A Combined Ordered Macro‐Mesoporous Architecture Design and Surface Engineering Strategy for High‐Performance Sulfur Immobilizer in Lithium–Sulfur Batteries

The practical application of lithium–sulfur (Li–S) batteries is hindered by the “shuttle” of lithium polysulfides (LiPS) and sluggish Li–S kinetics issues. Herein, a synergistic strategy combining mesoporous architecture design and defect engineering is proposed to synthesize multifunctional defective 3D ordered mesoporous cobalt sulfide (3DOM N‐Co₉S_8?x) to address the shuttling and sluggish reaction kinetics of polysulfide in Li–S batteries. The unique 3DOM design provides abundant voids for sulfur storage and enlarged active interfaces that reduce electron/ion diffusion pathways. Meanwhile, X‐ray absorption spectroscopy shows that the surface defect engineering tunes the CoS₄ tetrahedra to CoS₆ octahedra on Co₉S₈, endowing abundance of S vacancies on the Co₉S₈ octahedral sites. The ever‐increasing S vacancies over the course of electrochemical process further promotes the chemical trapping of LiPS and its conversion kinetics, rendering fast and durable Li–S chemistry. Benefiting from these features, the as‐developed 3DOM N‐Co₉S_8?x/S cathode delivers high areal capacity, superb rate capability, and excellent cyclic stability with ultralow capacity fading rate under raised sulfur loading and low electrolyte content. This design strategy promotes the development of practically viable Li–S batteries and sheds lights on the material engineering in related energy storage application.     

Constructing Patch‐Ni‐Shelled Pt@Ni Nanoparticles within Confined Nanoreactors for Catalytic Oxidation of Insoluble Polysulfides in Li‐S Batteries

Reducing the deposit of discharge products and suppressing the polysulfide shuttle are critical to enhancing reaction kinetics in Li‐S batteries. Herein, a Pt@Ni core–shell bimetallic catalyst with a patch‐like or complete Ni shell based on a confined catalysis reaction in porous carbon spheres is reported. The Pt nanodots can effectively direct and catalyze in situ reduction of Ni²⁺ ions to form core–shell catalysts with a seamless interface that facilitates the charge transfer between the two metals. Thus, the bimetallic catalysts offer a synergic effect on catalyzing reactions, which shows dual functions for catalytic oxidation of insoluble polysulfides to soluble polysulfides by effectively reducing the energy barrier with simultaneous strong adsorption, ensuring a high reversible capacity and cycling stability. A novel process based on the Pt@Ni core–shell bimetallic catalyst with a patch‐like Ni shell is proposed: electronic migration from Ni to Pt forces Ni to activate Li₂S₂/Li₂S molecules by promoting the transformation of Li‐S‐Li to Ni‐S‐Li, consequently releasing Li⁺ and free electrons, simultaneously enhancing protonic/electronic conductivity. The presence of the intermediate state Ni‐S‐Li is more active to oxidize Li₂S to polysulfides. The Li₂S bound to adjacent Pt sites reacts with abundant ‐S‐Li species and then releases the Pt sites for the next round of reactions.     

Low-Bandgap Se-Deficient Antimony Selenide as a Multifunctional Polysulfide Barrier toward High-Performance Lithium–Sulfur Batteries

The shuttling behavior and sluggish conversion kinetics of the intermediate lithium polysulfides (LiPSs) represent the main obstructions to the practical application of lithium–sulfur (Li–S) batteries. Herein, an anion-deficient design of antimony selenide (Sb₂Se_3−x) is developed to establish a multifunctional LiPS barrier toward the inhibition of polysulfide shuttling and enhancement of battery performance. The defect chemistry in the as-developed Sb₂Se_3−x promotes the intrinsic conductivity, strengthens the chemical affinity to LiPSs, and catalyzes the sulfur electrochemical conversion, which are verified by a series of computational and experimental results. Attributed to these unique superiorities, the obtained LiPS barrier efficiently promotes and stabilizes the sulfur electrochemistry, thus enabling excellent Li–S battery performance, e.g., outstanding cyclability over 500 cycles at 1.0 C with a minimum capacity fading rate of 0.027% per cycle, a superb rate capability up to 8.0 C, and a high areal capacity of 7.46 mAh cm⁻² under raised sulfur loading. This work offers a defect engineering strategy toward fast and durable sulfur electrochemistry, holding great promise in developing practically viable Li–S batteries as well as enlightening the material design of related energy storage and conversion systems.     

