Metal Sulfide‐Decorated Carbon Sponge as a Highly Efficient Electrocatalyst and Absorbant for Polysulfide in High‐Loading Li2S Batteries

Owing to its high theoretical specific capacity (1166 mA h g^?1) and particularly its advantage to be paired with a lithium‐metal‐free anode, lithium sulfide (Li₂S) is regarded as a much safer cathode for next‐generation advanced lithium–sulfur (Li–S) batteries. However, the low conductivity of Li₂S and particularly the severe “polysulfide shuttle” of lithium polysulfide (LiPS) dramatically hinder their practical application in Li–S batteries. To address such issues, herein a bifuctional 3D metal sulfide‐decorated carbon sponge (3DTSC), which is constructed by 1D carbon nanowires cross‐linked with 2D graphene nanosheets with high conductivity and polar 0D metal sulfide nanodots with efficient electrocatalytic activity and strong chemical adsorption capability for LiPSs, is presented. Benefiting from the well‐designed multiscale, multidimensional 3D porous nanoarchitecture with high conductivity, and efficient electrocatalytic and absorption ability, the 3DTSC significantly mitigates LiPS shuttle, improves the utilization of Li₂S, and facilitates the transport of electrons and ions. As a result, even with a high Li₂S loading of 8 mg cm^?2, the freestanding 3DTSC‐Li₂S cathode without a polymer binder and metallic current collector delivers outstanding electrochemical performance with a high areal capacity of 8.44 mA h cm^?2.     

Dual‐Confined Flexible Sulfur Cathodes Encapsulated in Nitrogen‐Doped Double‐Shelled Hollow Carbon Spheres and Wrapped with Graphene for Li–S Batteries

Batteries with high energy and power densities along with long cycle life and acceptable safety at an affordable cost are critical for large‐scale applications such as electric vehicles and smart grids, but is challenging. Lithium–sulfur (Li‐S) batteries are attractive in this regard due to their high energy density and the abundance of sulfur, but several hurdles such as poor cycle life and inferior sulfur utilization need to be overcome for them to be commercially viable. Li–S cells with high capacity and long cycle life with a dual‐confined flexible cathode configuration by encapsulating sulfur in nitrogen‐doped double‐shelled hollow carbon spheres followed by graphene wrapping are presented here. Sulfur/polysulfides are effectively immobilized in the cathode through physical confinement by the hollow spheres with porous shells and graphene wrapping as well as chemical binding between heteronitrogen atoms and polysulfides. This rationally designed free‐standing nanostructured sulfur cathode provides a well‐built 3D carbon conductive network without requiring binders, enabling a high initial discharge capacity of 1360 mA h g^?1 at a current rate of C/5, excellent rate capability of 600 mA h g^?1 at 2 C rate, and sustainable cycling stability for 200 cycles with nearly 100% Coulombic efficiency, suggesting its great promise for advanced Li–S batteries.     

MoN Supported on Graphene as a Bifunctional Interlayer for Advanced Li‐S Batteries

Rational design of effective polysulfide barriers is highly important for high‐performance lithium‐sulfur (Li‐S) batteries. A variety of adsorbents have been applied as interlayers to alleviate the shuttle effect. Nevertheless, the unsuccessful oxidation of Li₂S on interlayers leads to loss of active materials and blocks Li ion transport. In this work, a MoN‐based interlayer sandwiched between the C‐S cathode and the separator is developed. Such an interlayer not only strongly binds lithium polysulfides via Mo‐S bonding but also efficiently accelerates the decomposition of Li₂S. The acceleration mechanism toward Li₂S decomposition is determined to be a combination of contributions of catalytic cleavage of Li‐S bond in Li₂S based on the proposed covalence‐activation mechanism and rapid migration of the produced Li ions. As a result, the C–S cathodes with the as‐developed interlayer manifest a negligible charging potential barrier and outstanding cycling stability with a very low capacity fading rate of 0.023% per cycle during 1500 cycles at 1 C. High areal capacity of 6.02 mAh cm^?2 is achieved for high sulfur loading of 7.0 mg cm^?2 after cycling at 0.1 C. The material and strategy demonstrated in this work can open the door toward developing shuttle suppression interlayers without impairing cathode performance.     

