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The cycle life of high‐energy‐density lithium−sulfur (Li−S) batteries is severely plagued by the incessant parasitic reactions between Li metal anodes and reactive Li polysulfides (LiPSs). Encapsulating Li‐polysulfide electrolyte (EPSE) emerges as an effective electrolyte design to mitigate the parasitic reactions kinetically. Nevertheless, the rate performance of Li−S batteries with EPSE is synchronously suppressed. Herein, the sacrifice in rate performance by EPSE is circumvented while mitigating parasitic reactions by employing hexyl methyl ether (HME) as a co‐solvent. The specific capacity of Li−S batteries with HME‐based EPSE is nearly not decreased at 0.1 C compared with conventional ether electrolytes. With an ultrathin Li metal anode (50 μm) and a high‐areal‐loading sulfur cathode (4.4 mgS cm−2), a longer cycle life of 113 cycles was achieved in HME‐based EPSE compared with that of 65 cycles in conventional ether electrolytes at 0.1 C. Furthermore, both high energy density of 387 Wh kg−1 and stable cycle life of 27 cycles were achieved in a Li−S pouch cell (2.7 Ah). This work inspires the feasibility of regulating the solvation structure of LiPSs in EPSE for Li−S batteries with balanced performance. [ABSTRACT FROM AUTHOR]

Lithium–sulfur (Li–S) batteries are widely regarded as promising next‐generation battery systems due to their impressive theoretical energy density of 2600 Wh kg−1. However, practical high‐energy‐density Li–S pouch cells suffer from rapid performance degradation under high working rates. Herein, the performance degradation mechanism of 400 Wh kg−1 Li–S pouch cells is systematically investigated under a high cycling rate of 0.2 C. Focusing on the reduced specific capacity and increased cell polarization, the sluggish cathodic sulfur redox kinetics under lean‐electrolyte and high‐rate conditions is identified as the main limitation. Further polarization decoupling indicates the cathodic activation polarization contributes dominantly to the increased cell polarization. Accordingly, a delicately designed electrolyte using dimethyl diselenide as the kinetic promoter is proposed to enable the Li–S pouch cells to work at 0.2 C with reduced cell polarization. This work clarifies the sluggish cathodic interfacial charge transfer kinetics as the main challenge for high‐energy‐density Li–S batteries at high rates and is expected to inspire rational strategy design for achieving advanced Li–S batteries. [ABSTRACT FROM AUTHOR]

Practical lithium–sulfur (Li−S) batteries are severely plagued by the instability of solid electrolyte interphase (SEI) formed in routine ether electrolytes. Herein, an electrolyte with 1,3,5‐trioxane (TO) and 1,2‐dimethoxyethane (DME) as co‐solvents is proposed to construct a high‐mechanical‐stability SEI by enriching organic components in Li−S batteries. The high‐mechanical‐stability SEI works compatibly in Li−S batteries. TO with high polymerization capability can preferentially decompose and form organic‐rich SEI, strengthening mechanical stability of SEI, which mitigates crack and regeneration of SEI and reduces the consumption rate of active Li, Li polysulfides, and electrolytes. Meanwhile, DME ensures high specific capacity of S cathodes. Accordingly, the lifespan of Li−S batteries increases from 75 cycles in routine ether electrolyte to 216 cycles in TO‐based electrolyte. Furthermore, a 417 Wh kg−1 Li−S pouch cell undergoes 20 cycles. This work provides an emerging electrolyte design for practical Li−S batteries. [ABSTRACT FROM AUTHOR]

Lithium–sulfur (Li–S) batteries are regarded as promising high‐energy‐density energy storage devices. However, the cycling stability of Li–S batteries is restricted by the parasitic reactions between Li metal anodes and soluble lithium polysulfides (LiPSs). Encapsulating LiPS electrolyte (EPSE) can efficiently suppress the parasitic reactions but inevitably sacrifices the cathode sulfur redox kinetics. To address the above dilemma, a redox comediation strategy for EPSE is proposed to realize high‐energy‐density and long‐cycling Li–S batteries. Concretely, dimethyl diselenide (DMDSe) is employed as an efficient redox comediator to facilitate the sulfur redox kinetics in Li–S batteries with EPSE. DMDSe enhances the liquid–liquid and liquid–solid conversion kinetics of LiPS in EPSE while maintains the ability to alleviate the anode parasitic reactions from LiPSs. Consequently, a Li–S pouch cell with a high energy density of 359 Wh kg−1 at cell level and stable 37 cycles is realized. This work provides an effective redox comediation strategy for EPSE to simultaneously achieve high energy density and long cycling stability in Li–S batteries and inspires rational integration of multi‐strategies for practical working batteries. [ABSTRACT FROM AUTHOR]

