Free-standing graphene@carbon hollow sphere confining high-loading sulfur cathode for high-performance lithium–sulfur batteries

Practical applications of lithium–sulfur batteries are not satisfactory due to the poor conductivity, large volume expansion, dissolution of polysulfides, low sulfur content, and sulfur loading. Herein, free-standing graphene@carbon hollow sphere confining sulfur composite (G@C-HS@S) was prepared by ice template technology and vacuum immersion method for high-loading Li–S batteries. Ice template technology was used to adjust the vertical pore structure of the free-standing G@C-HS gel, allowing for easier ion transport. A three-dimensional G@C-HS framework with physical confinement improves the conductivity of cathode and inhibits the loss of sulfur and polysulfide, in which C-HS also greatly alleviates the volume expansion of sulfur. Sulfur is ingeniously encapsulated into G@C-HS framework by vacuum immersion method, achieving a high sulfur content of 81% and a high sulfur loading of 7.29 mg cm^?2. Benefiting from the above synergistic effects, G@C-HS@S delivers a specific capacity of 1187 mAh g^?1 at 0.1 C, a superior rate capability of 643 mAh g^?1 at 10 C, and an excellent cycle life of 61.8% after 700 cycles. The above results provide an effective route for high-performance Li–S batteries.

     

Interface-modulated fabrication of hierarchical yolk–shell Co<Subscript>3</Subscript>O<Subscript>4</Subscript>/C dodecahedrons as stable anodes for lithium and sodium storage

Transition-metal oxides (TMOs) have gradually attracted attention from researchers as anode materials for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) because of their high theoretical capacity.However,their poor cycling stability and inferior rate capability resulting from the large volume variation during the lithiation/sodiation process and their low intrinsic electronic conductivity limit their applications.To solve the problems of TMOs,carbon-based metal-oxide composites with complex structures derived from metal-organic frameworks (MOFs) have emerged as promising electrode materials for LIBs and SIBs.In this study,we adopted a facile interface-modulated method to synthesize yolk-shell carbon-based Co3O4 dodecahedrons derived from ZIF-67 zeolitic imidazolate frameworks.This strategy is based on the interface separation between the ZIF-67 core and the carbon-based shell during the pyrolysis process.The unique yolk-shell structure effectively accommodates the volume expansion during lithiation or sodiation,and the carbon matrix improves the electrical conductivity of the electrode.As an anode for LIBs,the yolk-shell Co3O4/C dodecahedrons exhibit a high specific capacity and excellent cycling stability (1,100 mAh·g-1 after 120 cycles at 200 mA·g-1).As an anode for SIBs,the composites exhibit an outstanding rate capability (307 mAh·g-1 at 1,000 mA·g-1 and 269 mAh·g-1 at 2,000 mA·g-1).Detailed electrochemical kinetic analysis indicates that the energy storage for Li+ and Na+ in yolk-shell Co3O4/C dodecahedrons shows a dominant capacitive behavior.This work introduces an effective approach for fabricating carbonbased metal-oxide composites by using MOFs as ideal precursors and as electrode materials to enhance the electrochemical performance of LIBs and SIBs.     

锂硫电池正极用钴掺杂空心多孔碳载体材料

锂硫电池被认为是新一代低成本、高能量密度的储能系统。但由于硫正极导电性差、穿梭效应严重以及氧化还原反应速率慢, 导致电池容量衰减严重, 倍率性能较差。本研究以柠檬酸钠为碳源制备了具有三维中空结构的多孔碳材料, 并在其骨架上负载钴纳米颗粒后作为硫正极的载体。引入的钴纳米颗粒可有效吸附多硫化物, 提升其转化反应的动力学, 进而明显改善电池的循环和倍率性能。所得的钴掺杂复合硫正极在0.5C (1C=1672 mAh·g^-1)的倍率下首圈放电比容量高达1280 mAh·g^-1, 在1C的倍率下稳定循环200圈后可保持770 mAh·g^-1, 并且具有优异的倍率性能, 即使在10C的大电流密度下仍可稳定循环。     

Promoting Reversible Redox Kinetics by Separator Architectures Based on CoS2/HPGC Interlayer as Efficient Polysulfide‐Trapping Shield for Li–S Batteries