Highly Dispersed Cobalt Clusters in Nitrogen‐Doped Porous Carbon Enable Multiple Effects for High‐Performance Li–S Battery

The lithium–sulfur (Li–S) battery is considered a promising candidate for the next generation of energy storage system due to its high specific energy density and low cost of raw materials. However, the practical application of Li–S batteries is severely limited by several weaknesses such as the shuttle effect of polysulfides and the insulation of the electrochemical products of sulfur and Li₂S/Li₂S₂. Here, by doping nitrogen and integrating highly dispersed cobalt catalysts, a porous carbon nanocage derived from glucose adsorbed metal–organic framework is developed as the host for a sulfur cathode. This host structure combines the reported positive effects, including high conductivity, high sulfur loading, effective stress release, fast lithium‐ion kinetics, fast interface charge transport, fast redox of Li₂S_n, and strong physical/chemical absorption, achieving a long cycle life (86% of capacity retention at 1C within 500 cycles) and high rate performance (600 mAh g^?1 at 5C) for a Li–S battery. By combining experiments and density functional theoretical calculations, it is demonstrated that the well‐dispersed cobalt clusters play an important role in greatly improving the diffusion dynamics of lithium, and enhance the absorption and conversion capability of polysulfides in the host structure.     

Covalent Encapsulation of Sulfur in a MOF‐Derived S,N‐Doped Porous Carbon Host Realized via the Vapor‐Infiltration Method Results in Enhanced Sodium–Sulfur Battery Performance

Practical applications of room temperature sodium–sulfur batteries are still inhibited by the poor conductivity and slow reaction kinetics of sulfur, and dissolution of intermediate polysulfides in the commonly used electrolytes. To address these issues, starting from a novel 3D Zn‐based metal–organic framework with 2,5‐thiophenedicarboxylic acid and 1,4‐bis(pyrid‐4‐yl) benzene as ligands, a S, N‐doped porous carbon host with 3D tubular holes for sulfur storage is fabricated. In contrast to the commonly used melt‐diffusion method to confine sulfur physically, a vapor‐infiltration method is utilized to achieve sulfur/carbon composite with covalent bonds, which can join electrochemical reaction without low voltage activation. A polydopamine derived N‐doped carbon layer is further coated on the composite to confine the high‐temperature‐induced gas‐phase sulfur inside the host. S and N dopants increase the polarity of the carbon host to restrict diffusion of sulfur, and its 3D porous structure provides a large storage area for sulfur. As a result, the obtained composite shows outstanding electrochemical performance with 467 mAh g^?1 (1262 mAh g^?1_(sulfur)) at 0.1 A g^?1, 270 mAh g^?1 (730 mAh g^?1_(sulfur)) after 1000 cycles at 1 A g^?1 and 201 mAh g^?1 (543 mAh g^?1_(sulfur)) at 5.0 A g^?1.     

A Conductive Molecular Framework Derived Li2S/N,P‐Codoped Carbon Cathode for Advanced Lithium–Sulfur Batteries

Li₂S is one of the most promising cathode materials for Li‐ion batteries because of its high theoretical capacity and compatibility with Li‐metal‐free anode materials. However, the poor conductivity and electrochemical reactivity lead to low initial capacity and severe capacity decay. In this communication, a nitrogen and phosphorus codoped carbon (N,P–C) framework derived from phytic acid doped polyaniline hydrogel is designed to support Li₂S nanoparticles as a binder‐free cathode for Li–S battery. The porous 3D architecture of N and P codoped carbon provides continuous electron pathways and hierarchically porous channels for Li ion transport. Phosphorus doping can also suppress the shuttle effect through strong interaction between sulfur and the carbon framework, resulting in high Coulombic efficiency. Meanwhile, P doping in the carbon framework plays an important role in improving the reaction kinetics, as it may help catalyze the redox reactions of sulfur species to reduce electrochemical polarization, and enhance the ionic conductivity of Li₂S. As a result, the Li₂S/N,P–C composite electrode delivers a stable capacity of 700 mA h g^?1 with average Coulombic efficiency of 99.4% over 100 cycles at 0.1C and an areal capacity as high as 2 mA h cm^?2 at 0.5C.     

