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.     

Design Principles for Heteroatom‐Doped Nanocarbon to Achieve Strong Anchoring of Polysulfides for Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries have been intensively concerned to fulfill the urgent demands of high capacity energy storage. One of the major unsolved issues is the complex diffusion of lithium polysulfide intermediates, which in combination with the subsequent paradox reactions is known as the shuttle effect. Nanocarbon with homogeneous nonpolar surface served as scaffolding materials in sulfur cathode basically cannot afford a sufficient binding and confining effect to maintain lithium polysulfides within the cathode. Herein, a systematical density functional theory calculation of various heteroatoms‐doped nanocarbon materials is conducted to elaborate the mechanism and guide the future screening and rational design of Li–S cathode for better performance. It is proved that the chemical modification using N or O dopant significantly enhances the interaction between the carbon hosts and the polysulfide guests via dipole–dipole electrostatic interaction and thereby effectively prevents shuttle of polysulfides, allowing high capacity and high coulombic efficiency. By contrast, the introduction of B, F, S, P, and Cl monodopants into carbon matrix is unsatisfactory. To achieve the strong‐couple effect toward Li₂S_x, the principles for rational design of doped carbon scaffolds in Li–S batteries to achieve a strong electrostatic dipole–dipole interaction are proposed. An implicit volcano plot is obtained to describe the dependence of binding energies on electronegativity of dopants. Moreover, the codoping strategy is predicted to achieve even stronger interfacial interaction to trap lithium polysulfides.     

Yolk–Shelled C@Fe3O4 Nanoboxes as Efficient Sulfur Hosts for High‐Performance Lithium–Sulfur Batteries

Owing to the high theoretical specific capacity (1675 mA h g^?1) and low cost, lithium–sulfur (Li–S) batteries offer advantages for next‐generation energy storage. However, the polysulfide dissolution and low electronic conductivity of sulfur cathodes limit the practical application of Li–S batteries. To address such issues, well‐designed yolk–shelled carbon@Fe₃O₄ (YSC@Fe₃O₄) nanoboxes as highly efficient sulfur hosts for Li–S batteries are reported here. With both physical entrapment by carbon shells and strong chemical interaction with Fe₃O₄ cores, this unique architecture immobilizes the active material and inhibits diffusion of the polysulfide intermediates. Moreover, due to their high conductivity, the carbon shells and the polar Fe₃O₄ cores facilitate fast electron/ion transport and promote continuous reactivation of the active material during the charge/discharge process, resulting in improved electrochemical utilization and reversibility. With these merits, the S/YSC@Fe₃O₄ cathodes support high sulfur content (80 wt%) and loading (5.5 mg cm^?2) and deliver high specific capacity, excellent rate capacity, and long cycling stability. This work provides a new perspective to design a carbon/metal‐oxide‐based yolk–shelled framework as a high sulfur‐loading host for advanced Li–S batteries with superior electrochemical properties.     

Recent Advances in Hollow Porous Carbon Materials for Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries are considered as one of the most potential next‐generation rechargeable batteries due to their high theoretical energy density. However, some critical issues, such as low capacity, poor cycling stability, and safety concerns, must be solved before Li–S batteries can be used practically. During the past decade, tremendous efforts have been devoted to the design and synthesis of electrode materials. Benefiting from their tunable structural parameters, hollow porous carbon materials (HPCM) remarkably enhance the performances of both sulfur cathodes and lithium anodes, promoting the development of high‐performance Li–S batteries. Here, together with the templated synthesis of HPCM, recent progresses of Li–S batteries based on HPCM are reviewed. Several important issues in Li–S batteries, including sulfur loading, polysulfide entrapping, and Li metal protection, are discussed, followed by a summary on recent research on HPCM‐based sulfur cathodes, modified separators, and lithium anodes. After the discussion on emerging technical obstacles toward high‐energy Li–S batteries, prospects for the future directions of HPCM research in the field of Li–S batteries are also proposed.     

