Cathode Material For Lithium-sulfur Batteries Research Articles

Insight into the effects of gas molecules-adsorbed on 2D-FeS2: A DFT study

Lithium-sulfur (Li-S) batteries are especially competitive in the energy sector due to their excellent performances, like preferable energy density and economic benefits. Studying the adsorption of gas molecules on electrode materials has potential engineering significance for Li-S batteries since they have a highly osmotic potential, which causes unavoidable damage to batteries. In this work, the adsorption phenomenon of common gas molecules (H2O, N2, H2, CO2, and O2) on the two-dimensional pyrite (2D-FeS2) cathode material surface, as well as the effects on the electronic and electrochemical properties, were investigated by the first-principles calculations. The adsorption capabilities were estimated by adsorption energy and Mulliken population analysis. Simulation results demonstrated that whole adsorption energies were less than -1.0 eV and larger than -0.6 eV, which shows a physisorption nature. Among them, the O-S bond of O2/2D-FeS2 has the strongest strength. Electronic structure calculations suggested that 2D-FeS2 maintained good conductivity after gas molecules were adsorbed, achieving efficient transfer between electron, lithium, and sulfur intermediates. Additionally, ab initio molecular dynamics (AIMD) simulations showed that Li+ exhibits excellent diffusion performance and low activation energy at different temperatures. 2D-FeS2 still has a stable electrochemical working window (1.87 ∼ 2.47 V), while the theoretical open current voltage is damaged by gas molecule adsorption. Consequently, this work theoretically reveals the effect of gas molecules on the cathode materials for Li-S batteries, which has guide meaning for engineering.

Heterokaryotic transition-metal dimers embedded monolayer g-C3N3 as promising anchoring and electrocatalytic materials for lithium-sulfur battery: First-principles calculations

g-C3N3 not only has high content of pyridine nitrogen, but also has a special two-dimensional porous structure, which is an ideal diatomic catalytic host materials. In this work, homonuclear and heteronuclear dual-atom catalysts (DACs, TM-TM@g-C3N3, TM = Mn, Fe, Co, Ni) were constructed using single-layer g-C3N3 as the carrier material of DACs, and their potential as sulfur-hosting materials and electrocatalytic materials for lithium-sulfur batteries was explored through first principles comprehensively. The results show that the coupling between the two metal atoms in heteronuclear DACs can regulate the spin state of each other's d-electrons, so that the anchoring and catalytic effects of heteronuclear DACs on polysulfide are more excellent than that of homonuclear DACs. Co-Mn@g-C3N3, when utilized as the cathode material in lithium-sulfur batteries, offers exceptional properties due to the hybridization between Mn2+ high-spin state d electron and Co2+ half-filled dz2 orbital. This unique interaction not only enables the polysulfide to exhibit the lowest Gibbs free energy during conversion, but also results in the lowest reaction energy barrier of 0.26 eV for the conversion of Li2S2 to Li2S. Furthermore, it is found that when 3d transition metal atoms act as heteronuclear DACs, the coupling between metal ions with high-spin states at the active site and metal ions with empty orbitals or half-full d-electrons has the most significant catalytic effect on polysulfides.

Sulfur Encapsulation into Carbon Nanospheres as an Effective Technique to Limit Sulfide Dissolution and Extend the Cycle Life of Lithium–Sulfur Batteries

Sulfur Encapsulation into Carbon Nanospheres as an Effective Technique to Limit Sulfide Dissolution and Extend the Cycle Life of Lithium–Sulfur Batteries

Mixed valence Mo2C-MoC/C catalyst enhances polysulfides conversion kinetics in lithium–sulfur batteries

Lithium-sulfur batteries have received extensive attention in the field of electrochemical energy storage systems due to their extremely high theoretical energy density (2600 Wh·kg−1) and low cost. However, poor electrical conductivity, shuttle effect, and volume expansion effect still need to be addressed. Here, we controllably synthesized hollow spherical Mo2C-MoC/C structure as the cathode material for lithium-sulfur batteries. Through high-temperature calcination, the synthesis of graphitized reticular carbon matrix and the loading of Mo2C and MoC nanoparticles with mixed valence of Mo2+ and Mo3+ were simultaneously achieved. The two synergistically improved the electronic conductivity and ensured excellent battery performance. From the experimental results, Mo2C-MoC/C structure strongly adsorbed polysulfides and promoted the conversion of polysulfides to lithium sulfide, accelerating the reaction kinetics and enhancing the battery performance. The initial discharge specific capacity of Mo2C-MoC/C electrode with 57.12 wt% sulfur content was 870.4 mAh·g−1 at 0.2 C, and remained at 770.7 mAh·g−1 at 0.5 C, which was significantly better than that of Mo2C/C/S. The rational design of the Mo2C-MoC/C structure in this study can be generalized to the advanced electrode materials of other Mo-based nanomaterials.