Lithium-sulfur (Li-S) battery is considered as a promising energy storage system due to its ultrahigh theoretical energy density of 2,600 Wh·kg−1. Redox mediation strategies have been proposed to promote the sluggish sulfur redox kinetics. Nevertheless, the applicability of redox mediators in practical high-energy-density Li-S batteries has seldomly been manifested. In this work, 5,7,12,14-pentacenetetrone (PT) is proposed as an effective redox mediator to promote the sulfur redox kinetics under practical working conditions. A high initial specific discharge capacity of 993 mAh·g−1 is achieved at 0.1 C with high-sulfur-loading cathodes of 4.0 mgS·cm−2 and low electrolyte/sulfur (E/S) ratio of 5 µL·mgS−1. More importantly, practical Li-S pouch cells with the PT mediator realize an actual initial energy density of 344 Wh·kg−1 and cycle stably for 20 cycles wih a high capacity retention of 88%. This work proposes an effective redox mediator and further verifies the redox mediation strategy for practical high-energy-density Li-S batteries. [ABSTRACT FROM AUTHOR]

The development of emerging rechargeable batteries is often hindered by limited chemical understanding composing of entangled patterns in an enormous space. Herein, we propose an interpretable hybrid machine learning framework to untangle intractable degradation chemistries of conversion‐type batteries. Rather than being a black box, this framework not only demonstrates an ability to accurately forecast lithium‐sulfur batteries (with a test mean absolute error of 8.9 % for the end‐of‐life prediction) but also generate useful physical understandings that illuminate future battery design and optimization. The framework also enables the discovery of a previously unknown performance indicator, the ratio of electrolyte amount to high‐voltage‐region capacity at the first discharge, for lithium‐sulfur batteries complying practical merits. The present data‐driven approach is readily applicable to other energy storage systems due to its versatility and flexibility in modules and inputs. [ABSTRACT FROM AUTHOR]

The lifespan of practical lithium (Li)‐metal batteries is severely hindered by the instability of Li‐metal anodes. Fluorinated solid electrolyte interphase (SEI) emerges as a promising strategy to improve the stability of Li‐metal anodes. The rational design of fluorinated molecules is pivotal to construct fluorinated SEI. Herein, design principles of fluorinated molecules are proposed. Fluoroalkyl (−CF2CF2−) is selected as an enriched F reservoir and the defluorination of the C−F bond is driven by leaving groups on β‐sites. An activated fluoroalkyl molecule (AFA), 2,2,3,3‐tetrafluorobutane‐1,4‐diol dinitrate is unprecedentedly proposed to render fast and complete defluorination and generate uniform fluorinated SEI on Li‐metal anodes. In Li–sulfur (Li−S) batteries under practical conditions, the fluorinated SEI constructed by AFA undergoes 183 cycles, which is three times the SEI formed by LiNO3. Furthermore, a Li−S pouch cell of 360 Wh kg−1 delivers 25 cycles with AFA. This work demonstrates rational molecular design principles of fluorinated molecules to construct fluorinated SEI for practical Li‐metal batteries. [ABSTRACT FROM AUTHOR]

Lithium (Li) metal has been considered a promising anode for next‐generation high‐energy‐density batteries. However, the low reversibility and intricate Li loss hinder the widespread implementation of Li metal batteries. Herein, we quantitatively differentiate the dynamic evolution of inactive Li, and decipher the fundamental interplay among dynamic Li loss, electrolyte chemistry, and the structure of the solid electrolyte interphase (SEI). The actual dominant form in inactive Li loss is practically determined by the relative growth rates of dead Li0 and SEI Li+ because of the persistent evolution of the Li metal interface during cycling. Distinct inactive Li evolution scenarios are disclosed by ingeniously tuning the inorganic anion‐derived SEI chemistry with a low amount of film‐forming additive. An optimal polymeric film enabler of 1,3‐dioxolane is demonstrated to derive a highly uniform multilayer SEI and decreased SEI Li+/dead Li0 growth rates, thus achieving enhanced Li cycling reversibility. [ABSTRACT FROM AUTHOR]

Lithium‐sulfur (Li−S) battery is considered as a promising energy storage system because of its high theoretical energy density of 2600 Wh kg−1, whose practical performance is limited by the sluggish sulfur redox kinetics. Homogeneous redox mediators (RMs) are effective promotors to propel the sulfur redox kinetics. However, most of the RMs only focus on a single reaction process. Herein, a strategy of mixed redox mediators (mixed‐RM) is proposed for full‐range redox mediation on the sulfur redox kinetics in working Li−S batteries. Concretely, one of the mixed‐RM mainly mediates the liquid‐solid reduction from polysulfides (LiPSs) to Li2S during discharge, while the other aims to promote the solid‐liquid conversion from Li2S to LiPSs and the liquid‐solid conversion from LiPSs to S8 during charge. Consequently, 2.5 Ah Li−S pouch cells with the mixed‐RM achieve an actual initial energy density of 354 Wh kg−1 alongside stable 20 cycles. This work provides an effective strategy on promoting the sulfur redox kinetics for high‐energy‐density Li−S batteries and inspires rational combination of novel functional molecules for practical energy storage systems. [ABSTRACT FROM AUTHOR]