Rational Design of a Dual‐Function Hybrid Cathode Substrate for Lithium–Sulfur Batteries

A unique 3D hybrid sponge with chemically coupled nickel disulfide‐reduced graphene oxide (NiS₂‐RGO) framework is rationally developed as an effective polysulfide reservoir through a biomolecule‐assisted self‐assembly synthesis. An optimized amount of NiS₂ (≈18 wt%) with porous nanoflower‐like morphology is uniformly in situ grown on the RGO substrate, providing abundant active sites to adsorb and localize polysulfides. The improved polysulfide adsorptivity from sulfiphilic NiS₂ is confirmed by experimental data and first‐principle calculations. Moreover, due to the chemical coupling between NiS₂ and RGO formed during the in situ synthesis, the conductive RGO substrate offers a 3D electron pathway to facilitate charge transfer toward the NiS₂‐polysulfide adsorption interface, triggering a fast redox kinetics of polysulfide conversion and excellent rate performance (C/20–4C). Therefore, the self‐assembled hybrid structure simultaneously promotes static polysulfide‐trapping capability and dynamic polysulfide‐conversion reversibility. As a result, the 3D porous sponge enables a high sulfur content (75 wt%) and a remarkably high sulfur loading (up to 21 mg cm^?2) and areal capacity (up to 16 mAh cm^?2), exceeding most of the reported values in the literature involving either RGO or metal sulfides/other metal compounds (sulfur content of <60 wt% and sulfur loading of <3 mg cm^?2).     

Dense Graphene Monolith for High Volumetric Energy Density Li–S Batteries

Despite the outstanding gravimetric performance of lithium–sulfur (Li–S) batteries, their practical volumetric energy density is normally lower than that of lithium‐ion batteries, mainly due to the low density of nanostructured sulfur as well as the porous carbon hosts. Here, a novel approach is developed to fabricate high‐density graphene bulk materials with “ink‐bottle‐like” mesopores by phosphoric acid (H₃PO₄) activation. These pores can effectively confine the polysulfides due to their unique structure with a wide body and narrow neck, which shows only a 0.05% capacity fade per cycle for 500 cycles (75% capacity retention) for accommodating polysulfides. With a density of 1.16 g cm^?3, a hybrid cathode containing 54 wt% sulfur delivers a high volumetric capacity of 653 mA h cm^?3. As a result, a device‐level volumetric energy density as high as 408 W h L^?1 is achieved with a cathode thickness of 100 µm. This is a periodic yet practical advance to improve the volumetric performance of Li–S batteries from a device perspective. This work suggests a design principle for the real use Li–S batteries although there is a long way ahead to bridge the gap between Li–S batteries and Li–ion batteries in volumetric performance.     

Separator Modified by Cobalt‐Embedded Carbon Nanosheets Enabling Chemisorption and Catalytic Effects of Polysulfides for High‐Energy‐Density Lithium‐Sulfur Batteries