Theoretical screening of electrocatalytic performance of Fe@BNC materials in lithium-sulfur batteries

Advanced cathode materials can suppress the shuttle effect and improve the slow sulfur reduction kinetics during discharge in lithium-sulfur batteries. The catalytic performance of Fe@BNC single-atom catalysts as cathode materials was evaluated through simulations based on density functional theory in this article. By calculating the Gibbs free energy curve and adsorption energy of polysulfides on the substrate, it was found that Fe@BNC has a reasonable adsorption energy range and good catalytic activity. Moreover, calculations of reaction energy barriers indicate that Fe@B1N3 performs well in delithiation when charged. The Research investigates in detail the electrocatalytic properties and electronic structure properties of Fe@BNC as a cathode material for lithium-sulfur batteries. This paper highlights its potential to improve battery performance by reducing the shuttle effect and accelerating the redox kinetics.

Hybrid Organosulfur Network/MWCNT Composite Cathodes for Li-S Batteries.

Lithium-sulfur (Li-S) batteries hold a promising position as candidates for next-generation high-energy storage systems. Here, we combine inverse vulcanization of sulfur with multiwalled carbon nanotubes (MWCNTs) to increase the conductivity of cathode materials for Li-S batteries. The mixing process of inversely vulcanized sulfur copolymer networks with MWCNTs is aided by shear in a two-roll mill to take advantage of the soft nature of the copolymer. The high-throughput mixing method demands a source of conductive carbon that can be intimately mixed with the S copolymer, rendering MWCNTs an excellent choice for this purpose. The resulting sulfur copolymer network-MWCNTs composites were thoroughly characterized in terms of structure, chemical composition, thermal, and electronic transport properties, and finally evaluated by electrochemical benchmarking. These promising hybrids yielded electrodes with high sulfur content and demonstrate stable electrochemical performance exhibiting a specific capacity of ca. 550 mAh·gsulfur-1 (380 mAh·gelectrode-1) even after 500 charge-discharge cycles at specific current of 167 mA·g-1 (corresponds to 0.1C discharge rate), and thus are superior to melt-infiltrated reference samples.

Theoretical investigation of synergistically boosting the anchoring and electrochemical performance of lithiophilic/sulfiphilic transition metal carbides for lithium-sulfur batteries.

Lithium-sulfur (Li-S) battery is one of the most promising next-generation energy-storage systems with a high energy density and low cost. However, their commercial applications face several challenges, such as the shuttle effect caused by the soluble lithium polysulfide (LiPSs) intermediates and the sluggish sulfur redox reaction. In this article, we systematically investigated the anchoring and electrochemical performance of a series of transition metal carbides (TMCs: TiC, VC, ZrC, NbC, HfC, TaC) as cathode materials for Li-S batteries by theoretical calculations. The lithiophilic/sulfiphilic non-polar (001) surfaces of TMCs can offer moderate binding strength with LiPS intermediates, ensuring good performance of sulfur immobilization. These TMCs can also facilitate lithium diffusion, indicating the good rate performance of Li-S batteries. We also demonstrated that the studied TMCs can be classified into two classes according to their catalytic activity for Li2S decomposition which originated from their different electronic structural features. Furthermore, TiC, ZrC, and HfC exhibited excellent bifunctional electrochemical activity through reducing the Gibbs free energy for sulfur reduction reactions (SRRs) and lowering the barrier for Li2S decomposition which facilitates accelerating electrode kinetics and elevating utilization of sulfur. Our results offer a systematic approach to designing and screening non-polar materials for high-performance Li-S batteries, based on the rational electronic structure and lattice match strategy.

N-doped CNTs wrapped sulfur-loaded hierarchical porous carbon cathode for Li-sulfur battery studies.