In this Editorial, Guest Editors Stefan Kaskel, Jia‐Qi Huang, and Hikari Sakaebe introduce the Special Collection of Batteries & Supercaps on Lithium–Sulfur batteries. They discuss the challenges that lithium‐ion batteries currently face and how they can be solved using lithium‐sulfur batteries using various interesting approaches from scientists around the world. [ABSTRACT FROM AUTHOR]

Lithium–sulfur (Li–S) batteries are deemed as future energy storage devices due to ultrahigh theoretical energy density. Cathodic polysulfide electrocatalysts have been widely investigated to promote sluggish sulfur redox kinetics. Probing the surface structure of electrocatalysts is vital to understanding the mechanism of polysulfide electrocatalysis. In this work, we for the first time identify surface gelation on disulfide electrocatalysts. Concretely, the Lewis acid sites on disulfides trigger the ring‐opening polymerization of the dioxolane solvent to generate a surface gel layer, covering disulfides and reducing the electrocatalytic activity. Accordingly, a Lewis base triethylamine (TEA) is introduced as a competitive inhibitor. Consequently, Li–S batteries with disulfide electrocatalysts and TEA afford high specific capacity and improved rate responses. This work affords new insights on the actual surface structure of electrocatalysts in Li–S batteries. [ABSTRACT FROM AUTHOR]

Lithium–sulfur (Li–S) battery is identified as one of the most promising next‐generation energy storage systems due to its ultra‐high theoretical energy density up to 2600 Wh kg−1. However, Li metal anode suffers from dramatic volume change during cycling, continuous corrosion by polysulfide electrolyte, and dendrite formation, rendering limited cycling lifespan. Considering Li metal anode as a double‐edged sword that contributes to ultrahigh energy density as well as limited cycling lifespan, it is necessary to evaluate Li‐based alloy as anode materials to substitute Li metal for high‐performance Li–S batteries. In this contribution, the authors systematically evaluate the potential and feasibility of using Li metal or Li‐based alloys to construct Li–S batteries with an actual energy density of 500 Wh kg−1. A quantitative analysis method is proposed by evaluating the required amount of electrolyte for a targeted energy density. Based on a three‐level (ideal material level, practical electrode level, and pouch cell level) analysis, highly lithiated lithium–magnesium (Li–Mg) alloy is capable to achieve 500 Wh kg−1 Li–S batteries besides Li metal. Accordingly, research on Li–Mg and other Li‐based alloys are reviewed to inspire a promising pathway to realize high‐energy‐density and long‐cycling Li–S batteries. [ABSTRACT FROM AUTHOR]

High‐energy‐density lithium (Li) metal batteries are severely hindered by the dendritic Li deposition dictated by non‐uniform solid electrolyte interphase (SEI). Despite its unique advantages in improving the uniformity of Li deposition, the current anion‐derived SEI is unsatisfactory under practical conditions. Herein regulating the electrolyte structure of anions by anion receptors was proposed to construct stable anion‐derived SEI. Tris(pentafluorophenyl)borane (TPFPB) anion acceptors with electron‐deficient boron atoms interact with bis(fluorosulfonyl)imide anions (FSI−) and decrease the reduction stability of FSI−. Furthermore, the type of aggregate cluster of FSI− in electrolyte changes, FSI− interacting with more Li ions in the presence of TPFPB. Therefore, the decomposition of FSI− to form Li2S is promoted, improving the stability of anion‐derived SEI. In working Li | LiNi0.5Co0.2Mn0.3O2 batteries under practical conditions, the anion‐derived SEI with TPFPB undergoes 194 cycles compared with 98 cycles of routine anion‐derived SEI. This work inspires a fresh ground to construct stable anion‐derived SEI by manipulating the electrolyte structure of anions. [ABSTRACT FROM AUTHOR]

The lithium–sulfur (Li–S) battery is regarded as a promising secondary battery. However, constant parasitic reactions between the Li anode and soluble polysulfide (PS) intermediates significantly deteriorate the working Li anode. The rational design to inhibit the parasitic reactions is plagued by the inability to understand and regulate the electrolyte structure of PSs. Herein, the electrolyte structure of PSs with anti‐reductive solvent shells was unveiled by molecular dynamics simulations and nuclear magnetic resonance. The reduction resistance of the solvent shell is proven to be a key reason for the decreased reactivity of PSs towards Li. With isopropyl ether (DIPE) as a cosolvent, DIPE molecules tend to distribute in the outer solvent shell due to poor solvating power. Furthermore, DIPE is more stable than conventional ether solvents against Li metal. The reactivity of PSs is suppressed by encapsulating PSs into anti‐reductive solvent shells. Consequently, the cycling performance of working Li–S batteries was significantly improved and a pouch cell of 300 Wh kg−1 was demonstrated. The fundamental understanding in this work provides an unprecedented ground to understand the electrolyte structure of PSs and the rational electrolyte design in Li–S batteries. [ABSTRACT FROM AUTHOR]