Lithium‐sulfur (Li‐S) batteries are considered to be one of the promising next‐generation energy storage systems. Considerable progress has been achieved in sulfur composite cathodes, but high cycling stability and discharging capacity at the expense of volumetric capacity have offset their advantages. Herein, a functional separator is presented by coating cobalt‐embedded nitrogen‐doped porous carbon nanosheets and graphene on one surface of a commercial polypropylene separator. The coating layer not only suppresses the polysulfide shuttle effect through chemical affinity, but also functions as an electrocatalyst to propel catalytic conversion of intercepted polysulfides. The slurry‐bladed carbon nanotubes/sulfur cathode with 90 wt% sulfur deliver high reversible capacity of 1103 mA h g^?1 and volumetric capacity of 1062 mA h cm^?3 at 0.2 C, and the freestanding carbon nanofibers/sulfur cathode provides a high discharging capacity of 1190 mA h g^?1 and volumetric capacity of 1136 mA h cm^?3 at high sulfur content of 78 wt% and sulfur loading of 10.5 mg cm^?2. The electrochemical performance is comparable with or even superior to those in the state‐of‐the‐art carbon‐based sulfur cathodes. The separator reported in this work holds great promise for the development of high‐energy‐density Li‐S batteries.     

High‐Performance Lithium‐Sulfur Batteries with a Self‐Supported, 3D Li2S‐Doped Graphene Aerogel Cathodes

Lithium‐sulfur (Li‐S) batteries are being considered as the next‐generation high‐energy‐storage system due to their high theoretical energy density. However, the use of a lithium‐metal anode poses serious safety concerns due to lithium dendrite formation, which causes short‐circuiting, and possible explosions of the cell. One feasible way to address this issue is to pair a fully lithiated lithium sulfide (Li₂S) cathode with lithium metal‐free anodes. However, bulk Li₂S particles face the challenges of having a large activation barrier during the initial charge, low active‐material utilization, poor electrical conductivity, and fast capacity fade, preventing their practical utility. Here, the development of a self‐supported, high capacity, long‐life cathode material is presented for Li‐S batteries by coating Li₂S onto doped graphene aerogels via a simple liquid infiltration–evaporation coating method. The resultant cathodes are able to lower the initial charge voltage barrier and attain a high specific capacity, good rate capability, and excellent cycling stability. The improved performance can be attributed to the (i) cross‐linked, porous graphene network enabling fast electron/ion transfer, (ii) coated Li₂S on graphene with high utilization and a reduced energy barrier, and (iii) doped heteroatoms with a strong binding affinity toward Li₂S/lithium polysulfides with reduced polysulfide dissolution based on first‐principles calculations.     

3D Printing Sulfur Copolymer‐Graphene Architectures for Li‐S Batteries

3D printing is becoming an efficient approach to facilely and accurately fabricate diverse complex architectures with broad applications. However, suitable inks and 3D print favorable architectures with high electrochemical performances for energy storage are still being explored. Here, sulfur copolymer‐graphene architectures with well‐designed periodic microlattices are 3D printed as a cathode for Li‐S batteries using a suitable ink composed of sulfur particles, 1,3‐diisopropenylbenzene (DIB), and condensed graphene oxide dispersion. Using thermal treatment, elemental sulfur can be reacted with DIB to produce sulfur copolymer, which can partially suppress the dissolution of polysulfides. Moreover, graphene in the architecture can provide high electrical conductivity for whole electrode. Hence, 3D printed sulfur copolymer‐graphene architecture exhibits a high reversible capacity of 812.8 mA h g^?1 and good cycle performance. Such a simple 3D printing approach can be further extended to construct many complex architectures for various energy storage devices.     

Sandwich‐Like Ultrathin TiS2 Nanosheets Confined within N,S Codoped Porous Carbon as an Effective Polysulfide Promoter in Lithium‐Sulfur Batteries

