Correlating Polysulfide Solvation Structure with Electrode Kinetics towards Long-Cycling Lithium–Sulfur Batteries

Lithium–sulfur (Li−S) batteries are promising due to ultrahigh theoretical energy density. However, their cycling lifespan is crucially affected by the electrode kinetics of lithium polysulfides. Herein, the polysulfide solvation structure is correlated with polysulfide electrode kinetics towards long-cycling Li−S batteries. The solvation structure derived from strong solvating power electrolyte induces fast anode kinetics and rapid anode failure, while that derived from weak solvating power electrolyte causes sluggish cathode kinetics and rapid capacity loss. By contrast, the solvation structure derived from medium solvating power electrolyte balances cathode and anode kinetics and improves the cycling performance of Li−S batteries. Li−S coin cells with ultra-thin Li anodes and high-S-loading cathodes deliver 146 cycles and a 338 Wh kg⁻¹ pouch cell undergoes stable 30 cycles. This work clarifies the relationship between polysulfide solvation structure and electrode kinetics and inspires rational electrolyte design for long-cycling Li−S batteries.     

Pomegranate‐Structured Silica/Sulfur Composite Cathodes for High‐Performance Lithium–Sulfur Batteries

Porous materials have many structural advantages for energy storage and conversion devices such as rechargeable batteries, supercapacitors, and fuel cells. When applied as a host material in lithium‐sulfur batteries, porous silica materials with a pomegranate‐like architecture can not only act as a buffer matrix for accommodating a large volume change of sulfur, but also suppress the polysulfide shuttle effect. The porous silica/sulfur composite cathodes exhibit excellent electrochemical performances including a high specific capacity of 1450 mA h g^?1, a reversible capacity of 82.9 % after 100 cycles at a rate of C/2 (1 C=1672 mA g^?1) and an extended cyclability over 300 cycles at 1 C‐rate. Furthermore, the high polysulfide adsorption property of porous silica has been proven by ex‐situ analyses, showing a relationship between the surface area of silica and polysulfide adsorption ability. In particular, the modified porous silica/sulfur composite cathode, which is treated by a deep‐lithiation process in the first discharge step, exhibits a highly reversible capacity of 94.5 % at 1C‐rate after 300 cycles owing to a formation of lithiated‐silica frames and stable solid‐electrolyte‐interphase layers.     

Beyond the Polysulfide Shuttle and Lithium Dendrite Formation: Addressing the Sluggish Sulfur Redox Kinetics for Practical High‐Energy Li‐S Batteries

Electrolyte modulation simultaneously suppresses polysulfide the shuttle effect and lithium dendrite formation of lithium–sulfur (Li‐S) batteries. However, the sluggish S redox kinetics, especially under high S loading and lean electrolyte operation, has been ignored, which dramatically limits the cycle life and energy density of practical Li‐S pouch cells. Herein, we demonstrate that a rational combination of selenium doping, core–shell hollow host structure, and fluorinated ether electrolytes enables ultrastable Li stripping/plating and essentially no polysulfide shuttle as well as fast redox kinetics. Thus, high areal capacity (>4 mAh cm^?2) with excellent cycle stability and Coulombic efficiency were both demonstrated in Li metal anode and thick S cathode (4.5 mg cm^?2) with a low electrolyte/sulfur ratio (10 μL mg^?1). This research further demonstrates a durable Li‐Se/S pouch cell with high specific capacity, validating the potential practical applications.     

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→Li₂S₄, while the missing cluster defects can catalyze the reaction of Li₂S₄→Li₂S, 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.     

Ferrocene‐Promoted Long‐Cycle Lithium–Sulfur Batteries

Confining lithium polysulfide intermediates is one of the most effective ways to alleviate the capacity fade of sulfur‐cathode materials in lithium–sulfur (Li–S) batteries. To develop long‐cycle Li–S batteries, there is an urgent need for material structures with effective polysulfide binding capability and well‐defined surface sites; thereby improving cycling stability and allowing study of molecular‐level interactions. This challenge was addressed by introducing an organometallic molecular compound, ferrocene, as a new polysulfide‐confining agent. With ferrocene molecules covalently anchored on graphene oxide, sulfur electrode materials with capacity decay as low as 0.014 % per cycle were realized, among the best of cycling stabilities reported to date. With combined spectroscopic studies and theoretical calculations, it was determined that effective polysulfide binding originates from favorable cation–π interactions between Li⁺ of lithium polysulfides and the negatively charged cyclopentadienyl ligands of ferrocene.     