Polysulfide intermediates (PSs), the liquid‐phase species of active materials in lithium–sulfur (Li‐S) batteries, connect the electrochemical reactions between insulative solid sulfur and lithium sulfide and are key to full exertion of the high‐energy‐density Li‐S system. Herein, the concept of sulfur container additives is proposed for the direct modification on the PSs species. By reversible storage and release of the sulfur species, the container molecule converts small PSs into large organosulfur species. The prototype di(tri)sulfide‐polyethylene glycol sulfur container is highly efficient in the reversible PS transformation to multiply affect electrochemical behaviors of sulfur cathodes in terms of liquid‐species clustering, reaction kinetics, and solid deposition. The stability and capacity of Li‐S cells was thereby enhanced. The sulfur container is a strategy to directly modify PSs, enlightening the precise regulation on Li‐S batteries and multi‐phase electrochemical systems. [ABSTRACT FROM AUTHOR]

The development of energy‐storage devices has received increasing attention as a transformative technology to realize a low‐carbon economy and sustainable energy supply. Lithium–sulfur (Li–S) batteries are considered to be one of the most promising next‐generation energy‐storage devices due to their ultrahigh energy density. Despite the extraordinary progress in the last few years, the actual energy density of Li–S batteries is still far from satisfactory to meet the demand for practical applications. Considering the sulfur electrochemistry is highly dependent on solid‐liquid‐solid multi‐phase conversion, the electrolyte amount plays a primary role in the practical performances of Li–S cells. Therefore, a lean electrolyte volume with low electrolyte/sulfur ratio is essential for practical Li–S batteries, yet under these conditions it is highly challenging to achieve acceptable electrochemical performances regarding sulfur kinetics, discharge capacity, Coulombic efficiency, and cycling stability especially for high‐sulfur‐loading cathodes. In this Review, the impact of the electrolyte/sulfur ratio on the actual energy density and the economic cost of Li–S batteries is addressed. Challenges and recent progress are presented in terms of the sulfur electrochemical processes: the dissolution–precipitation conversion and the solid–solid multi‐phasic transition. Finally, prospects of future lean‐electrolyte Li–S battery design and engineering are discussed. [ABSTRACT FROM AUTHOR]

Lithium–sulfur (Li–S) batteries are highly regarded as the next‐generation energy‐storage devices because of their ultrahigh theoretical energy density of 2600 Wh kg−1. Sulfurized polyacrylonitrile (SPAN) is considered a promising sulfur cathode to substitute carbon/sulfur (C/S) composites to afford higher Coulombic efficiency, improved cycling stability, and potential high‐energy‐density Li–SPAN batteries. However, the instability of the Li‐metal anode threatens the performances of Li–SPAN batteries bringing limited lifespan and safety hazards. Li‐metal can react with most kinds of electrolyte to generate a protective solid electrolyte interphase (SEI), electrolyte regulation is a widely accepted strategy to protect Li‐metal anodes in rechargeable batteries. Herein, the basic principles and current challenges of Li–SPAN batteries are addressed. Recent advances on electrolyte regulation towards stable Li‐metal anodes in Li–SPAN batteries are summarized to suggest design strategies of solvents, lithium salts, additives, and gel electrolyte. Finally, prospects for future electrolyte design and Li anode protection in Li–SPAN batteries are discussed. [ABSTRACT FROM AUTHOR]

Regulating the solid product growth is critical for achieving high capacities in rechargeable batteries based upon multiphase and multielectron dissolution–precipitation chemistries (e.g., lithium–sulfur chemistry). The intrinsic redox mediators, polysulfides, are insufficient for effective regulation due to the dynamically changed species and concentration. Herein cobaltocene (CoCp2) is introduced as a persistent extrinsic redox mediator to dictate an alternative growing pathway toward three‐dimensional lithium sulfide growth, which enables at most 8.1 times enhancement in discharge capacities at harsh conditions of high‐rate (>1 C) or electrolyte‐lean operation (electrolyte/sulfur ratio of 4.7 µL mgS−1). The faster kinetics and higher diffusivity of CoCp2 play an essential role in regulating lithium sulfide growth and increasing discharge capacities. This work not only illustrates an effective strategy to increase the capacity of high‐rate or electrolyte‐lean lithium–sulfur batteries but also paves a way toward the rational design of novel redox mediators for dissolution–precipitation energy chemistries. [ABSTRACT FROM AUTHOR]