Main obstacles from the shuttle effect and slow conversion rate of soluble polysulfide compromise the sulfur utilization and cycling life for lithium sulfur (Li–S) batteries. In pursuit of a practically viable high performance Li–S battery, a separator configuration (CoS₂/HPGC/interlayer) as efficient polysulfide trapping barrier is reported. This configuration endows great advantages, particularly enhanced conductivity, promoted polysulfide trapping capability, accelerated sulfur electrochemistry, when using the functional interlayer for Li–S cells. Attributed to the above merits, such cell shows excellent cyclability, with a capacity of 846 mAh g^?1 after 250 cycles corresponding to a high capacity retention of 80.2% at 0.2 C, and 519 mAh g^?1 after 500 cycles at 1C (1C = 1675 mA g^?1). In addition, the optimized separator exhibits a high initial areal capacity of 4.293 mAh cm^?2 at 0.1C. Moreover, with CoS₂/HPGC/interlayer, the sulfur cell enables a low self‐discharge rate with a very high capacity retention of 97.1%. This work presents a structural engineering of the separator toward suppressing the dissolution of soluble Li₂Sn moieties and simultaneously promoting the sulfur conversion kinetics, thus achieving durable and high capacity Li–S batteries.     

Highly Safe Electrolyte Enabled via Controllable Polysulfide Release and Efficient Conversion for Advanced Lithium–Sulfur Batteries

Conventional lithium–sulfur batteries often suffer from fatal problems such as high flammability, polysulfide shuttling, and lithium dendrites growth. Here, highly‐safe lithium–sulfur batteries based on flame‐retardant electrolyte (dimethoxyether/1,1,2,2‐tetrafluoroethyl 2,2,3,3‐tetrafluoropropyl ether) coupled with functional separator (nanoconductive carbon‐coated cellulose nonwoven) to resolve aforementioned bottle‐neck issues are demonstrated. It is found that this flame‐retardant electrolyte exhibits excellent flame retardancy and low solubility of polysulfide. In addition, Li/Li symmetrical cells using such flame‐retardant electrolyte deliver extraordinary long‐term cycling stability (less than 10 mV overpotential) for over 2500 h at 1.0 mA cm^?2 and 1.0 mAh cm^?2. Moreover, bare sulfur cathode–based lithium–sulfur batteries using this flame retardant electrolyte coupled with nanoconductive carbon‐coated cellulose separator can retain 83.6% discharge capacity after 200 cycles at 0.5 C. Under high charge/discharge rate (4 C), lithium–sulfur cells still show high charge/discharge capacity of ≈350 mAh g^?1. Even at an elevated temperature of 60 °C, discharge capacity of 870 mAh g^?1 can be retained. More importantly, high‐loading bare sulfur cathode (4 mg cm^?2)–based lithium–sulfur batteries can also deliver high charge/discharge capacity over 806 mAh g^?1 after 56 cycles. Undoubtedly, the strategy of flame retardant electrolyte coupled with carbon‐coated separator enlightens highly safe lithium–sulfur batteries at a wide range of temperature.     

Nickel-decorated TiO2 nanotube arrays as a self-supporting cathode for lithium--sulfur batteries

Lithium–sulfur batteries are considered to be one of the strong competitors to replace lithium-ion batteries due to their large energy density. However, the dissolution of discharge intermediate products to the electrolyte, the volume change and poor electric conductivity of sulfur greatly limit their further commercialization. Herein, we proposed a self-supporting cathode of nickel-decorated TiO₂ nanotube arrays (TiO₂ NTs@Ni) prepared by an anodization and electrodeposition method. The TiO₂ NTs with large specific surface area provide abundant reaction space and fast transmission channels for ions and electrons. Moreover, the introduction of nickel can enhance the electric conductivity and the polysulfide adsorption ability of the cathode. As a result, the TiO₂ NTs@Ni–S electrode exhibits significant improvement in cycling and rate performance over TiO₂ NTs, and the discharge capacity of the cathode maintains 719 mA·h·g⁻¹ after 100 cycles at 0.1 C.     