Fast,Reversible Lithium Storage with a Sulfur/Long‐Chain‐Polysulfide Redox Couple

The cathodic reactions in Li–S batteries can be divided into two steps. Firstly, elemental sulfur is transformed into long‐chain polysulfides (S₈?Li₂S₄), which are highly soluble in the electrolyte. Next, long‐chain polysulfides undergo nucleation reaction and convert into solid‐state Li₂S₂ and Li₂S (Li₂S₄?Li₂S) by slow processes. As a result, the second‐step of the electrochemical reaction hinders the high‐rate application of Li–S batteries. In this report, the kinetics of the sulfur/long‐chain‐polysulfide redox couple (theoretical capacity=419 mA h g^?1) are experimentally demonstrated to be very fast in the Li–S system. A Li–S cell with a blended carbon interlayer retains excellent cycle stability and possesses a high percentage of active material utilization over 250 cycles at high C rates. The meso‐/micropores in the interlayer are responsible for accommodating the shuttling polysulfides and offering sufficient electrolyte accessibility. Therefore, utilizing the sulfur/long‐chain polysulfide redox couple with an efficient interlayer configuration in Li–S batteries may be a promising choice for high‐power applications.     

Beyond the Polysulfide Shuttle and Lithium Dendrite Formation: Addressing the Sluggish Sulfur Redox Kinetics for Practical High-Energy Li-S Batteries

Electrolyte modulation simultaneously suppresses polysulfide the shuttle effect and lithium dendrite formation of lithium–sulfur (Li-S) batteries. However, the sluggish S redox kinetics, especially under high S loading and lean electrolyte operation, has been ignored, which dramatically limits the cycle life and energy density of practical Li-S pouch cells. Herein, we demonstrate that a rational combination of selenium doping, core–shell hollow host structure, and fluorinated ether electrolytes enables ultrastable Li stripping/plating and essentially no polysulfide shuttle as well as fast redox kinetics. Thus, high areal capacity (>4 mAh cm⁻²) with excellent cycle stability and Coulombic efficiency were both demonstrated in Li metal anode and thick S cathode (4.5 mg cm⁻²) with a low electrolyte/sulfur ratio (10 μL mg⁻¹). This research further demonstrates a durable Li-Se/S pouch cell with high specific capacity, validating the potential practical applications.     

Engineering Functional Interface with Built-in Catalytic and Self-Oxidation Sites for Highly Stable Lithium–Sulfur Batteries

Lithium−sulfur (Li−S) batteries have attracted great attention due to their high theoretical energy density. The rapid redox conversion of lithium polysulfides (LiPS) is effective for solving the serious shuttle effect and improving the utilization of active materials. The functional design of the separator interface with fast charge transfer and active catalytic sites is desirable for accelerating the conversion of intermediates. Herein, a graphene-wrapped MnCO₃ nanowire (G@MC) was prepared and utilized to engineer the separator interface. G@MC with active Mn²⁺ sites can effectively anchor the LiPS by forming the Mn−S chemical bond according to our theoretical calculation results. In addition, the catalytic Mn²⁺ sites and conductive graphene layer of G@MC could accelerate the reversible conversion of LiPS via the spontaneous “self-redox” reaction and the rapid electron transfer in electrochemical process. As a result, the G@MC-based battery exhibits only 0.038 % capacity decay (per cycle) after 1000 cycles at 2.0 C. This work affords new insights for designing the integrated functional interface for stable Li−S batteries.     