In situ evolution of electrocatalysts is of paramount importance in defining catalytic reactions. Catalysts for aprotic electrochemistry such as lithium–sulfur (Li‐S) batteries are the cornerstone to enhance intrinsically sluggish reaction kinetics but the true active phases are often controversial. Herein, we reveal the electrochemical phase evolution of metal‐based pre‐catalysts (Co4N) in working Li‐S batteries that renders highly active electrocatalysts (CoSx). Electrochemical cycling induces the transformation from single‐crystalline Co4N to polycrystalline CoSx that are rich in active sites. This transformation propels all‐phase polysulfide‐involving reactions. Consequently, Co4N enables stable operation of high‐rate (10 C, 16.7 mA cm−2) and electrolyte‐starved (4.7 μL mgS−1) Li‐S batteries. The general concept of electrochemically induced sulfurization is verified by thermodynamic energetics for most of low‐valence metal compounds. [ABSTRACT FROM AUTHOR]

Surface reactions constitute the foundation of various energy conversion/storage technologies, such as the lithium–sulfur (Li‐S) batteries. To expedite surface reactions for high‐rate battery applications demands in‐depth understanding of reaction kinetics and rational catalyst design. Now an in situ extrinsic‐metal etching strategy is used to activate an inert monometal nitride of hexagonal Ni3N through iron‐incorporated cubic Ni3FeN. In situ etched Ni3FeN regulates polysulfide‐involving surface reactions at high rates. Electron microscopy was used to unveil the mechanism of in situ catalyst transformation. The Li‐S batteries modified with Ni3FeN exhibited superb rate capability, remarkable cycling stability at a high sulfur loading of 4.8 mg cm−2, and lean‐electrolyte operability. This work opens up the exploration of multimetallic alloys and compounds as kinetic regulators for high‐rate Li‐S batteries and also elucidates catalytic surface reactions and the role of defect chemistry. Inert hexagonal Ni3N can be activated by an extrinsic metal‐incorporating strategy with in situ etching that uses cubic Ni3FeN. Vacancy‐rich Ni3FeN catalysts kinetically regulate polysulfide‐involving reactions at high rates for use in advanced lithium–sulfur batteries. [ABSTRACT FROM AUTHOR]

High‐dielectric solvents were explored for enhancing the sulfur utilization in lithium–sulfur (Li−S) batteries, but their applications have been impeded by low stability at the lithium metal anode. Now a radical‐directed, lithium‐compatible, and strongly polysulfide‐solvating high‐dielectric electrolyte based on tetramethylurea is presented. Over 200 hours of cycling was realized in Li|Li symmetric cells, showing good compatibility of the tetramethylurea‐based electrolyte with lithium metal. The high solubility of short‐chain polysulfides, as well as the presence of active S3.− radicals, enabled pouch cells to deliver a discharge capacity of 1524 mAh g−1 and an energy density of 324 Wh kg−1. This finding suggests an alternative recipe to ether‐based electrolytes for Li−S batteries. Li−S batteries: A lithium‐compatible and strongly polysulfide‐solvating high‐dielectric electrolyte based on tetramethylurea was proposed to direct a solvation‐mediated radical reaction pathway. It enables Li−S pouch cells to deliver an energy density of 324 Wh kg−1. Key: red=electrochemical, black=chemical, dashed=diffusion/precipitation. [ABSTRACT FROM AUTHOR]

Abstract: Lithium–sulfur (Li–S) batteries deliver a high theoretical energy density of 2600 Wh kg−1, and hold great promise to serve as a next‐generation high‐energy‐density battery system. Great progress has been achieved in cathode design to deal with the intrinsic problems of sulfur cathodes, including low conductivity, the dissolution of polysulfide intermediate, and volume fluctuation. However, aiming at the practical applications of Li–S batteries, the weight percentage of sulfur in cathode materials and the overall areal sulfur loading need to be significantly increased, which inevitably complicate the process and cause heavy shuttle effect, slow redox kinetics, and more undesirable reaction pathways. Recently, rationally designing efficient mediators, as well as incorporating them into a working battery, emerges to be a promising method to construct high‐energy‐density Li–S batteries. The influence of mediators on Li–S batteries appears to be the enhancement in redox kinetics and the increase in reaction efficiency. In this feature article, the mechanistic understanding of redox kinetics in Li–S reactions is discussed, and then a comprehensive analysis of the recent advances in both heterogeneous and homogeneous mediator design is provided. A mediator perspective in building high‐energy‐density Li–S batteries is also included. [ABSTRACT FROM AUTHOR]