Lithium-sulfur (Li-S) batteries are considered promising next-generation energy storage devices due to their low cost and high energy density (2600 W h kg-1). However, the practical applicability of Li-S batteries is hindered by the insulating nature of sulfur cathodes, and the high solubility of polysulfides (Li2Sx, 3 < x ≤ 8) which are formed during the electrochemical process. Integrating sulfur into the carbon host is an effective way to enhance the conductivity of the electrode which hampers the shuttling effect of the polysulfides. Here in this study, hierarchical porous carbon structures (HPC) are prepared from spent coffee waste (SCW) by the KOH activation process and are encapsulated with sulfur (SHPC) which increases the interaction between sulfur and carbon and enhances both the electronic and ionic conductivities. Further wrapping of SHPC with N-doped multi-walled carbon nanotubes (NCNTs) gives a SHPC-NCNT composite, which alleviates the shuttling of polysulfides by trapping them and ensures the required conductivity to the sulfur cathode during the Li+ reactions. When studied as a cathode material for Li-S batteries, the prepared cathode showed 664 and 532 mA h g-1 specific capacities after 150 cycles at 0.2C and 0.5C, respectively. The stable cyclability and rate capability properties of SPHCNCNT suggest that the prepared sulfur composite is suitable as a cathode material for Li+ energy storage applications.

First-row transition metal carbide nanosheets as high-performance cathode materials for lithium-sulfur batteries.

Despite the prodigious potential of lithium-sulfur (Li-S) batteries as future rechargeable electrochemical systems, their commercial implementation is hindered by several vital issues, including the shuttle effect and sluggish migration of lithium-polysulfides leading to rapid capacity fading. Here, we systematically investigate the potential of first-row two-dimensional transition metal carbides (TMCs) as sulfur cathodes for Li-S batteries. The adsorption strength of lithium-polysulfides on TMCs is induced by the amount of charge transfer from the former to the latter and the proposed periodic relationship between sulfur in Li2S and 3d-transition metals. Our findings show that the VC nanosheet possesses immense anchoring potential and exhibits a comparatively low migration energy barrier for lithium-ion and Li2S molecules. Additionally, we report ab initio molecular dynamics simulations for lithiated polysulfide species anchored on a TMC-based model with a liquid-electrolyte medium. The microscopic reaction mechanism, revealed by the evolution of the reaction voltage during lithiation, demonstrates that the dissolution of high-order lithium-polysulfides in the electrolytes can be prevented due to their robust interaction with TMC-based cathode materials. These appealing features suggest that TMCs present colossal performance improvements for anchoring lithium-polysulfides, stimulating the active design of sulfur cathodes for practical Li-S batteries.

Retracted: MoWS2 Nanosheet Composite with MXene as Lithium-Sulfur Battery Cathode Material

Retracted: MoWS₂ Nanosheet Composite with MXene as Lithium-Sulfur Battery Cathode Material

Tandem Carbon Hollow Spheres with Tailored Inner Structure as Sulfur Immobilization for Superior Lithium–Sulfur Batteries

AbstractThe construction of lithium–sulfur battery cathode materials while simultaneously achieving high areal sulfur‐loading, adequate sulfur utilization, efficient polysulfides inhibition, rapid ion diffusion, etc. remains a major challenge. Herein, an internal regulatory strategy to fabricate the unique walnut‐like yolk–shell carbon flower@carbon nanospheres is presented (WSYCS) as sulfur hosts. The internal carbon flower, suitable cavity, and external carbon layer effectively disperse the insulate sulfur, accommodate volumetric expansion, and confine polysulfides, thus improving the performance of lithium–sulfur batteries. The finite element simulation method also deduces the enhanced Li+ diffusion and lithium–sulfur reaction kinetics. More importantly, WSYCS2 is grafted onto carbon fiber (CF) by electro‐spinning method to form a tandem WSYCS2@CF 3D film as a sulfur host for the free‐standing electrode. The corresponding battery exhibits an extremely high areal capacity of 15.5 mAh cm−2 with a sulfur loading of 13.4 mg cm−2. Particularly, the flexible lithium–sulfur pouch cell delivers a high capacity of 8.1 mAh cm−2 and excellent capacity retention of 65% over 800 cycles at a relatively high rate of 1C, corresponding to a calculated energy density of 539 Wh kg−1 and 591 Wh L−1. This work not only provides guidance for tailoring thick carbon/sulfur electrodes but also boosts the development of practical lithium–sulfur batteries.

