Search

The chemical binding between metal compounds and polysulfides provides a good solution to inhibit shuttle effect in Li‐S batteries. However, the Sabatier principle predicts that overly strong adsorption will commonly hinder the conversion of polysulfides, so building the synergetic effect mechanism between "strong adsorption" and "fast conversion" for polysulfides is a significant strategy. To realize this goal, in this study, the defect‐enriched Co9S8 hollow prisms (DHCPs) as both S host and catalyst material for Li‐S batteries are designed. Based on in situ UV–vis spectroscopy results, it is found that DHCPs can profitably promote the generation of S3·−${\rm{S}}_3^{\cdot{\bm{ - }}}$ radicals during the discharge process. In the case of the relatively high conversion barrier of "liquid–liquid" reaction, the generated S3·−${\rm{S}}_3^{\cdot{\bm{ - }}}$ radicals are responsible for the fast conversion reaction via a unique reaction pathway. When the sulfur loading is 4.63 mg cm−2, the cell with DHCP/S cathode delivers a high areal capacity of 4.75 mAh cm−2 at 0.1 C and keeps a high capacity of 2.99 mAh cm−2 after 100 cycles at 0.5 C. This study provides a positive attempt to achieve "strong adsorption" and "fast conversion" of polysulfides simultaneously, which will convincingly boost the development and practical process of Li‐S batteries. [ABSTRACT FROM AUTHOR]

[Display omitted] • Polar and conductive titanium carbide is introduced for redox regulation. • Lithium sulfide plays as sulfur source in this study. • Sulfur redox and lithium sulfide precipitation are remarkably promoted. • The electrochemical characteristics of as-prepared batteries are boosted. The lithium-sulfur batteries (LSBs) have attracted more and more attention in recent years owing to its high theoretical energy density, abundant sulfur source and relatively low cost. However, the serious polysulfides shuttle and sluggish sulfur redox kinetics hinder the development and commercial application of high-performance lithium-sulfur batteries. In this paper, the titanium carbide (TiC)-decorated carbon matrix is considered as the mediator, anchor and electrocatalyst for polysulfides redox reaction. It has been proved that the conductive and polar titanium carbide can not only chemisorbs lithium polysulfides via titanium-sulfur (Ti-S) coordination, but also optimize the lithium sulfide (Li 2 S) nucleation/precipitation mechanism for better redox reaction. Especially, the graphene oxide and carbon nanotube matrix (GO-CNT) in this case can act as both host for Li 2 S loading and TiC precipitation. Accordingly, the as-fabricated lithium sulfide-graphene oxide–carbon nanotube-titanium carbide (LS-GO-CNT-TiC) cathode delivers the high initial discharge capacity of 956 mAh g−1 at 0.1C and good rate capability of 508 mAh g−1 at 2C. These results consequently manifest that the conductive and polar matrix of LS-GO-CNT-TiC can perform as a promising cathode of the high performance LSBs. [ABSTRACT FROM AUTHOR]

• Polypyrrole coating is utilized for polysulfides immobilization. • Lithium sulfide is wrapped inside cathode from exposure. • Activation barrier and polysulfides shuttle are greatly suppressed. • Electrochemical performances of as-prepared cells are promoted. The significantly-high theoretical energy density and eco-sustainability of lithium sulfur batteries (LSBs) arouses a rapid surge of interest in recent years. However, some key issues of cathode, for instance, the polysulfides confinement, low ion/electrons transfer and etc., hinder the practical utilization of LSBs. Herein, such issues could be carefully handled by using the conductive polypyrrole as polysulfides wrapper. The polypyrrole with pyrrole rings can efficiently confine polysulfides inside cathode for redox. Meanwhile, the conductive polypyrrole with delocalized π-electron cloud can facilitate electrons transfer. Besides, the addition of carbon nanotube (CNT) and oxidized graphene (GO) can enhance the conductivity of cathode material. As a result, the Li 2 S/CNT/GO/PPy cathode delivers a cycling capacity of 525 mAh g−1 with a low-capacity decay rate of 0.065 % cycle−1 after 400 cycles. Therefore, the lithium-sulfur battery with Li 2 S-based and PPy-wrapped cathode could reasonably be counted as a potential alternative of long-cycling Li-ion cells. [Display omitted] [ABSTRACT FROM AUTHOR]