Abstract: Lithium–sulfur (Li–S) batteries hold great promise as a next‐generation battery system because of their extremely high theoretical energy density and low cost. However, ready lithium polysulfide (LiPS) diffusion and sluggish redox kinetics hamper their cyclability and rate capability. Herein, porphyrin‐derived graphene‐based nanosheets (PNG) are proposed for Li–S batteries, which are achieved by pyrolyzing a conformal and thin layer of 2D porphyrin organic framework on graphene to form carbon nanosheets with a spatially engineered nitrogen‐dopant‐enriched skin and a highly conductive skeleton. The atomic skin is decorated with fully exposed lithiophilic sites to afford strong chemisorption to LiPSs and improve electrolyte wettability, while graphene substrate provides speedy electron transport to facilitate redox kinetics of sulfur species. The use of PNG as a lightweight interlayer enables efficient operation of Li–S batteries in terms of superb cycle stability (cyclic decay rate of 0.099% during 300 cycles at 0.5 C), good rate capability (988 mAh g−1 at 2.0 C), and impressive sulfur loading (areal capacity of 8.81 mAh cm−2 at a sulfur loading of 8.9 mg cm−2). The distinct interfacial strategy is expected to apply to other conversion reaction batteries relying on dissolution–precipitation mechanisms and requiring interfacial charge‐ and mass‐transport‐mediation concurrently. [ABSTRACT FROM AUTHOR]

Due to the high theoretical energy density of 2600 Wh kg-1, lithium-sulfur batteries are strongly regarded as the promising nextgeneration energy storage devices. However, the practical applications of lithium-sulfur batteries are challenged by several obstacles, including the low sulfur utilization and poor lifespan, which are partly attributed to the shuttle of lithium polysulfides and lithium dendrite growth in working lithium-sulfur batteries. Suppressing lithium dendrite growth is a necessary step not only for a safe and efficient Li metal anode, but also for a high capacity cell with a high Coulombic efficiency. Herein we review the lithium metal anode protection in a polysulfide-rich environment, relative to most reviews on lithium metal anode without considering the effect of lithium polysulfides in lithium metal batteries. Firstly, the importance and dilemma of Li metal anode issues in lithium-sulfur batteries are underscored, aiming to arouse the attentions to Li metal anode protection. Specific attentions are paid to the surface chemistry of Li metal anode in a polysulfide-rich lithium-sulfur battery. Next, the proposed strategies to stabilize solid electrolyte interface and protect Li metal anode are included. Finally, a general conclusion and a perspective on the current limitations, as well as recommended future research directions of Li metal anode in lithium-sulfur batteries are presented. [ABSTRACT FROM AUTHOR]

Owing to high specific energy, low cost, and environmental friendliness, lithium-sulfur (Li-S) batteries hold great promise to meet the increasing demand for advanced energy storage beyond portable electronics, and to mitigate environmental problems. However, the application of Li-S batteries is challenged by several obstacles, including their short life and low sulfur utilization, which become more serious when sulfur loading is increased to the practically accepted level above 3-5 mg cm−2. More and more efforts have been made recently to overcome the barriers toward commercially viable Li-S batteries with a high sulfur loading. This review highlights the recent progress in high-sulfur-loading Li-S batteries enabled by hierarchical design principles at multiscale. Particularly, basic insights into the interfacial reactions, strategies for mesoscale assembly, unique architectures, and configurational innovation in the cathode, anode, and separator are under specific concerns. Hierarchy in the multiscale design is proposed to guide the future development of high-sulfur-loading Li-S batteries. [ABSTRACT FROM AUTHOR]

Supramolecular materials, in which small organic molecules are assembled into regular structures by non-covalent interactions, attract tremendous interests because of their highly tunable functional groups and porous structure. Supramolecular adsorbents are expected to fully expose their abundant adsorptive sites in a dynamic framework. In this contribution, we introduced cucurbit[6]uril as a supramolecular capsule for reversible storage/delivery of mobile polysulfides in lithium-sulfur (Li-S) batteries to control undesirable polysulfide shuttle. The Li-S battery equipped with the supramolecular capsules retains a high Coulombic efficiency and shows a large increase in capacity from 300 to 900 mAh g−1 at a sulfur loading of 4.2 mg cm−2. The implementation of supramolecular capsules offers insights into intricate multi-electron-conversion reactions and manifests as an effective and efficient strategy to enhance Li-S batteries and analogous applications that involve complex transport phenomena and intermediate manipulation. [ABSTRACT FROM AUTHOR]