Theoretically unraveling the performance of 2D-FeS2 as cathode material for Li-S batteries

The construction of electrode materials with high conductivity and satisfactory safety for lithium-sulfur (Li-S) batteries remains critical to enhancing the performance of energy storage devices. In recent years, two-dimensional (2D) materials with layered structures have been a hot spot for research due to their unique electronic properties and large specific surface area. As an emerging electrochemically active material, 2D-FeS2 has short ion diffusion paths and a high specific surface area. Based on theoretical calculations, we have systematically studied the performance of the 2D-FeS2 monolayer as cathode material for Li-S batteries from five aspects: obtainability of structure, thermodynamic stability, electrical, surface activity, and electrochemical properties. Simulation results show that the 2D-FeS2 monolayer structure is easy to form due to the small exfoliation energy and interlayer binding energy. The layered structure surface enhances the anchoring effect of polysulfide. Excellent stability was verified by tdynamics simulation. Additionally, the DOS results show that the 2D-FeS2 monolayer has higher conductivity, which effectively improves the mobility of Li+ and electrons. The theoretical specific capacity of the 2D-FeS2 monolayer is 446.96 mAh/g, and the lower Li+ diffusion barrier is 0.19 eV. Compared to traditional FeS2, the 2D-FeS2 monolayer has higher conductivity and stability. In brief, the 2D-FeS2 monolayer is a promising cathode material for Li-S batteries. This work opens up a new path for the application of 2D materials to new energy batteries and also deepens our understanding of 2D materials at the nanoscale.

Synergistic effect of Fe3C quantum dots, N-doped carbon and selenium on high conductive stable host for lithium sulfur batteries

Lithium-sulfur batteries are considered as one of the most promising energy storage devices. However, their development is still hindered by significant obstacles, particularly the well-known "shuttle effect". To overcome the issues, a three-dimensional porous biochar composite GC(Fe3C)x with Fe3C quantum dots/ C heterostructure is prepared by a simple one-stage chemical activation method as a sulfur host. A small amount of selenium is also added to form GC/Fe3C@SSe and improved electrochemical performances are obtained. The influence of Fe3C content on the structure and properties of the composites is investigated. It has been observed that an increase in Fe3C content leads to a reduction in specific surface area, thereby enhancing chemical adsorption while simultaneously weakening physical adsorption. When the Fe3C content reached 2.7%, the composite achieved a specific surface area of 1150.0 m² g−1. The synergistic effect of Fe3C quantum dots, N-doped carbon, and selenium resulted in outstanding electrochemical properties exhibited by the composite. At 1 C, GC/(Fe3C)2.7@SSe provides an initial specific discharge capacity of 803.7 mAh g−1. After 1000 long cycles, the specific discharge capacity is maintained at 363.1 mAh g−1, and the per-cycle capacity loss rate is 0.055%. Even at the current density of 5 C, the initial discharge capacity is 424.5 mAh g−1, and the capacity after 500 cycles is 322.9 mAh g−1, with a single cycle capacity decay rate of 0.048%. This work provides guidance for the design of lithium-sulfur battery cathode materials with synergetic physisorption and chemisorption for inhibiting shuttle effect.

Conductive Metal Organic Framework as Trapping Cathode Additive for High Performance Lithium-Sulfur Batteries

Lithium-Sulfur (Li-S) batteries with high capacity and energy density have arisen as one of the most promising secondary batteries. However, higher order lithium polysulfide (LiPSs) shuttling and insulating nature of sulfur cathode results in capacity degradation and premature failure of the cell [1]. Here for the first time, we have implemented conductive Cu metal-based Metal organic framework (Cu-MOF) as a Li-S battery cathode material. Cu-MOF cathode catalyst not only reduce the LiPSs shuttle effect but also increase the conductivity of Li-S battery cathode [2].Here, Cu-MOF pore morphology will trap the polysulfides and further prevent LiPSs shuttling. In addition, the well-defined architecture of organic ligands of Cu-MOF also participate to explicate the involved surface-binding mechanisms of S and polysulfide products. Furthermore, Cu-MOF improve the diffusion rate of Li ions, shackling LiPSs, upsurging conduction of electrons/ions, and regulating the deposition of Li2S2/Li2S towards cathode side [3]. Furthermore, sulfur active material is well percolated inside the pores of conductive Cu-MOF which shows the long-cycling performance as shown in Figure 1.Benefiting from the unique fibrous, porous, interwoven structure, the conductive MOF@S-composite cathode demonstrates a high initial capacity of 1671 mAh g–1 at 0.05 C rate with a good coulombic efficiency of >95% and the outstanding capacity of 849 mAh g-1 cycles even after 200 cycles at the 0.5 C-rate with coulombic efficiency of 98.3%. It is believed that, the experimental findings and mechanistic understanding of Cu-MOF cathode in this work will open a new avenue for the further development of other conductive MOFs in the Li-S batteries. Figure 1: Cycling performance of S@Cu-MOF composite at 0.5 C-rate. References Mingyue Wang, Zhongchao Bai, Ting Yang, Chuanhao Nie, Xun Xu, Yunxiao Wang, Jian Yang, Shixue Dou, and Nana Wan."Advances in High Sulfur Loading Cathodes for Practical Lithium-Sulfur Batteries." Energy Mater, no.12 (2022): 2201585.Dan Luo, Chaojie Li, Yongguang Zhang, Qianyi Ma, Chuyin Ma, Yihang Nie, Matthew Li, Xuefei Weng, Rong Huang, Yan Zhao, Lingling Shui, Xin Wang, Zhongwei Chen. "Design of Quasi-MOF Nanospheres as a Dynamic Electrocatalyst toward Accelerated Sulfur Reduction Reaction for High-Performance Lithium–Sulfur Batteries." Mater, no.34 (2022): 210554. Jun Zhang, Ye Shi, Yu Ding, Lele Peng, Wenkui Zhang, Guihua Yu. "A Conductive Molecular Framework Derived Li2S/N,P-Codoped Carbon Cathode for Advanced Lithium–Sulfur Batteries." Energy Mater, no.7 (2017): 1602876. Figure 1