Integrating Conductivity,Immobility, and Catalytic Ability into High-N Carbon/Graphene Sheets as an Effective Sulfur Host

Lithium–sulfur (Li–S) batteries are considered to be one of the most promising candidate systems for next-generation electrochemical energy storage. The major challenge of this system is the polysulfide shuttle, which results in poor cycling efficiency. In this work, a highly N-doped carbon/graphene (NC/G) sheet is designed as a sulfur host, which combines the merits of abundant N active sites and high electrical conductivity to achieve in situ anchoring–conversion of lithium polysulfides (LiPSs). Such a host not only has strong binding with LiPSs but also promotes redox kinetics, which are revealed by both experimental investigations and theoretical studies. The sulfur cathode based on the NC/G host exhibits a high initial capacity of 1380 mA h g⁻¹ and a superior cycle stability with a low capacity decay of 0.037% per cycle within 500 cycles at 2 C. Steady areal capacity with a high sulfur loading (5.6 mg cm⁻²) is also attained even without the addition of LiNO₃ in the electrolyte. This work proposes and illustrates the importance of in situ anchoring–conversion of LiPSs, offering a new strategy to design multifunctional sulfur hosts for high-performance Li–S batteries.     

Dual‐Function,Tunable, Nitrogen‐Doped Carbon for High‐Performance Li Metal–Sulfur Full Cell

Lithium metal–sulfur (Li–S) batteries are attracting broad interest because of their high capacity. However, the batteries experience the polysulfide shuttle effect in cathode and dendrite growth in the Li metal anode. Herein, a bifunctional and tunable mesoporous carbon sphere (MCS) that simultaneously boosts the performance of the sulfur cathode and the Li anode is designed. The MCS homogenizes the flux of Li ions and inhibits the growth of Li dendrites due to its honeycomb structure with high surface area and abundance of nitrogen sites. The Li@MCS cell exhibits a small overpotential of 29 mV and long cycling performance of 350 h under the current density of 1 mA cm^‐2. Upon covering one layer of amorphous carbon on the MCS (CMCS), an individual carbon cage is able to encapsulate sulfur inside and reduce the polysulfide shuttle, which improves the cycling stability of the Li–S battery. As a result, the S@CMCS has a maximum capacity of 411 mAh g^‐1 for 200 cycles at a current density of 3350 mA g^‐1. Based on the excellent performance, the full Li–S cell assembled with Li@MCS anode and S@CMCS cathode shows much higher capacity than a cell assembled with Li@Cu anode and S@CMCS cathode.     

Superhierarchical Cobalt‐Embedded Nitrogen‐Doped Porous Carbon Nanosheets as Two‐in‐One Hosts for High‐Performance Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries, based on the redox reaction between elemental sulfur and lithium metal, have attracted great interest because of their inherently high theoretical energy density. However, the severe polysulfide shuttle effect and sluggish reaction kinetics in sulfur cathodes, as well as dendrite growth in lithium‐metal anodes are great obstacles for their practical application. Herein, a two‐in‐one approach with superhierarchical cobalt‐embedded nitrogen‐doped porous carbon nanosheets (Co/N‐PCNSs) as stable hosts for both elemental sulfur and metallic lithium to improve their performance simultaneously is reported. Experimental and theoretical results reveal that stable Co nanoparticles, elaborately encapsulated by N‐doped graphitic carbon, can work synergistically with N heteroatoms to reserve the soluble polysulfides and promote the redox reaction kinetics of sulfur cathodes. Moreover, the high‐surface‐area pore structure and the Co‐enhanced lithiophilic N heteroatoms in Co/N‐PCNSs can regulate metallic lithium plating and successfully suppress lithium dendrite growth in the anodes. As a result, a full lithium–sulfur cell constructed with Co/N‐PCNSs as two‐in‐one hosts demonstrates excellent capacity retention with stable Coulombic efficiency.     