Boosting the “Solid–Liquid–Solid” Conversion Reaction via Bifunctional Carbonate-Based Electrolyte for Ultra-long-life Potassium–Sulfur Batteries

Potassium–sulfur (K−S) batteries have attracted wide attention owing to their high theoretical energy density and low cost. However, the intractable shuttle effect of K polysulfides results in poor cyclability of K−S batteries, which severely limits their practical application. Herein, a bifunctional concentrated electrolyte (3 mol L⁻¹ potassium bis(trifluoromethanesulfonyl)imide in ethylene carbonate (EC)) with high ionic conductivity and low viscosity is developed to regulate the dissolution behavior of polysulfides and induce uniform K deposition. The organic groups in the cathode electrolyte interphase layer derived from EC can effectively block the polysulfide shuttle and realize a “solid–liquid–solid” reaction mechanism. The KF-riched solid-electrolyte interphase inhibits K dendrite growth during cycling. As a result, the achieved K−S batteries display a high reversible capacity of 654 mAh g⁻¹ at 0.5 A g⁻¹ after 800 cycles and a long lifespan over 2000 cycles at 1 A g⁻¹.     

Sulfur Cathodes Based on Conductive MXene Nanosheets for High‐Performance Lithium–Sulfur Batteries

Lithium–sulfur batteries are amongst the most promising candidates to satisfy emerging energy‐storage demands. Suppression of the polysulfide shuttle while maintaining high sulfur content is the main challenge that faces their practical development. Here, we report that 2D early‐transition‐metal carbide conductive MXene phases—reported to be impressive supercapacitor materials—also perform as excellent sulfur battery hosts owing to their inherently high underlying metallic conductivity and self‐functionalized surfaces. We show that 70 wt % S/Ti₂C composites exhibit stable long‐term cycling performance because of strong interaction of the polysulfide species with the surface Ti atoms, demonstrated by X‐ray photoelectron spectroscopy studies. The cathodes show excellent cycling performance with specific capacity close to 1200 mA h g^?1 at a five‐hour charge/discharge (C/5) current rate. Capacity retention of 80 % is achieved over 400 cycles at a two‐hour charge/discharge (C/2) current rate.     

A Supramolecular Capsule for Reversible Polysulfide Storage/Delivery in Lithium‐Sulfur Batteries

Supramolecular materials, in which small organic molecules are assembled into regular structures by non‐covalent interactions, attract tremendous interests because of their highly tunable functional groups and porous structure. Supramolecular adsorbents are expected to fully expose their abundant adsorptive sites in a dynamic framework. In this contribution, we introduced cucurbit[6]uril as a supramolecular capsule for reversible storage/delivery of mobile polysulfides in lithium‐sulfur (Li‐S) batteries to control undesirable polysulfide shuttle. The Li‐S battery equipped with the supramolecular capsules retains a high Coulombic efficiency and shows a large increase in capacity from 300 to 900 mAh g⁻¹ at a sulfur loading of 4.2 mg cm⁻². The implementation of supramolecular capsules offers insights into intricate multi‐electron‐conversion reactions and manifests as an effective and efficient strategy to enhance Li‐S batteries and analogous applications that involve complex transport phenomena and intermediate manipulation.     

Unique Octupolar 2D-Polymer Frameworks as Mixed Conductors and Metal-Free Catalysts for Dual-Promoted Li and S Electrochemistry: Multi-regulation Role of Ethoxylation Chemistry

Here, we for the first time introduce ethoxylation chemistry to develop a new octupolar cyano-vinylene-linked 2D polymer framework (Cyano-OCF-EO) capable of acting as efficient mixed electron/ion conductors and metal-free sulfur evolution catalysts for dual-promoted Li and S electrochemistry. Our strategy creates a unique interconnected network of strongly-coupled donor 3-(acceptor-core) octupoles in Cyano-OCF-EO, affording enhanced intramolecular charge transfer, substantial active sites and crowded open channels. This enables Cyano-OCF-EO as a new versatile separator modifier, which endows the modified separator with superior catalytic activity for sulfur conversion and rapid Li ion conduction with the high Li⁺ transference number up to 0.94. Thus, the incorporation of Cyano-OCF-EO can concurrently regulate sulfur redox reactions and Li-ion flux in Li−S cells, attaining boosted bidirectional redox kinetics, inhibited polysulfide shuttle and dendrite-free Li anodes. The Cyano-OCF-EO-involved Li−S cell is endowed with excellent overall electrochemical performance especially large areal capacity of 7.5 mAh cm⁻² at high sulfur loading of 8.7 mg cm⁻². Mechanistic studies unveil the dominant multi-promoting effect of the triethoxylation on electron and ion conduction, polysulfide adsorption and catalytic conversion as well as previously-unexplored −CN/C−O dual-site synergistic effect for enhanced polysulfide adsorption and reduced energy barrier toward Li₂S conversion.     