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.     

Multifunctional Interlayer Based on Molybdenum Diphosphide Catalyst and Carbon Nanotube Film for Lithium–Sulfur Batteries

A multifunctional interlayer, composed of molybdenum diphosphide (MoP₂) nanoparticles and a carbon nanotube (CNT) film, is introduced into a lithium–sulfur (Li–S) battery system to suppress polysulfide migration. Molybdenum diphosphide acts as the catalyst and can capture polysulfides and improve the polysulfide conversion activity during the discharge/charge processes. The CNT film acts as a conductive skeleton to support the MoP₂ nanoparticles and to ensure their uniform distribution. The CNT film physically hinders polysulfide migration, acts as a current collector, and provides abundant electron pathways. The Li–S battery containing the multifunctional MoP₂/CNT interlayer exhibits excellent electrochemical performance. It delivers a reversible specific capacity of 905 mA h g^?1 over 100 cycles at 0.2 C, with a capacity decay of 0.152% per cycle. These results suggest the introduction of the multifunctional CNT/MoP₂ interlayer as an effective and practical method for producing high‐performance Li–S batteries.     

Integration of Binary Active Sites: Co3V2O8 as Polysulfide Traps and Catalysts for Lithium‐Sulfur Battery with Superior Cycling Stability

Lithium‐sulfur (Li‐S) batteries as a promising energy storage candidate have attracted attention due to their high energy density (2600 Wh kg^?1). However, the serious shuttle effect caused by the dissolution of the lithium polysulfides (LiPS) in electrolyte significantly degrades their cycling life and rate performance. Herein, the “binary active sites” concept in a Li‐S battery system via the design of a cobalt vanadium oxide (CVO) modified multifunctional separator is designed. In the case of CVO, active vanadium sites simultaneously anchor the LiPS through the chemical affinity and active cobalt sites can dominate a rapid kinetic conversion. Such a synergistic effect contributes to improving the utilization of sulfur in the electrochemical process for the enhanced electrochemical performance. As a result, the Li‐S battery with the CVO modified separator possesses a high reversible capacity of 1585.5 mAh g^?1 at 0.1 C and superior cycling stability with 0.012% capacity decay cycle^?1 after 3000 cycles. More impressively, the assembled soft‐packaged Li‐S devices can exhibit the excellent stability under bending states. This binary active sites strategy provides a route to design the functional materials for modifying separators of Li‐S batteries to improve the performance.     

A Bifunctional Perovskite Promoter for Polysulfide Regulation toward Stable Lithium–Sulfur Batteries

Lithium‐sulfur (Li? S) batteries are strongly considered as the next‐generation rechargeable cells. However, both the shuttle of lithium polysulfides (LiPSs) and sluggish kinetics in random deposition of lithium sulfides (Li₂S) significantly degrade the capacity, rate performance, and cycling life of Li? S cells. Herein, bifunctional Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ perovskite nanoparticles (PrNPs) are proposed as a promoter to immobilize LiPSs and guide the deposition of Li₂S in a Li? S cell. The oxygen vacancy in PrNPs increases the metal reactivity to anchor LiPSs, and co‐existence of lithiophilic (O) and sulfiphilic (Sr) sites in PrNP favor the dual‐bonding (Li? O and Sr? S bonds) to anchor LiPSs. The high catalytic nature of PrNP facilitates the kinetics of LiPS redox reaction. The PrNP with intrinsic LiPS affinity serves as nucleation sites for Li₂S deposition and guides its uniform propagation. Therefore, the bifunctional LiPS promoter in Li? S cell yields high rate performance and ultralow capacity decay rate of 0.062% (a quarter of pristine Li? S cells). The proposed strategy to immobilize LiPSs, promotes the conversion of LiPS, and regulates deposition of Li₂S by an emerging perovskite promoter and is also expected to be applied in other energy conversion and storage devices based on multi‐electron redox reactions.     