Stabilizing Lithium–Sulfur Batteries through Control of Sulfur Aggregation and Polysulfide Dissolution

Lithium–sulfur (Li–S) batteries are investigated intensively as a promising large‐scale energy storage system owing to their high theoretical energy density. However, the application of Li–S batteries is prevented by a series of primary problems, including low electronic conductivity, volumetric fluctuation, poor loading of sulfur, and shuttle effect caused by soluble lithium polysulfides. Here, a novel composite structure of sulfur nanoparticles attached to porous‐carbon nanotube (p‐CNT) encapsulated by hollow MnO₂ nanoflakes film to form p‐CNT@Void@MnO₂/S composite structures is reported. Benefiting from p‐CNTs and sponge‐like MnO₂ nanoflake film, p‐CNT@Void@MnO₂/S provides highly efficient pathways for the fast electron/ion transfer, fixes sulfur and Li₂S aggregation efficiently, and prevents polysulfide dissolution during cycling. Besides, the additional void inside p‐CNT@Void@MnO₂/S composite structure provides sufficient free space for the expansion of encapsulated sulfur nanoparticles. The special material composition and structural design of p‐CNT@Void@MnO₂/S composite structure with a high sulfur content endow the composite high capacity, high Coulombic efficiency, and an excellent cycling stability. The capacity of p‐CNT@Void@MnO₂/S electrode is ≈599.1 mA h g^?1 for the fourth cycle and ≈526.1 mA h g^?1 after 100 cycles, corresponding to a capacity retention of ≈87.8% at a high current density of 1.0 C.     

A Delicately Designed Sulfide Graphdiyne Compatible Cathode for High‐Performance Lithium/Magnesium–Sulfur Batteries

Novel sulfur cathodes hold the key to the development of metal–sulfur batteries, the promising candidate of next‐generation high‐energy‐storage systems. Herein, a fascinating sulfur cathode based on sulfide graphdiyne (SGDY) is designed with a unique structure, which is composed of a conducting carbon skeleton with high Li⁺ mobility and short sulfur energy‐storing unites. The SGDY cathode can essentially avoid polysulfide dissolution and be compatible with commercially available carbonate‐based electrolytes and Grignard reagent‐based electrolytes (all phenyl complex (APC) type electrolytes). Both the assembled Li–S and Mg–S batteries exhibit excellent electrochemical performances including large capacity, superior rate capability, high capacity retention, and high Coulombic efficiency. More importantly, this is the first implementation case of a reliable Mg–S system based on nucleophilic APC electrolytes.     

Single Nickel Atoms on Nitrogen‐Doped Graphene Enabling Enhanced Kinetics of Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries have arousing interest because of their high theoretical energy density. However, they often suffer from sluggish conversion of lithium polysulfides (LiPS) during the charge/discharge process. Single nickel (Ni) atoms on nitrogen‐doped graphene (Ni@NG) with Ni–N₄ structure are prepared and introduced to modify the separators of Li–S batteries. The oxidized Ni sites of the Ni–N₄ structure act as polysulfide traps, efficiently accommodating polysulfide ion electrons by forming strong S_x ^2????Ni? N bonding. Additionally, charge transfer between the LiPS and oxidized Ni sites endows the LiPS on Ni@NG with low free energy and decomposition energy barrier in an electrochemical process, accelerating the kinetic conversion of LiPS during the charge/discharge process. Furthermore, the large binding energy of LiPS on Ni@NG also shows its ability to immobilize the LiPS and further suppresses the undesirable shuttle effect. Therefore, a Li–S battery based on a Ni@NG modified separator exhibits excellent rate performance and stable cycling life with only 0.06% capacity decay per cycle. It affords fresh insights for developing single‐atom catalysts to accelerate the kinetic conversion of LiPS for highly stable Li–S batteries.     