Boron-doped microporous nano carbon as cathode material for high-performance Li-S batteries

In this study,a boron-doped microporous carbon (BMC)/sulfur nanocomposite is synthesized and applied as a novel cathode material for advanced Li-S batteries.The cell with this cathode exhibits an ultrahigh cycling stability and rate capability.After activation,a capacity of 749.5 mAh/g was obtained on the 54th cycle at a discharge current of 3.2 A/g.After 500 cycles,capacity of 561.8 mAh/g remained (74.96％ retention),with only a very small average capacity decay of 0.056％.The excellent reversibility and stability of the novel sulfur cathode can be attributed to the ability of the boron-doped microporous carbon host to both physically confine polysulfides and chemically bind these species on the host surface.Theoretical calculations confirm that boron-doped carbon is capable of significantly stronger interactions with the polysulfide species than undoped carbon,most likely as a result of the lower electronegativity of boron.We believe that this doping strategy can be extended to other metal-air batteries and fuel cells,and that it has promising potential for many different applications.     

Implanting Niobium Carbide into Trichoderma Spore Carbon: a New Advanced Host for Sulfur Cathodes

Tailored construction of advanced carbon hosts is playing a great role in the development of high‐performance lithium–sulfur batteries (LSBs). Herein, a novel N,P‐codoped trichoderma spore carbon (TSC) with a bowl structure, prepared by a “trichoderma bioreactor” and annealing process is reported. Moreover, TSC shows excellent compatibility with conductive niobium carbide (NbC), which is in situ implanted into the TSC matrix in the form of nanoparticles forming a highly porous TSC/NbC host. Importantly, NbC plays a dual role in TSC for not only pore formation but also enhancement of conductivity. Excitingly, the sulfur can be well accommodated in the TSC/NbC host forming a high‐performance TSC/NbC‐S cathode, which exhibits greatly enhanced rate performance (810 mAh g^?1 at 5 C) and long cycling life (937.9 mAh g^?1 at 0.1 C after 500 cycles), superior to TSC‐S and other carbon/S counterparts due to the larger porosity, higher conductivity, and better synergetic trapping effect for the soluble polysulfide intermediate. The synergetic work of porous the conductive architecture, heterodoped N&P polar sites in TSC and polar conductive NbC provides new opportunities for enhancing physisorption and chemisorption of polysulfides leading to higher capacity and better rate capability.     

Encapsulation of Sulfur into N‐Doped Porous Carbon Cages by a Facile,Template‐Free Method for Stable Lithium‐Sulfur Cathode

Lithium‐sulfur (Li‐S) batteries with a high energy density and long lifespan are considered as promising candidates for next‐generation electrochemical energy‐storage devices. However, the sluggish redox kinetics of electrochemistry and high solubility of polysulfide during cycling render insufficient sulfur utilization and poor cycling stability. Herein, a facile, template‐free procedure based on controlled pyrolysis of polydopamine vesicles is described to prepare N‐doped porous carbon cages (NHSC) as a new sulfur host, which significantly improves both the sulfur utilization and cycling stability. As NHSC shows a high pore volume, continuous electron and ion transport paths, and good catalytic activity, encapsulation of S nanoparticles into NHSC endows the resulting S@NHSC electrode with a good energy storage capacity and exceptionally high electrochemical stability. Consequently, a Li‐S cell with the S@NHSC as the cathode achieves a high initial capacity of 1280.7 mAh g^?1, and cycling stability over 500 cycles with the capacity decay as low as 0.0373% per cycle.     

S,N-codoped carbon capsules with microsized entrance: Highly stable S reservoir for Li-S batteries

Nanostructured carbon materials are extensively applied as host materials to improve the utilization rate and reversibility of elemental sulfur in lithium sulfur (Li-S) batteries. Here, S, N-codoped carbon capsules (SNCCs) with microporous walls, prepared by a self-assembly process, are used as the sulfur host material in Li-S batteries. The SNCCs provide plenty of micron-sized cavities to accommodate a high S loading, which are sealed by thick walls with microsized entrance to efficently suppress the shuttle effect of lithium polysulfides. As the cathode in Li-S battery, the SNCCs/sulfur composite with a sulfur mass loading of 70 wt% exhibits a high average reversible capacity of 1220 and 1116 mA h g^?1 at 0.5C and 1C, respectively, superior rate performance (905 and 605 mAh g^?1 at 5C and 10C, respectively) and excellent cycling stability (capacity fading rate of 0.03% per cycle in 500 cycles). Even at a high sulfur areal loading of 7.3 mg/cm², the SNCCs/0.7S electrode still deliver a high initial discharge capacity of 838 mAh g^?1 and keeps at 730 mAh g^?1 after 100 cycles, corresponding to an extraordinary capacity retention of 87.1%, showing an excellent cyclic stability. The outstanding electrochemical performance is associated with the unique capsule structure with abundant volume, microsized entrance and high conductivity. Our results provides a new strategy to prepare highly stable sulfur-carbon composites for the application in Li-S batteries.     