Promoting the Transformation of Li2S2 to Li2S: Significantly Increasing Utilization of Active Materials for High‐Sulfur‐Loading Li–S Batteries

Lithium–sulfur (Li–S) batteries with high sulfur loading are urgently required in order to take advantage of their high theoretical energy density. Ether‐based Li–S batteries involve sophisticated multistep solid–liquid–solid–solid electrochemical reaction mechanisms. Recently, studies on Li–S batteries have widely focused on the initial solid (sulfur)–liquid (soluble polysulfide)–solid (Li₂S₂) conversion reactions, which contribute to the first 50% of the theoretical capacity of the Li–S batteries. Nonetheless, the sluggish kinetics of the solid–solid conversion from solid‐state intermediate product Li₂S₂ to the final discharge product Li₂S (corresponding to the last 50% of the theoretical capacity) leads to the premature end of discharge, resulting in low discharge capacity output and low sulfur utilization. To tackle the aforementioned issue, a catalyst of amorphous cobalt sulfide (CoS₃) is proposed to decrease the dissociation energy of Li₂S₂ and propel the electrochemical transformation of Li₂S₂ to Li₂S. The CoS₃ catalyst plays a critical role in improving the sulfur utilization, especially in high‐loading sulfur cathodes (3–10 mg cm^?2). Accordingly, the Li₂S/Li₂S₂ ratio in the discharge products increased to 5.60/1 from 1/1.63 with CoS₃ catalyst, resulting in a sulfur utilization increase of 20% (335 mAh g^?1) compared to the counterpart sulfur electrode without CoS₃.     

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.     

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.     

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.     

Molybdenum Boride as an Efficient Catalyst for Polysulfide Redox to Enable High-Energy-Density Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries, despite having high theoretical specific energy, possess many practical challenges, including lithium polysulfide (LiPS) shuttling. To address the issues, here, hydrophilic molybdenum boride (MoB) nanoparticles are presented as an efficient catalytic additive for sulfur cathodes. The high conductivity and rich catalytically active sites of MoB nanoparticles allow for a fast kinetics of LiPS redox in high-sulfur-loading electrodes (6.1 mg cm⁻²). Besides, the hydrophilic properties and good wettability toward electrolyte of MoB can facilitate electrolyte penetration and LiPS redox, guaranteeing a high utilization of sulfur under a lean-electrolyte condition. Therefore, the cells with MoB achieve impressive electrochemical performance, including a high capacity (1253 mA h g⁻¹) and ultralong lifespan (1000 cycles) with a low capacity fade rate of 0.03% per cycle. Also, pouch cells fabricated with the MoB additive deliver an ultrahigh discharge capacity of 947 mA h g⁻¹, corresponding to a low electrolyte-to-capacity ratio of about 4.8 µL (mA h)⁻¹, and remain stable over 55 cycles under practically necessary conditions with a low electrolyte-to-sulfur ratio of 4.5 µL mg⁻¹.     

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.     

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.     

High Rate Magnesium–Sulfur Battery with Improved Cyclability Based on Metal–Organic Framework Derivative Carbon Host

Mg batteries have the advantages of resource abundance, high volumetric energy density, and dendrite‐free plating/stripping of Mg anodes. However the injection of highly polar Mg²⁺ cannot maintain the structural integrity of intercalation‐type cathodes even for open framework prototypes. The lack of high‐voltage electrolytes and sluggish Mg²⁺ diffusion in lattices or through interfaces also limit the energy density of Mg batteries. Mg–S system based on moderate‐voltage conversion electrochemistry appears to be a promising solution to high‐energy Mg batteries. However, it still suffers from poor capacity and cycling performances so far. Here, a ZIF‐67 derivative carbon framework codoped by N and Co atoms is proposed as effective S host for highly reversible Mg–S batteries even under high rates. The discharge capacity is as high as ≈600 mA h g^?1 at 1 C during the first cycle, and it is still preserved at ≈400 mA h g^?1 after at least 200 cycles. Under a much higher rate of 5 C, a capacity of 300–400 mA h g^?1 is still achievable. Such a superior performance is unprecedented among Mg–S systems and benefits from multiple factors, including heterogeneous doping, Li‐salt and Cl^? addition, charge mode, and cut‐off capacity, as well as separator decoration, which enable the mitigation of electrode passivation and polysulfide loss.     