Graphical abstract Abstract Lithium-sulfur (Li-S) batteries with intrinsic merits in high theoretical energy density are the most promising candidate as the next-generation power sources. The strategy to achieve a high utilization of active materials with high energy efficiency is strongly requested for practical applications with less energy loss during repeated cycling. In this contribution, a metal/nanocarbon layer current collector is proposed to enhance the redox reactions of polysulfides in a working Li-S cell. Such a concept is demonstrated by coating graphene–carbon nanotube hybrids (GNHs) on routine aluminum (Al) foil current collectors. The interfacial conductivity and adhesion between the current collector and active material are significantly enhanced. Such novel cell configuration with metal/nanocarbon layer current collectors affords abundant Li ions for rapid redox reactions with small overpotential. Consequently, the Li-S cells with nanostructured current collectors exhibit an initial discharge capacity of 1,113 mAh g−1 at 0.5 C, which is ∼300 mAh g−1 higher than those without a GNH coating layer. The capacity retention is 73% for cells with GNH after 300 cycles. A reduced voltage hysteresis and a high energy efficiency of ca. 90% are therefore achieved. Moreover, the Al/GNH layer current collectors are easily implanted into current cell assembly process for energy storage devices based on complex multi-electron redox reactions (e.g., Li-S batteries, Li-O 2 batteries, fuel cells, and flow batteries). [ABSTRACT FROM AUTHOR]

Flexible energy storage systems are imperative for emerging flexible devices that are revolutionizing our life. Lithium-ion batteries, the current main power sources, are gradually approaching their theoretical limitation in terms of energy density. Therefore, alternative battery chemistries are urgently required for next-generation flexible power sources with high energy densities, low cost, and inherent safety. Flexible lithium–sulfur (Li–S) batteries and analogous flexible alkali metal–chalcogen batteries are of paramount interest owing to their high energy densities endowed by multielectron chemistry. In this review, we summarized the recent progress of flexible Li–S and analogous batteries. A brief introduction to flexible energy storage systems and general Li–S batteries has been provided first. Progress in flexible materials for flexible Li–S batteries are reviewed subsequently, with a detailed classification of flexible sulfur cathodes as those based on carbonaceous (e.g., carbon nanotubes, graphene, and carbonized polymers) and composite (polymers and inorganics) materials and an overview of flexible lithium anodes and flexible solid-state electrolytes. Advancements in other flexible alkali metal–chalcogen batteries are then introduced. In the next part, we emphasize the importance of cell packaging and flexibility evaluation, and two special flexible battery prototypes of foldable and cable-type Li–S batteries are highlighted. In the end, existing challenges and future development of flexible Li–S and analogous alkali metal–chalcogen batteries are summarized and prospected. [ABSTRACT FROM AUTHOR]

The lithium-sulfur (Li-S) battery is a promising high-energy-density storage system. The strong anchoring of intermediates is widely accepted to retard the shuttle of polysulfides in a working battery. However, the understanding of the intrinsic chemistry is still deficient. Inspired by the concept of hydrogen bond, herein we focus on the Li bond chemistry in Li-S batteries through sophisticated quantum chemical calculations, in combination with 7Li nuclear magnetic resonance (NMR) spectroscopy. Identified as Li bond, the strong dipole-dipole interaction between Li polysulfides and Li-S cathode materials originates from the electron-rich donors (e.g., pyridinic nitrogen (pN)), and is enhanced by the inductive and conjugative effect of scaffold materials with π-electrons (e.g., graphene). The chemical shift of Li polysulfides in 7Li NMR spectroscopy, being both theoretically predicted and experimentally verified, is suggested to serve as a quantitative descriptor of Li bond strength. These theoretical insights were further proved by actual electrochemical tests. This work highlights the importance of Li bond chemistry in Li-S cell and provides a deep comprehension, which is helpful to the cathode materials rational design and practical applications of Li-S batteries. [ABSTRACT FROM AUTHOR]

The lithium-sulfur (Li-S) batteries are potential candidates for next-generation power sources with very high-energy-density. The rational integration of three dimensional (3D) carbon skeletons into sulfur cathode is an efficient and effective route to full use of conductive scaffolds with chemical and mechanical stability and ability to accommodate large amount of active materials. Herein, a 3D free-standing electrode composed of nitrogen-doped porous graphene/sulfur composite granular and super-long carbon nanotube (CNT) skeleton is proposed for Li-S batteries with high volumetric energy density. With a facile calendering process, the mechanical properties, bulk conductivity, and the pore distribution of the flexible graphene@S-CNT electrodes were tuned. The high rate capability, long-life stability, and high volumetric energy density of Li-S batteries are highly depended on the nanostructure evolution of composite carbon/sulfur electrode. A high rate capability of 40% retention of discharge capacity of 2.0 C against that at 0.05 C, a high cyclic stability of 0.1%/cycle within 180 cycles, and a high volumetric energy density over 850 Wh L −1 are demonstrated with the pressed graphene@S-CNT electrode. This work unfolded a general strategy to modulate the bulk structure of electrodes, which is an efficient route towards Li-S batteries with high volumetric energy density. [ABSTRACT FROM AUTHOR]