Design Multifunctional Catalytic Interface: Toward Regulation of Polysulfide and Li2S Redox Conversion in Li–S Batteries

The polysulfide shuttle effect and sluggish reaction kinetics hamper the practical applications of lithium–sulfur (Li–S) batteries. Incorporating a functional interlayer to trapping and binding polysulfides has been found effective to block polysulfide migration. Furthermore, surface chemistry at soluble polysulfides/electrolyte interface is a crucial step for Li–S battery in which stable cycling depends on adsorption and reutilization of blocked polysulfides in the electrolyte. A multifunctional catalytic interface composed of niobium nitride/N‐doped graphene (NbN/NG) along the soluble polysulfides/electrolyte is designed and constructed to regulate corresponding interface chemical reaction, which can afford long‐range electron transfer surfaces, numerous strong chemisorption, and catalytic sites in a working lithium–sulfur battery. Both experimental and theoretical calculation results suggest that a new catalytic interface enabled by metal‐like NbN with superb electrocatalysis anchored on NG is highly effective in regulating the blocked polysulfide redox reaction and tailoring the Li₂S nucleation–growth–decomposition process. Therefore, the Li–S batteries with multifunctional NbN/NG barrier exhibit excellent rate performance (621.2 mAh g^?1 at 3 C) and high stable cycling life (81.5% capacity retention after 400 cycles). This work provides new insights to promote Li–S batteries via multifunctional catalytic interface engineering.     

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.     

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.     

Lithium–Sulfur Batteries: Progress and Prospects

Development of advanced energy‐storage systems for portable devices, electric vehicles, and grid storage must fulfill several requirements: low‐cost, long life, acceptable safety, high energy, high power, and environmental benignity. With these requirements, lithium–sulfur (Li–S) batteries promise great potential to be the next‐generation high‐energy system. However, the practicality of Li–S technology is hindered by technical obstacles, such as short shelf and cycle life and low sulfur content/loading, arising from the shuttling of polysulfide intermediates between the cathode and anode and the poor electronic conductivity of S and the discharge product Li₂S. Much progress has been made during the past five years to circumvent these problems by employing sulfur–carbon or sulfur–polymer composite cathodes, novel cell configurations, and lithium‐metal anode stabilization. This Progress Report highlights recent developments with special attention toward innovation in sulfur‐encapsulation techniques, development of novel materials, and cell‐component design. The scientific understanding and engineering concerns are discussed at the end in every developmental stage. The critical research directions needed and the remaining challenges to be addressed are summarized in the Conclusion.     

Self‐Supported and Flexible Sulfur Cathode Enabled via Synergistic Confinement for High‐Energy‐Density Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries have attracted much attention in the field of electrochemical energy storage due to their high energy density and low cost. However, the “shuttle effect” of the sulfur cathode, resulting in poor cyclic performance, is a big barrier for the development of Li–S batteries. Herein, a novel sulfur cathode integrating sulfur, flexible carbon cloth, and metal–organic framework (MOF)‐derived N‐doped carbon nanoarrays with embedded CoP (CC@CoP/C) is designed. These unique flexible nanoarrays with embedded polar CoP nanoparticles not only offer enough voids for volume expansion to maintain the structural stability during the electrochemical process, but also promote the physical encapsulation and chemical entrapment of all sulfur species. Such designed CC@CoP/C cathodes with synergistic confinement (physical adsorption and chemical interactions) for soluble intermediate lithium polysulfides possess high sulfur loadings (as high as 4.17 mg cm^–2) and exhibit large specific capacities at different C‐rates. Specially, an outstanding long‐term cycling performance can be reached. For example, an ultralow decay of 0.016% per cycle during the whole 600 cycles at a high current density of 2C is displayed. The current work provides a promising design strategy for high‐energy‐density Li–S batteries.     

A Highly Conductive MOF of Graphene Analogue Ni3(HITP)2 as a Sulfur Host for High‐Performance Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries have been considered as one of the most promising energy storage systems owing to their high theoretical capacity and energy density. However, their commercial applications are obstructed by sluggish reaction kinetics and rapid capacity degradation mainly caused by polysulfide shuttling. Herein, the first attempt to utilize a highly conductive metal–organic framework (MOF) of Ni₃(HITP)₂ graphene analogue as the sulfur host material to trap and transform polysulfides for high‐performance Li–S batteries is made. Besides, the traditional conductive additive acetylene black is replaced by carbon nanotubes to construct matrix conduction networks for triggering the rate and cycling performance of the active cathode. As a result, the S@Ni₃(HITP)₂ with sulfur content of 65.5 wt% shows excellent sulfur utilization, rate performance, and cyclic durability. It delivers a high initial capacity of 1302.9 mAh g^?1 and good capacity retention of 848.9 mAh g^?1 after 100 cycles at 0.2 C. Highly reversible discharge capacities of 807.4 and 629.6 mAh g^?1 are obtained at 0.5 and 1 C for 150 and 300 cycles, respectively. Such kinds of pristine MOFs with high conductivity and abundant polar sites reveal broad promising prospect for application in the field of high‐performance Li–S batteries.     