TiO2-聚吡咯纳米复合材料的电化学制备及其在锂硫电池中的应用

采用电化学沉积的方法,以阳极氧化法制备的二氧化钛纳米管阵列为基底,制备出高度有序的TiO_2-聚吡咯(PPy)纳米阵列,再通过共热法,将单质硫颗粒负载到基底阵列中,得到S/PPy/TiO_2纳米阵列结构复合材料。扫描电镜(SEM)、透射电镜(TEM)、能谱(EDX)、傅里叶变换红外光谱(FT-IR)和热重分析(TGA)表征结果表明,TiO_2纳米管高度有序平行排列,管径约120nm,聚吡咯均匀沉积在纳米管壁上,复合材料中硫的质量分数约为61.9%。电化学测试结果表明,在0.1C电流密度下,S/PPy/TiO_2纳米复合材料首次循环比容量达1155mAh·g-1,100次循环后比容量为648.4mAh·g-1,库伦效率保持在96.8%。高容量下良好的循环稳定性能显示出S/TiO_2/PPy纳米阵列结构复合材料作为锂硫电池正极材料的优势。     

In-situ encapsulation of α-Fe2O3 nanoparticles into ZnFe2O4 micro-sized capsules as high-performance lithium-ion battery anodes

Transition metal oxides as anode materials for high-performance lithium-ion batteries suffer from severe capacity decay,originating primarily from particle pulverization upon volume expansion/shrinkage and the intrinsically sluggish electron/ion transport.Herein,in-situ encapsulation of α-Fe2O3 nanoparticles into micro-sized ZnFe2O4 capsules is facilely fulfilled through a co-precipitation process and followed by heat-treatment at optimal calcination temperature.The porous ZnFe2C4 scaffold affords a synergistic confinement effect to suppress the grain growth of α-Fe2O3 nanocrystals during the calcination process and to accommodate the stress generated by volume expansion during the charge/discharge process,leading to an enhanced interfacial conductivity and inhibit electrode pulverization and mechanical failure in the active material.With these merits,the prepared α-Fe2O3/ZnFe2O4 composite delivers prolonged cycling stability and improved rate capability with a higher specific capacity than sole α-Fe2O3 and ZnFe2O4.The discharge capacity is retained at 700 mAh g-1 after 500 cycles at 200 mA g-1 and 940 mAh g-1 after 50 cycles at 100 mA g-1.This work provides a new perspective in designing transition metal oxides for advanced lithium-ion batteries with superior electrochemical properties.     

NaFeTiO4 nanorod/multi-walled carbon nanotubes composite as an anode material for sodium-ion batteries with high performances in both half and full cells

NaFeTiO4 nanorods of high yields (with diameters in the range of 30-50 nm and lengths of up to 1-5 μm) were synthesized by a facile sol-gel method and were utilized as an anode material for sodium-ion batteries for the first time.The obtained NaFeTiO4 nanorods exhibit a high initial discharge capacity of 294 mA·h·g-1 at 0.2 C (1 C =177 mA·g-1),and remain at 115 mA·h·g-1 after 50 cycles.Furthermore,multi-walled carbon nanotubes (MWCNTs) were mechanically milled with the pristine material to obtain NaFeTiO4/MWCNTs.The NaFeTiO4/MWCNTs electrode exhibits a significantly improved electrochemical performance with a stable discharge capacity of 150 mA·h·g-1 at 0.2 C after 50 cycles,and remains at 125 mA·h·g-1 at 0.5 C after 420 cycles.The NaFeTiO4/MWCNTs//Na3V2(PO4)3/C full cell was assembled for the first time;it displays a discharge capacity of 70 mA·h·g-1 after 50 cycles at 0.05 C,indicating its excellent performances.X-ray photoelectron spectroscopy,ex situ X-ray diffraction,and Raman measurements were performed to investigate the initial electrochemical mechanisms of the obtained NaFeTiO4/MWCNTs.     