As the lightest member of transition metal dichalcogenides, 2D titanium disulfide (2D TiS₂) nanosheets are attractive for energy storage and conversion. However, reliable and controllable synthesis of single‐ to few‐layered TiS₂ nanosheets is challenging due to the strong tendency of stacking and oxidation of ultrathin TiS₂ nanosheets. This study reports for the first time the successful conversion of Ti₃C₂T_x MXene to sandwich‐like ultrathin TiS₂ nanosheets confined by N, S co‐doped porous carbon (TiS₂@NSC) via an in situ polydopamine‐assisted sulfuration process. When used as a sulfur host in lithium–sulfur batteries, TiS₂@NSC shows both high trapping capability for lithium polysulfides (LiPSs), and remarkable electrocatalytic activity for LiPSs reduction and lithium sulfide oxidation. A freestanding sulfur cathode integrating TiS₂@NSC with cotton‐derived carbon fibers delivers a high areal capacity of 5.9 mAh cm^?2 after 100 cycles at 0.1 C with a low electrolyte/sulfur ratio and a high sulfur loading of 7.7 mg cm^?2, placing TiS₂@NSC one of the best LiPSs adsorbents and sulfur conversion catalysts reported to date. The developed nanospace‐confined strategy will shed light on the rational design and structural engineering of metal sulfides based nanoarchitectures for diverse applications.     

A Li2S‐TiS2‐Electrolyte Composite for Stable Li2S‐Based Lithium–Sulfur Batteries

Li₂S is a fully lithiated sulfur‐based cathode with a high theoretical capacity of 1166 mAh g^?1 that can be coupled with lithium‐free anodes to develop high‐energy‐density lithium–sulfur batteries. Although various approaches have been pursued to obtain a high‐performance Li₂S cathode, there are still formidable challenges with it (e.g., low conductivity, high overpotential, and irreversible polysulfide diffusion) and associated fabrication processes (e.g., insufficient Li₂S, excess electrolyte, and low reversible capacity), which have prevented the realization of high electrochemical utilization and stability. Here, a new cathode design composed of a homogeneous Li₂S‐TiS₂‐electrolyte composite that is prepared by a simple two‐step dry/wet‐mixing process is demonstrated, allowing the liquid electrolyte to wet the powder mixture consisting of insulating Li₂S and conductive TiS₂. The close‐contact, three‐phase boundary of this system improves the Li₂S‐activation efficiency and provides fast redox‐reaction kinetics, enabling the Li₂S‐TiS₂‐electrolyte cathode to attain stable cyclability at C/7 to C/3 rates, superior long‐term cyclability over 500 cycles, and promising high‐rate performance up to 1C rate. More importantly, this improved performance results from a cell design attaining a high Li₂S loading of 6 mg cm^?2, a high Li₂S content of 75 wt%, and a low electrolyte/Li₂S ratio of 6.     

Chemical Immobilization and Conversion of Active Polysulfides Directly by Copper Current Collector: A New Approach to Enabling Stable Room‐Temperature Li‐S and Na‐S Batteries

Room‐temperature Li/Na‐S batteries are promising energy storage solutions, but unfortunately suffer from serious cycling problems rooted in their polysulfide intermediates. The conventional strategy to tackle this issue is to design host materials for trapping polysulfides via weak physical confinement and interfacial chemical interactions. Even though beneficial, their capability for the polysulfide immobilization is still limited. Herein, the unique sulfiphilic nature of metallic Cu is revisited. Upon the exposure to polysulfide in aqueous or aprotic solution, the surface sulfidization rapidly takes place, resulting in the formation of Cu₂S nanoflake arrays with tunable texture. When the sulfidized Cu current collector is directly used as the sulfur‐equivalent cathode, it enables high‐performance Li/Na‐S batteries at room temperature with reasonable high sulfur loading. Specific capacities up to ≈1200 mAh g^?1 for Li‐S and ≈400 mAh g^?1 for Na‐S are measured when normalized to the amount of equivalent sulfur, and can be readily sustained for >1000 cycles.     