锂硫电池硫膨胀石墨正极材料的电化学性能

应用高温气相扩散沉积法由单质硫制备硫膨胀石墨.该硫膨胀石墨正极可降低反应界面电荷传递阻抗,提高扩散阻抗抑制单质硫或多硫化物在充放电过程的穿梭.其首次放电容量达到972 mAh.g-1,容量保持率为78%,循环效率在80%以上.     

Enhanced cycle performance of Li/S battery with the reduced graphene oxide/activated carbon functional interlayer

The high-energy lithium/sulfur(Li/S) battery has become a very popular topic of research in recent years due to its high theoretical capacity of 1672 m Ah/g. However, the polysulfide shuttle effect remains of great concern with a great number of publications dedicated to its mitigation. In this contribution, a three-dimensional(3D) reduced graphene oxide/activated carbon(RGO/AC) film, synthesized by a simple hydrothermal method and convenient mechanical pressing, is sandwiched between the separator and the sulfur-based cathode, acting as a functional interlayer to capture and trap polysulfide species. Consequently, the Li/S cell with this interlayer shows an impressive initial discharge capacity of 1078 m Ah/g and a reversible capacity of 655 m Ah/g even after 100 cycles. The RGO/AC interlayer impedes the movement of polysulfide while providing unimpeded channels for lithium ion mass transfer. Therefore, the RGO/AC interlayer with a well-designed structure represents strong potential for high-performance Li/S batteries.     

Dual Dopamine Derived Polydopamine Coated N-Doped Porous Carbon Spheres as a Sulfur Host for High-Performance Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries are considered to be one of the most promising energy storage systems owing to their high energy density and low cost. However, their wide application is still limited by the rapid capacity fading. Herein, polydopamine (PDA)-coated N-doped hierarchical porous carbon spheres (NPC@PDA) are reported as sulfur hosts for high-performance Li-S batteries. The NPC core with abundant and interconnected pores provides fast electron/ion transport pathways and strong trapping ability towards lithium polysulfide intermediates. The PDA shell could further suppress the loss of lithium polysulfide intermediates through polar–polar interactions. Benefiting from the dual function design, the NPC/S@PDA composite cathode exhibits an initial capacity of 1331 mAh g⁻¹ and remains at 720 mAh g⁻¹ after 200 cycles at 0.5 C. At the pouch cell level with a high sulfur mass loading, the NPC/S@PDA composite cathode still exhibits a high capacity of 1062 mAh g⁻¹ at a current density of 0.4 mA cm⁻².     

Coaxial Carbon/MnO2 Hollow Nanofibers as Sulfur Hosts for High‐Performance Lithium‐Sulfur Batteries

Lithium‐sulfur (Li‐S) batteries have recently attracted a large amount of attention as promising candidates for next‐generation high‐power energy storage devices because of their high theoretical capacity and energy density. However, the shuttle effect of polysulfides and poor conductivity of sulfur are still vital issues that constrain their specific capacity and cyclic stability. Here, we design coaxial MnO₂‐graphitic carbon hollow nanofibers as sulfur hosts for high‐performance lithium‐sulfur batteries. The hollow C/MnO₂ coaxial nanofibers are synthesized via electrospinning and carbonization of the carbon nanofibers (CNFs), followed by an in situ redox reaction to grow MnO₂ nanosheets on the surface of CNFs. The inner graphitic carbon layer not only maintains intimate contact with sulfur and outer MnO₂ shell to significantly increase the overall electrical conductivity but also acts as a protective layer to prevent dissolution of polysulfides. The outer MnO₂ nanosheets restrain the shuttle effect greatly through chemisorption and redox reaction. Therefore, the robust S@C/MnO₂ nanofiber cathode delivers an extraordinary rate capability and excellent cycling stability with a capacity decay rate of 0.044 and 0.051 % per cycle after 1000 cycles at 1.0 C and 2.0 C, respectively. Our present work brings forward a new facile and efficient strategy for the functionalization of inorganic metal oxide on graphitic carbons as sulfur hosts for high performance Li‐S batteries.     