MXene surface-attached Ni2P on lithium-sulfur battery catalytic effect

Because lithium-sulfur batteries have inherent internal problems that hinder their commercial development, this work effectively improves the aforementioned defects from the cathode material. MXene functions as a conductive substrate to optimize the conductivity of lithium-sulfur battery cathode material. Simultaneously, the addition of Ni2P is capable of significantly limiting the shuttle effect. This is mostly owing to the high polar Ni2P adsorption action on polar intermediate polysulfides. When a sufficient amount of Ni2P is added, electrochemical performance tests reveal that the battery has a low polarization voltage, which is conducive to the reversible process. Furthermore, at a current density of 0.1C, the initial discharge specific capacity of MXene@Ni2P-1/S is 1311.2 mAh/g. The discharge specific capacity of the battery remained at 626.7 mAh/g after 200 cycles at 0.2C, and the coulomb efficiency remained above 97.5%, demonstrating that the MXene@Ni2P-1/S composite material could significantly increase the battery's reaction kinetic performance.

VS4/MoS2 heterostructures grown along graphene to boost reaction kinetics and reversibility for high performance lithium-sulfur batteries

Lithium-sulfur batteries are regarded as one of the most promising next-generation energy storage systems due to their high theoretical volumetric and high weight energy density. However, there are severe problems in the application of lithium-sulfur batteries. The shuttle effect of soluble lithium polysulfide (LiPs) and the low conductivity of sulfur, which leads to slow redox kinetics, are hindering the more significant application of lithium-sulfur batteries. One of the viable solutions to the cathode problem of lithium-sulfur batteries is heterostructured materials. The built-in electric field provided by the heterostructure can significantly accelerate the kinetics of charge transport. In this work, we constructed a heterogeneous structure of G-VS4/MoS2 composites(PVM) modified by Polyvinylpyrrolidone(PVP) is constructed based on graphene, which consists of VS4 nanosheets and MoS2 nanosheets grown vertically on graphene lamellae. With weak van der Waals interactions, the one-dimensional (1D) chain-like VS4 crystal structure enables fast charge transfer in Li-ion batteries. The two-dimensional (2D) lamellar MoS2 crystals contain Mo-S bonds that also have adsorption effects on polysulfides. Density functional theory (DFT) calculations show that VS4 and MoS2 can increase the binding energy of the anode to the polysulfide. Therefore, the S@PVM cathode material provides a large capacity of 1061.4 mAh/g at 0.5 C and can still get to 808.3 mAh/g after 400th cycles. A capacity retention rate of 76.15% is obtained at the same time. It can also boast an initial discharge capacity of 834.8 mAh/g at 1 C. These works can provide more thoughts for developing cathode materials for lithium-sulfur batteries.

Synthesis of Deliquescent Lithium Sulfide in Air.