Compactly Coupled Nitrogen‐Doped Carbon Nanosheets/Molybdenum Phosphide Nanocrystal Hollow Nanospheres as Polysulfide Reservoirs for High‐Performance Lithium–Sulfur Chemistry

Lithium–sulfur (Li–S) batteries have been disclosed as one of the most promising energy storage systems. However, the low utilization of sulfur, the detrimental shuttling behavior of polysulfides, and the sluggish kinetics in electrochemical processes, severely impede their application. Herein, 3D hierarchical nitrogen‐doped carbon nanosheets/molybdenum phosphide nanocrystal hollow nanospheres (MoP@C/N HCSs) are introduced to Li–S batteries via decorating commercial separators to inhibit polysulfides diffusion. It acts not only as a polysulfides immobilizer to provide strong physical trapping and chemical anchoring toward polysulfides, but also as an electrocatalyst to accelerate the kinetics of the polysulfides redox reaction, and to lower the Li₂S nucleation/dissolution interfacial energy barrier and self‐discharge capacity loss in working Li–S batteries, simultaneously. As a result, the Li–S batteries with MoP@C/N HCS‐modified separators show superior rate capability (920 mAh g^?1 at 2 C) and stable cycling life with only 0.04% capacity decay per cycle over 500 cycles at 1 C with nearly 100% Coulombic efficiency. Furthermore, the Li–S battery can achieve a high area capacity of 5.1 mAh cm^?2 with satisfied capacity retention when the cathode loading reaches 5.5 mg cm^?2. This work offers a brand new guidance for rational separator design into the energy chemistry of high‐stable Li–S batteries.     

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.     

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.     

Pyrrolic‐Type Nitrogen‐Doped Hierarchical Macro/Mesoporous Carbon as a Bifunctional Host for High‐Performance Thick Cathodes for Lithium‐Sulfur Batteries

Lithium‐sulfur (Li‐S) batteries are highly considered as a next‐generation energy storage device due to their high theoretical energy density. For practical viability, reasonable active‐material loading of >4.0 mg cm^?2 must be employed, at a cost to the intrinsic instability of sulfur cathodes. The incursion of lithium polysulfides (LiPS) at higher sulfur loadings results in low active material utilization and poor cell cycling capability. The use of high‐surface‐area hierarchical macro/mesoporous inverse opal (IOP) carbons to investigate the effects of pore volume and surface area on the electrochemical stability of high‐loading, high‐thickness cathodes for Li‐S batteries is presented here. The IOP carbons are additionally doped with pyrrolic‐type nitrogen groups (N‐IOP) to act as a polar polysulfide mediator and enhance the active‐material reutilization. With a high sulfur loading of 6.0 mg cm^?2, the Li‐S cells assembled with IOP and N‐IOP carbons are able to attain a high specific capacity of, respectively, 1242 and 1162 mA h g^?1. The N‐IOP enables the Li‐S cells to demonstrate good electrochemical performance over 300 cycles.     

Designing a Multifunctional Separator for High‐Performance Li–S Batteries at Elevated Temperature

The practical applications of lithium–sulfur (Li–S) batteries are seriously limited by the undesirable polysulfide shuttling and lithium dendrite growth. Herein, a multifunctional membrane is designed and prepared by coating a lithiated Nafion (Li@Nafion) layer and an Al₂O₃ layer on the two sides of a routine polymer membrane (polypropylene/polyethylene/polypropylene, PEP). The Li@Nafion layer faced to the sulfur cathode builds a “polysulfide‐phobic” surface to restrain the shuttle effect via Coulomb repulsion, while the Al₂O₃ layer with a uniform porous structure aids in regulating homogeneous Li⁺ fluxes to achieve stable Li electrodeposition. As a result, the Li//Li symmetric cell with a Li@Nafion/PEP/Al₂O₃ (LNPA) separator realizes stable Li plating/striping even after 1000 h at a high current density (5 mA cm^?2). Moreover, the Li–S batteries incorporating LNPA separators not only can achieve excellent outstanding cyclic stability at an ultrahigh sulfur loading (7.6 mg cm^?2), but also exhibit impressive electrochemical performance at an elevated temperature (60 °C). The rational design of the LNPA separator presents new insights to develop high‐performance Li–S batteries.