Stabilization of Insoluble Discharge Products by Facile Aniline Modification for High Performance Li‐S Batteries

Continuous efforts have been made to attain high performance Li‐S batteries by preventing loss of soluble polysulfides, whereas issues related to insoluble discharge products, Li₂S₂ and Li₂S, have been underestimated. A facile and mild method, diazotization, that enables uniform functionalization on the surface of ordered mesoporous carbon (CMK‐3) with aniline functional groups while not deteriorating the original CMK‐3 microstructure is demonstrated. The aniline groups possess favorable interactions with insoluble discharge products. Thus, they homogeneously distribute the insoluble discharge products during cycling. The proposed materials exhibit outstanding electrochemical properties with regard to stability (920 mAh g^?1 at 0.2 C after 100 cycles) and rate capability (814 mAh g^?1 at 1 C) when evaluated as a cathode material for Li‐S batteries.     

Polysulfide‐Shuttle Control in Lithium‐Sulfur Batteries with a Chemically/Electrochemically Compatible NaSICON‐Type Solid Electrolyte

A NaSICON‐type Li⁺‐ion conductive membrane with a formula of Li_{1+ x} Y _x Zr_{2? x} (PO₄)₃ (LYZP) (x = 0–0.15) has been explored as a solid‐electrolyte/separator to suppress polysulfide‐crossover in lithium‐sulfur (Li‐S) batteries. The LYZP membrane with a reasonable Li⁺‐ion conductivity shows both favorable chemical compatibility with the lithium polysulfide species and exhibits good electrochemical stability under the operating conditions of the Li‐S batteries. Through an integration of the LYZP solid electrolyte with the liquid electrolyte, the hybrid Li‐S batteries show greatly enhanced cyclability in contrast to the conventional Li‐S batteries with the porous polymer (e.g., Celgard) separator. At a rate of C/5, the hybrid Li ||LYZP|| Li₂S₆ batteries developed in this study (with a Li‐metal anode, a liquid/LYZP hybrid electrolyte, and a dissolved lithium polysulfide cathode) delivers an initial discharge capacity of ≈1000 mA h g^?1 (based on the active sulfur material) and retains ≈90% of the initial capacity after 150 cycles with a low capacity fade‐rate of <0.07% per cycle.     

Elastic Sandwich‐Type rGO–VS2/S Composites with High Tap Density: Structural and Chemical Cooperativity Enabling Lithium–Sulfur Batteries with High Energy Density

Driven by increasing demand for high‐energy‐density batteries for consumer electronics and electric vehicles, substantial progress is achieved in the development of long‐life lithium–sulfur (Li–S) batteries. Less attention is given to Li–S batteries with high volume energy density, which is crucial for applications in compact space. Here, a series of elastic sandwich‐structured cathode materials consisting of alternating VS₂‐attached reduced graphene oxide (rGO) sheets and active sulfur layers are reported. Due to the high polarity and conductivity of VS₂, a small amount of VS₂ can suppress the shuttle effect of polysulfides and improve the redox kinetics of sulfur species in the whole sulfur layer. Sandwich‐structured rGO–VS₂/S composites exhibit significantly improved electrochemical performance, with high discharge capacities, low polarization, and excellent cycling stability compared with their bare rGO/S counterparts. Impressively, the tap density of rGO–VS₂/S with 89 wt% sulfur loading is 1.84 g cm^?3, which is almost three times higher than that of rGO/S with the same sulfur content (0.63 g cm^?3), and the volumetric specific capacity of the whole cell is as high as 1182.1 mA h cm^?3, comparable with the state‐of‐the‐art reported for energy storage devices, demonstrating the potential for application of these composites in long‐life and high‐energy‐density Li–S batteries.     