In the field of lithium-sulfur batteries (LSBs) and all-solid-state batteries, lithium sulfide (Li2S) is a critical raw material. However, its practical application is greatly hindered by its high price due to its deliquescent property and production at high temperatures (above 700 °C) with carbon emission. Hereby, we report a new method of preparing Li2S, in air and at low temperatures (∼200 °C), which presents enriched and surprising chemistry. The synthesis relies on the solid-state reaction between inexpensive and air-stable raw materials of lithium hydroxide (LiOH) and sulfur (S), where lithium sulfite (Li2SO3), lithium thiosulfate (Li2S2O3), and water are three major byproducts. About 57% of lithium from LiOH is converted into Li2S, corresponding to a material cost of ∼$64.9/kg_Li2S, less than 10% of the commercial price. The success of conducting this water-producing reaction in air lies in three-fold: (1) Li2S is stable with oxygen below 220 °C; (2) the use of excess S can prevent Li2S from water attack, by forming lithium polysulfides (Li2Sn); and (3) the byproduct water can be expelled out of the reaction system by the carrier gas and also absorbed by LiOH to form LiOH·H2O. Two interesting and beneficial phenomena, i.e., the anti-hydrolysis of Li2Sn and the decomposition of Li2S2O3 to recover Li2S, are explained with density functional theory computations. Furthermore, our homemade Li2S (h-Li2S) is at least comparable with the commercial Li2S (c-Li2S), when being tested as cathode materials for LSBs.

Graphene/Heterojunction Composite Prepared by Carbon Thermal Reduction as a Sulfur Host for Lithium-Sulfur Batteries.

An interlayer nanocomposite (CC@rGO) consisting of a graphene heterojunction with CoO and Co9S8 was prepared using a simple and low-cost hydrothermal calcination method, which was tested as a cathode sulfur carrier for lithium-sulfur batteries. The CC@rGO composite comprises a spherical heterostructure uniformly distributed between graphene sheet layers, preventing stacking the graphene sheet layer. After the introduction of cobalt heterojunction on a graphene substrate, the Co element content increases the reactive sites of the composite and improves its electrochemical properties to some extent. The composite exhibited good cycling performance with an initial discharge capacity of 847.51 mAh/g at 0.5 C and a capacity decay rate of 0.0448% after 500 cycles, which also kept 452.91 mAh/g at 1 C and in the rate test from 3 C back to 0.1 C maintained 993.27 mAh/g. This article provides insight into the design of cathode materials for lithium-sulfur batteries.

Activation of Bulk Li2S as Cathode Material for Lithium-Sulfur Batteries through Organochalcogenide-Based Redox Mediation Chemistry.

Lithium sulfide (Li2S) is considered as a promising cathode material for sulfur-based batteries. However, its activation remains to be one of the key challenges against its commercialization. The extraction of Li+ from bulk Li2S has a high activation energy (Ea) barrier, which is fundamentally responsible for the initial large overpotential. Herein, a systematic investigation of accelerated bulk Li2S oxidation reaction kinetics was studied by using organochalcogenide-based redox mediators, in which phenyl ditelluride (PDTe) can significantly reduce the Ea of Li2S and lower the initial charge potential. Simultaneously, it can alleviate the polysulfides shuttling effect by covalently anchoring the soluble polysulfides and converting them into insoluble lithium phenyl tellusulfides (PhTe-SxLi, x > 1). This alters the redox pathway and accelerates the reaction kinetics of Li2S cathode. Consequently, the Li||Li2S-PDTe cell shows excellent rate capability and enhanced cycling stability. The Si||Li2S-PDTe full cell delivers a considerable capacity of 953.5 mAh g-1 at 0.2 C.

Sulfur-rich polymer/Ketjen Black composites as lithium-sulfur battery cathode with high cycling stability

Lithium-sulfur (Li-S) battery is considered as one of the most promising energy storage devices due to its exceptional energy density. However, its development is largely hampered by the shuttle effect of lithium polysulfide and the sluggish electrochemical kinetics of sulfur cathode. In this study, a novel sulfur-rich polymer is synthesized through the inverse vulcanization of sulfur with 2,4,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane (TVTCSi) and used as cathode material for Li-S batteries, which can effectively immobilize the lithium polysulfides through covalent bonds to impede its shuttling, leading to marked improvement in the cycling performance of the batteries. Furtherly, with the addition of Ketjen Black, the resulting composite cathode exhibited faster electrochemical reaction kinetics and higher cycling stability, which could deliver a reversible discharge capacity of 652 mAh g−1 after 500 cycles at a high current density of 0.5 C,0.5C with quite a low capacity decay rate of only 0.037% per cycle, which indicates broad perspectives of sulfur-rich polymer/Ketjen Black composite as cathode material in lithium-sulfur battery.