysts.

The sluggish sulfur redox kinetics and shuttle effect of lithium polysulfides (LiPSs) are recognized as the main obstacles to the practical applications of the lithium-sulfur (Li-S) batteries. Accelerated conversion by catalysis can mitigate these issues, leading to enhanced Li-S performance. However, a catalyst with single active site cannot simultaneously accelerate multiple LiPSs conversion. Herein, we developed a novel dual-defect (missing linker and missing cluster defects) metal-organic framework (MOF) as a new type of catalyst to achieve synergistic catalysis for the multi-step conversion reaction of LiPSs. Electrochemical tests and first-principle density functional theory (DFT) calculations revealed that different defects can realize targeted acceleration of stepwise reaction kinetics for LiPSs. Specifically, the missing linker defects can selectively accelerate the conversion of S8 →Li2 S4 , while the missing cluster defects can catalyze the reaction of Li2 S4 →Li2 S, so as to effectively inhibit the shuttle effect. Hence, the Li-S battery with an electrolyte to sulfur (E/S) ratio of 8.9 mL g-1 delivers a capacity of 1087 mAh g-1 at 0.2 C after 100 cycles. Even at high sulfur loading of 12.9 mg cm-2 and E/S=3.9 mL g-1 , an areal capacity of 10.4 mAh cm-2 for 45 cycles can still be obtained.

Single Zinc Atom Aggregates: Synergetic Interaction to Boost Fast Polysulfide Conversion in Lithium-Sulfur Batteries.

Single-atom catalysts (SACs) pave new possibilities to improve the utilization efficiency of sulfur electrodes arising from polysulfide shuttle effects and sluggish kinetics due to their excellent applicability in atomic-scale reaction mechanisms and structure-activity relationships. Herein, nitrogen (N)-anchored SACs on the highly ordered N-doped carbon nanotube arrays are reported as the sulfur host for fast redox conversion in lithium-sulfur (Li-S) batteries. The cube structure of the aligned carbon nanotubes can promote the rapid mass transfer under high sulfur loadings, and abundant single-atom active sites further accelerate the conversion of lithium polysulfides (LiPSs). The synergistic enhancement effect induced by adjacent single atoms with interatomic distances <1 nm further accelerates the rapid multi-step reaction of sulfur at high sulfur loadings. As a result, the obtained Li-S batteries exhibit outstanding cycle stability with a high areal capacity of 5.6 mAh cm-2 after 100 cycles under a high sulfur loading of 7.2 mg cm-2 (electrolyte to sulfur ratio is ≈3.7 mL g-1 ). Even assembled into a pouch cell, it still delivers a high capacity of 953.4 mAh g-1 after 100 cycles at 0.1 C, contributing to the development of the practically viable Li-S batteries.

Interspersing Partially Oxidized V2C Nanosheets and Carbon Nanotubes toward Multifunctional Polysulfide Barriers for High-Performance Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries have attracted much attention attributed to their high theoretical energy density, whereas the parasitic shuttling behavior of lithium polysulfides (LiPS) hinders this technology from yielding practically competitive performance. Targeting this critical challenge, we develop an advanced polysulfide barrier by modifying the conventional separator with CNTs-interspersed V2C/V2O5 nanosheets to alleviate the shuttle effect. The partial oxidization of V2C MXene constructs the V2C/V2O5 composite with V2O5 nanoparticles uniformly dispersed on few-layered V2C nanosheets, which synergistically and concurrently improves the sulfur confinement and redox reaction kinetics. Moreover, the interstacking between the 1D CNTs and the 2D V2C/V2O5 not only prevents the agglomeration of nanosheets for efficient exposure of active interfaces but also constructs a robust conductive network for fast charge and mass transfers. The Li-S cells with V2C/V2O5/CNTs-modified separator realize a high initial capacity (1240.4 mAh g-1 at 0.2 C), decent capacity retention (82.6% over 500 cycles), and favorable areal capacity (5.9 mAh cm-2) at a raised sulfur loading (6.0 mg cm-2). This work affords a unique multifunctional separator design toward durable and efficient sulfur electrochemistry, holding great promise for improving the electrochemical properties of Li-S batteries.