Nitrogen‐Doped Graphene‐Supported Mixed Transition‐Metal Oxide Porous Particles to Confine Polysulfides for Lithium–Sulfur Batteries

The intricate charge–discharge reactions and bad conductivity nature of sulfur determine the extreme importance of cathode engineering for Li–S batteries. Herein, spinel ZnCo₂O₄ porous particles@N‐doped reduced graphene oxide (ZnCo₂O₄@N‐RGO) are prepared via the combined procedures of refluxing and hydrothermal treatment, consisting of interconnected uniform ZnCo₂O₄ nanocubes with an average size of 5 nm anchored on graphene nanosheets. The as‐obtained composite can act as an inimitable cathode scaffold to suppress the shuttling of polysulfides by chemical confinement of ZnCo₂O₄ and N‐RGO for the first time, as demonstrated by the adsorption energy of ZnCo₂O₄ to Li₂S₄ via the strong chemical bonding between Zn or Co and S. The RGO nanosheets with a relatively high specific surface area provide a good conductive network and structural stability. The introduction of doped N atoms and numerous ZnCo₂O₄ porous nanoparticles can inhibit the transfer of lithium polysulfides between the cathode and anode. Due to the unique structural and compositional features, the as‐obtained hybrid materials with the high sulfur loading of 71% and even 82% still deliver high specific capacity, good rate capability, and enhanced cycling stability with exceptionally high initial Coulombic efficiency, which displays a high utilization of sulfur.     

Boosting Polysulfide Redox Kinetics by Graphene‐Supported Ni Nanoparticles with Carbon Coating

Lithium–sulfur batteries have attracted extensive attention because of their high energy density. However, their application is still impeded by the inherent sluggish kinetics and solubility of intermediate products (i.e., polysulfides) of the sulfur cathode. Herein, graphene‐supported Ni nanoparticles with a carbon coating are fabricated by directly carbonizing a metal–organic framework/graphene oxide composite, which is then dispersed on a commercial glass fiber membrane to form a separator with electrocatalytic activity. In situ analysis and electrochemical investigation demonstrate that this modified separator can effectively suppress the shuttle effect and regulate the catalytic conversion of intercepted polysulfides, which is also confirmed by density functional theory calculations. It is found that Ni–C sites can chemically interact with polysulfides and stabilize the radical S₃^?? through Ni? S bonds to enable fast dynamic equilibrium with S₆^2?, while Ni nanoparticles reduce the oxidation barrier of Li₂S and accelerate ion/electron transport. As a result, the corresponding lithium–sulfur battery shows a high cycle stability (88% capacity retention over 100 cycles) even with a high sulfur mass loading of 8 mg cm^?2 and lean electrolyte (6.25 µ L mg^?1). Surprisingly, benefitting from the improved kinetics, the battery can work well at ?50 °C, which is rarely achieved by conventional Li–S batteries.     

Interfacial Charge Field in Hierarchical Yolk–Shell Nanocapsule Enables Efficient Immobilization and Catalysis of Polysulfides Conversion

Inhibiting the shuttle effect of lithium polysulfides and accelerating their conversion kinetics are crucial for the development of high‐performance lithium–sulfur (Li–S) batteries. Herein, a modified template method is proposed to synthesize the robust yolk–shell sulfur host that is constructed by enveloping dispersive Fe₂O₃ nanoparticles within Mn₃O₄ nanosheet‐grafted hollow N‐doped porous carbon capsules (Fe₂O₃@N‐PC/Mn₃O₄‐S). When applied as a cathode for Li–S batteries, the as‐prepared Fe₂O₃@N‐PC/Mn₃O₄‐S can deliver capacities as high as 1122 mAh g^?1 after 200 cycles at 0.5 C and 639 mAh g^?1 after 1500 cycles at 10 C, respectively. Remarkably, even as the areal sulfur loading is increased to 5.1 mg cm^?2, the cathode can still maintain a high areal specific capacity of 5.08 mAh cm^?2 with a fading rate of only 0.076% per cycle over 100 cycles at 0.1 C. By a further combination analysis of electron holography and electron energy loss spectroscopy, the outstanding performance is revealed to be mainly traced to the oxygen‐vacancy‐induced interfacial charge field, which immobilizes and catalyzes the conversion of lithium polysulfides, assuring low polarization, fleet redox reaction kinetics, and sufficient utilization of sulfur. These new findings may shed light on the dependence of electrochemical performance on the heterostructure of sulfur hosts.