The high theoretical energy density, high environmental adaptability and safety of lithium sulfide (Li 2 S)-oriented cathodes attract enough attention among lithium-sulfur batteries (LSBs). In this work, the lithium sulfide (Li 2 S)-oriented composite is fabricated via an in-situ carbothermic reduction method, in which lithium sulfate is reduced by CMK3 at an optimized temperature and subsequently the as-prepared Li 2 S is protected via the conformal carbon layer by carbonization of phenol-formaldehyde resin (PF). With the aid of the porous carbon structure of CMK3 and protection of PF-derived conformal carbon layer, the dispersity of Li 2 S and conductivity of cathode are availably enhanced. It has been found that the Li 2 S@CMK3-C prepared at optimum carbothermic reduction temperature of 835 °C has excellent electrochemical performance. The lithium-sulfur battery using Li 2 S@CMK3-C as cathode and metal Li as anode can deliver a high initial discharge capacity of 979 mAh g−1 at 0.1 C, the capacity retention after running at various current density is 94%, and the discharge specific capacity is still 530 mAh g−1 at 2 C after 450 cycles. Therefore, the preparation of CMK3-supported Li 2 S-based cathode material provides a new approach for the development and industrialization of new high-performance Li–S battery. Image 1 • An in-situ carbothermic reduction method is employed. • Lithium sulfide is in-situ formed inside cathode matrix as sulfur source. • The shuttle of polysulfides and activation energy barrier is suppressed. • The as-fabricated batteries deliver elevated electrochemical performance. [ABSTRACT FROM AUTHOR]

We present a separator modification strategy to suppress polysulfide shuttle and accelerate polysulfide conversion through transition metal coordinated g-C 3 N 4 with crystalline carbons. The Li-S batteries with Ni-C 3 N 4 /C-modified separator manifest improved electrochemical performance even at high sulfur loading and lean electrolyte condition, due to catalytic effect. • Transition metal coordinated g-C 3 N 4 with crystalline carbons is prepared. • Hybrid nanosheets efficiently prevent polysulfide diffusion by absorption effect. • This structure endows the lean-electrolyte Li-S batteries higher capacity. • Cell with Ni-C 3 N 4 /C-modified separator exhibits the best electrochemical performances. Lithium-sulfur batteries have been regarded as promising energy storage candidates because of their high energy density and low cost. However, the low electrical conductivity of sulfur, infamous polysulfides shuttle and slow redox kinetics result in fast capacity fade and poor rate capabilities. To solve these barriers, herein a modification strategy of functional separator is presented by coating transition metal coordinated graphitic carbon nitride (g-C 3 N 4) with crystalline carbons (M-C 3 N 4 /C) on the surface of a commercial separator. The coating layer exhibits both satisfactory interception ability for polysulfides shuttle and fast polysulfides conversion ability. It has been found that the uniformly distributed transition metal on g-C 3 N 4 /C acts as an active center to regulate polysulfides behavior via strong chemisorption capability and high catalytic activity towards polysulfide conversion, while the transition metal-interface guarantees the rapid electron transfer, which can consequently facilitate the utilization of active sulfur species. Notably, after considerable assessments from density functional theory calculations, spectroscopy and electrochemical performances, it can be concluded that the Ni-C 3 N 4 /C can strongly bind polysulfides and expedite polysulfides conversion kinetics as well as promote electrons/ion transfer. As a result, the lithium-sulfur batteries with Ni-C 3 N 4 /C-modified separator can deliver 999 mAh g−1 at 0.5 A g−1 with high capacity retention of 89.4% after 300 cycles. Even at a great sulfur loading of 4.6 mg cm−2 and a low electrolyte/sulfur ratio of 6 µL mg−1, a large initial capacity of 724.6 mAh g−1 is still obtained at 1.0 A g−1. The separator reported in this work initiates the exploration of transition metals coordination as dynamic regulators of high-performance lithium-sulfur batteries and also reveals an understanding of the catalytic reactions. [ABSTRACT FROM AUTHOR]