Anode Interface Engineering and Architecture Design for High‐Performance Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries are considered as one of the most promising options to realize rechargeable batteries with high energy capacity. Previously, research has mainly focused on solving the polysulfides' shuttle, cathode volume changes, and sulfur conductivity problems. However, the instability of anodes in Li–S batteries has become a bottleneck to achieving high performance. Herein, the main efforts to develop highly stable anodes for Li–S batteries, mainly including lithium metal anodes, carbon‐based anodes, and alloy‐based anodes, are considered. Based on these anodes, their interfacial engineering and structure design are identified as the two most important directions to achieve ideal anodes. Because of high reactivity and large volume change during cycling, Li anodes suffer from severe side reactions and structure collapse. The solid electrolyte interphase formed in situ by modified electrolytes and ex situ artificial coating layers can enhance the interfacial stability of anodes. Replacing common Li foil with rationally designed anodes not only suppresses the formation of dendritic Li but also delays the failure of Li anodes. Manipulating the anode interface engineering and rationally designing anode architecture represents an attractive path to develop high‐performance Li–S batteries.     

Optimization of Microporous Carbon Structures for Lithium–Sulfur Battery Applications in Carbonate‐Based Electrolyte

Developing appropriate sulfur cathode materials in carbonate‐based electrolyte is an important research subject for lithium‐sulfur batteries. Although several microporous carbon materials as host for sulfur reveal the effect, methods for producing microporous carbon are neither easy nor well controllable. Moreover, due to the complexity and limitation of microporous carbon in their fabrication process, there has been rare investigation of influence on electrochemical behavior in the carbonate‐based electrolyte for lithium‐sulfur batteries by tuning different micropore size(0–2 nm) of carbon host. Here, we demonstrate an immediate carbonization process, self‐activation strategy, which can produce microporous carbon for a sulfur host from alkali‐complexes. Besides, by changing different alkali‐ion in the previous complex, the obtained microporous carbon exhibits a major portion of ultramicropore (<0.7 nm, from 54.9% to 25.8%) and it is demonstrated that the micropore structure of the host material plays a vital role in confining sulfur molecule. When evaluated as cathode materials in a carbonate‐based electrolyte for Li‐S batteries, such microporous carbon/sulfur composite can provide high reversible capacity, cycling stability and good rate capability.     

In Situ 1D Carbon Chain-Mail Catalyst Assembly for Stable Lithium–Sulfur Full Batteries

The main obstacles for the commercial application of Lithium–Sulfur (Li–S) full batteries are the large volume change during charging/discharging process, the shuttle effect of lithium polysulfide (LiPS), sluggish redox kinetics, and the indisciplinable dendritic Li growth. Especially the overused of metal Li leads to the low utilization of active Li, which seriously drags down the actual energy density of Li–S batteries. Herein, an efficient design of dual-functional CoSe electrocatalyst encapsulated in carbon chain-mail (CoSe@CCM) is employed as the host both for the cathode and anode regulation simultaneously. The carbon chain-mail constituted by carbon encapsulated layer cross-linking with carbon nanofibers protects CoSe from the corrosion of chemical reaction environment, ensuring the high activity of CoSe during the long-term cycles. The Li–S full battery using this carbon chain-mail catalyst with a lower negative/positive electrode capacity ratio (N/P < 2) displays a high areal capacity of 9.68 mAh cm⁻² over 150 cycles at a higher sulfur loading of 10.67 mg cm⁻². Additionally, a pouch cell is stable for 80 cycles at a sulfur loading of 77.6 mg, showing the practicality feasibility of this design.     

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.