Three‐Dimensional Hierarchical Constructs of MOF‐on‐Reduced Graphene Oxide for Lithium–Sulfur Batteries

A three‐dimensional (3D) hierarchical MOF‐on‐reduced graphene oxide (MOF‐on‐rGO) compartment was successfully synthesized through an in situ reduced and combined process. The unique properties of the MOF‐on‐rGO compartment combining the polarity and porous features of MOFs with the high conductivity of rGO make it an ideal candidate as a sulfur host in lithium–sulfur (Li‐S) batteries. A high initial discharge capacity of 1250 mAh g^?1 at a current density of 0.1 C (1.0 C=1675 mAh g^?1) was reached using the MOF‐on‐rGO based electrode. At the rate of 1.0 C, a high specific capacity of 601 mAh g^?1 was still maintained after 400 discharge–charge cycles, which could be ascribed to the synergistic effect between MOFs and rGO. Both the hierarchical structures of rGO and the polar pore environment of MOF retard the diffusion and migration of soluble polysulfide, contributing to a stable cycling performance. Moreover, the spongy‐layered rGO can buffer the volume expansion and contraction changes, thus supplying stable structures for Li‐S batteries.     

Nafion/Titanium Dioxide‐Coated Lithium Anode for Stable Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries have shown great potential as high energy‐storage devices. However, the stability of the Li metal anode is still a major concern. This is due to the formation of lithium dendrites and severe side reactions with polysulfide intermediates. We herein develop an anode protection method by coating a Nafion/TiO₂ composite layer on the Li anode to solve these problems. In this architecture, Nafion suppresses the growth of Li dendrites, protects the Li anode, and prevents side reactions between polysulfides and the Li anode. Moreover, doped TiO₂ further improves the ionic conductivity and mechanical properties of the Nafion membrane. Li–S batteries with a Nafion/TiO₂‐coated Li anode exhibit better cycling stability (776 mA h g^?1 after 100 cycles at 0.2 C, 1 C=1672 mA g^?1) and higher rate performance (787 mA h g^?1 at 2 C) than those with a pristine Li anode. This work provides an alternative way to construct stable Li anodes for high‐performance Li–S batteries.     

Functional Organosulfide Electrolyte Promotes an Alternate Reaction Pathway to Achieve High Performance in Lithium–Sulfur Batteries

Lithium–sulfur (Li‐S) batteries have recently received great attention because they promise to provide energy density far beyond current lithium ion batteries. Typically, Li‐S batteries operate by conversion of sulfur to reversibly form different soluble lithium polysulfide intermediates and insoluble lithium sulfides through multistep redox reactions. Herein, we report a functional electrolyte system incorporating dimethyl disulfide as a co‐solvent that enables a new electrochemical reduction pathway for sulfur cathodes. This pathway uses soluble dimethyl polysulfides and lithium organosulfides as intermediates and products, which can boost cell capacity and lead to improved discharge–charge reversibility and cycling performance of sulfur cathodes. This electrolyte system can potentially enable Li‐S batteries to achieve high energy density.     

Enhanced Electrochemical Kinetics on Conductive Polar Mediators for Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries have been recognized as promising substitutes for current energy‐storage technologies owing to their exceptional advantage in energy density. The main challenge in developing highly efficient and long‐life Li–S batteries is simultaneously suppressing the shuttle effect and improving the redox kinetics. Polar host materials have desirable chemisorptive properties to localize the mobile polysulfide intermediates; however, the role of their electrical conductivity in the redox kinetics of subsequent electrochemical reactions is not fully understood. Conductive polar titanium carbides (TiC) are shown to increase the intrinsic activity towards liquid–liquid polysulfide interconversion and liquid–solid precipitation of lithium sulfides more than non‐polar carbon and semiconducting titanium dioxides. The enhanced electrochemical kinetics on a polar conductor guided the design of novel hybrid host materials of TiC nanoparticles grown within a porous graphene framework (TiC@G). With a high sulfur loading of 3.5 mg cm^?2, the TiC@G/sulfur composite cathode exhibited a substantially enhanced electrochemical performance.