Implanting Atomic Cobalt within Mesoporous Carbon toward Highly Stable Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries hold great promise to serve as next‐generation energy storage devices. However, the practical performances of Li–S batteries are severely limited by the sulfur cathode regarding its low conductivity, huge volume change, and the polysulfide shuttle effect. The first two issues have been well addressed by introducing mesoporous carbon hosts to the sulfur cathode. Unfortunately, the nonpolar nature of carbon materials renders poor affinity to polar polysulfides, leaving the shuttling issue unaddressed. In this contribution, atomic cobalt is implanted within the skeleton of mesoporous carbon via a supramolecular self‐templating strategy, which simultaneously improves the interaction with polysulfides and maintains the mesoporous structure. Moreover, the atomic cobalt dopants serve as active sites to improve the kinetics of the sulfur redox reactions. With the atomic‐cobalt‐decorated mesoporous carbon host, a high capacity of 1130 mAh g_S^?1 at 0.5 C and a high stability with a retention of 74.1% after 300 cycles are realized. Implanting atomic metal in mesoporous carbon demonstrates a feasible strategy to endow nanomaterials with targeted functions for Li–S batteries and broad applications.     

Graphene-wrapped sulfur particles as a rechargeable lithium-sulfur battery cathode material with high capacity and cycling stability

We report the synthesis of a graphene-sulfur composite material by wrapping poly(ethylene glycol) (PEG) coated submicrometer sulfur particles with mildly oxidized graphene oxide sheets decorated by carbon black nanoparticles. The PEG and graphene coating layers are important to accommodating volume expansion of the coated sulfur particles during discharge, trapping soluble polysulfide intermediates, and rendering the sulfur particles electrically conducting. The resulting graphene-sulfur composite showed high and stable specific capacities up to ～600 mAh/g over more than 100 cycles, representing a promising cathode material for rechargeable lithium batteries with high energy density.     

Long‐Life Lithium–Sulfur Batteries with a Bifunctional Cathode Substrate Configured with Boron Carbide Nanowires

Developing high‐energy‐density lithium–sulfur (Li–S) batteries relies on the design of electrode substrates that can host a high sulfur loading and still attain high electrochemical utilization. Herein, a new bifunctional cathode substrate configured with boron‐carbide nanowires in situ grown on carbon nanofibers (B₄C@CNF) is established through a facile catalyst‐assisted process. The B₄C nanowires acting as chemical‐anchoring centers provide strong polysulfide adsorptivity, as validated by experimental data and first‐principle calculations. Meanwhile, the catalytic effect of B₄C also accelerates the redox kinetics of polysulfide conversion, contributing to enhanced rate capability. As a result, a remarkable capacity retention of 80% after 500 cycles as well as stable cyclability at 4C rate is accomplished with the cells employing B₄C@CNF as a cathode substrate for sulfur. Moreover, the B₄C@CNF substrate enables the cathode to achieve both high sulfur content (70 wt%) and sulfur loading (10.3 mg cm^?2), delivering a superb areal capacity of 9 mAh cm^?2. Additionally, Li–S pouch cells fabricated with the B₄C@CNF substrate are able to host a high sulfur mass of 200 mg per cathode and deliver a high discharge capacity of 125 mAh after 50 cycles.     

Three-dimensionally ordered,ultrathin graphitic-carbon frameworks with cage-like mesoporosity for highly stable Li-S batteries

Mesoporous carbons have been widely utilized as the sulfur host for lithium-sulfur (Li-S) batteries.The ability to engineer the porosity,wall thickness,and graphitization degree of the carbon host is essential for addressing issues that hamper commercialization of Li-S batteries,such as fast capacity decay and poor high-rate performance.In this work,highly ordered,ultrathin mesoporous graphitic-carbon frameworks (MGFs) having unique cage-like mesoporosity,derived from self-assembled Fe3O4 nanoparticle superlattices,are demonstrated to be an excellent host for encapsulating sulfur.The resulting S@MGFs exhibit high specific capacity (1,446 mAh·g-1 at 0.15 C),good rate capability (430 mAh.g-1 at 6 C),and exceptional cycling stability (～0.049％ capacity decay per cycle at 1 C) when used as Li-S cathodes.The superior electrochemical performance of the S@MGFs is attributed to the many unique and advantageous structural features of MGFs.In addition to the interconnected,ultrathin graphitic-carbon framework that ensures rapid electron and lithium-ion transport,the microporous openings between adjacent mesopores efficiently suppress the diffusion of polysulfides,leading to improved capacity retention even at high current densities.     

3D Printing of a V8C7–VO2 Bifunctional Scaffold as an Effective Polysulfide Immobilizer and Lithium Stabilizer for Li–S Batteries

Lithium–sulfur (Li–S) batteries have heretofore attracted tremendous interest due to low cost and high energy density. In this realm, both the severe shuttling of polysulfide and the uncontrollable growth of dendritic lithium have greatly hindered their commercial viability. Recent years have witnessed the rapid development of rational approaches to simultaneously regulate polysulfide behaviors and restrain lithium dendritic growth. Nevertheless, the major obstacles for high-performance Li–S batteries still lie in little knowledge of bifunctional material candidates and inadequate explorations of advanced technologies for customizable devices. Herein, a “two-in-one” strategy is put forward to elaborate V₈C₇–VO₂ heterostructure scaffolds via the 3D printing (3DP) technique as dual-effective polysulfide immobilizer and lithium dendrite inhibitor for Li–S batteries. A thus-derived 3DP-V₈C₇–VO₂/S electrode demostrates excellent rate capability (643.5 mAh g⁻¹ at 6.0 C) and favorable cycling stability (a capacity decay of 0.061% per cycle at 4.0 C after 900 cycles). Importantly, the integrated Li–S battery harnessing both 3DP hosts realizes high areal capacity under high sulfur loadings (7.36 mAh cm⁻² at a sulfur loading of 9.2 mg cm⁻²). This work offers insight into solving the concurrent challenges for both S cathode and Li anode throughout 3DP.     

Nickel embedded porous macrocellular carbon derived from popcorn as sulfur host for high-performance lithium-sulfur batteries

Due to the demands for high performance and ecological and economical alternatives to conventional lithium-ion batteries (LiBs),the development of lithium-sulfur (Li-S) batteries with remarkably higher theoretical capacity (1675 mA h g-1) has become one of the extensive research focus directions world-wide.However,poor conductivity of sulfur,critical cyclability problems due to shuttle of polysulfides as intermediate products of the cathodic reaction,and large volume variation of the sulfur composite cathode upon operation are the major bottlenecks impeding the implementation of the next-generation Li-S batteries.In this work,a unique three-dimensional (3D) interconnected macrocellular porous carbon (PC) architecture decorated with metal Ni nanopatticles was synthesized by a simple and facile strategy.The as-fabricated Ni/PC composite combines the merits of conducting carbon skeleton and highly adsorptive abilities of Ni,which resulted in efficient trapping of lithium polysulfides (LiPSs) and their fast conversion in the electrochemical process.Owing to these synergistic advantageous features,the composite exhibited good cycling stability (512.3 mA h g-1 after 1000 cycles at 1 C with an extremely low capacity fading rate 0.03 ％ per cycle),and superior rate capability (747.5 mAh g-1 at 2 C).Accordingly,such Ni nanoparticles embedded in a renewable puffed corn-derived carbon prepared via a simple and effective route represent a promising active type of sulfur host matrix to fabricate high-performance Li-S batteries.     

B,N Codoped Graphitic Nanotubes Loaded with Co Nanoparticles as Superior Sulfur Host for Advanced Li–S Batteries

Lithium–sulfur batteries (LSBs) are considered as one of the best candidates for novel rechargeable batteries due to their high energy densities and abundant required materials. However, the poor conductivity and large volume expansion of sulfur and the “shuttle effect” of lithium polysulfides (LPSs) have significantly hindered the development and successful commercialization of LSBs. Bean‐like B,N codoped carbon nanotubes loaded with Co nanoparticles (Co@BNTs), which can act as advanced sulfur hosts for the novel LSB cathode, are fabricated. Uniform graphitic nanotubes improve the conductivity of the electrode and load more electroactive sulfur and buffer volume expansion during the electrochemical reaction. In addition, loaded Co nanoparticles and codoped B,N sites can significantly suppress the “shuttle effect” of LPSs with strong chemical interaction. It is established that the Co nanoparticles and codoped B,N can provide more active sites to catalyze the redox reaction of sulfur cathode. This stable Co@BNTs‐S cathode displays an exceptional electrochemical performance (1160 mA h g^?1 after 200 cycles at 0.1 C) and outstanding stable cycle performance (1008 mA h g^?1 after 400 cycles at 1.0 C with an extremely low attenuation rate of 0.038% per cycle).