Lithium-sulfur (Li-S) batteries have been recognized as promising substitutes for current energy-storage technologies owing to their exceptional advantage in energy density. The main challenge in developing highly efficient and long-life Li-S batteries is simultaneously suppressing the shuttle effect and improving the redox kinetics. Polar host materials have desirable chemisorptive properties to localize the mobile polysulfide intermediates; however, the role of their electrical conductivity in the redox kinetics of subsequent electrochemical reactions is not fully understood. Conductive polar titanium carbides (TiC) are shown to increase the intrinsic activity towards liquid-liquid polysulfide interconversion and liquid-solid precipitation of lithium sulfides more than non-polar carbon and semiconducting titanium dioxides. The enhanced electrochemical kinetics on a polar conductor guided the design of novel hybrid host materials of TiC nanoparticles grown within a porous graphene framework (TiC@G). With a high sulfur loading of 3.5 mg cm−2, the TiC@G/sulfur composite cathode exhibited a substantially enhanced electrochemical performance. [ABSTRACT FROM AUTHOR]

The cycling stability of high-sulfur-loading lithium-sulfur (Li-S) batteries remains a great challenge owing to the exaggerated shuttle problem and interface instability. Despite enormous efforts on design of advanced electrodes and electrolytes, the stability issue raised from current collectors has been rarely concerned. This study demonstrates that rationally designing a 3D carbonaceous macroporous current collector is an efficient and effective 'two-in-one' strategy to improve the cycling stability of high-sulfur-loading Li-S batteries, which is highly versatile to enable various composite cathodes with sulfur loading >3.7 mAh cm−2. The best cycling performance can be achieved upon 950 cycles with a very low decay rate of 0.029%. Moreover, the origin of such a huge enhancement in cycling stability is ascribed to (1) the inhibition of electrochemical corrosion, which severely occurs on the typical Al foil and disables its long-term sustainability for charge transfer, and (2) the passivation of cathode surface. The role of the chemical resistivity against corrosion and favorable macroscopic porous structure is highlighted for exploiting novel current collectors toward exceptional cycling stability of high-sulfur-loading Li-S batteries. [ABSTRACT FROM AUTHOR]

The self-discharge of a lithium-sulfur cell decreases the shelf-life of the battery and is one of the bottlenecks that hinders its practical applications. New insights into both the internal chemical reactions in a lithium-sulfur system and effective routes to retard self-discharge for highly stable batteries are crucial for the design of lithium-sulfur cells. Herein, a lithium-sulfur cell with a carbon nanotube/sulfur cathode and lithium-metal anode in lithium bis(trifluoromethanesulfonyl)imide/1,3-dioxolane/dimethyl ether electrolyte was selected as the model system to investigate the self-discharge behavior. Both lithium anode passivation and polysulfide anion diffusion suppression strategies are applied to reduce self-discharge of the lithium-sulfur cell. When the lithium-metal anode is protected by a high density passivation layer induced by LiNO3, a very low shuttle constant of 0.017 h−1 is achieved. The diffusion of the polysulfides is retarded by an ion-selective separator, and the shuttle constants decreased. The cell with LiNO3 additive maintained a discharge capacity of 97 % (961 mAh g−1) of the initial capacity after 120 days at open circuit, which was around three times higher than the routine cell (32 % of initial capacity, corresponding to 320 mAh g−1). It is expected that lithium-sulfur batteries with ultralow self-discharge rates may be fabricated through a combination of anode passivation and polysulfide shuttle control, as well as optimization of the lithium-sulfur cell configuration. [ABSTRACT FROM AUTHOR]

The rational combination of conductive nanocarbon with sulfur leads to the formation of composite cathodes that can take full advantage of each building block; this is an effective way to construct cathode materials for lithium-sulfur (Li-S) batteries with high energy density. Generally, the areal sulfur-loading amount is less than 2.0 mg cm−2, resulting in a low areal capacity far below the acceptable value for practical applications. In this contribution, a hierarchical free-standing carbon nanotube (CNT)-S paper electrode with an ultrahigh sulfur-loading of 6.3 mg cm−2 is fabricated using a facile bottom-up strategy. In the CNT-S paper electrode, short multi-walled CNTs are employed as the short-range electrical conductive framework for sulfur accommodation, while the super-long CNTs serve as both the long-range conductive network and the intercrossed mechanical scaffold. An initial discharge capacity of 6.2 mA·h cm−2 (995 mA·h g−1), a 60% utilization of sulfur, and a slow cyclic fading rate of 0.20%/cycle within the initial 150 cycles at a low current density of 0.05 C are achieved. The areal capacity can be further increased to 15.1 mA·h cm−2 by stacking three CNT-S paper electrodes-resulting in an areal sulfur-loading of 17.3 mg cm−2-for the cathode of a Li-S cell. The as-obtained free-standing paper electrode are of low cost and provide high energy density, making them promising for flexible electronic devices based on Li-S batteries. [ABSTRACT FROM AUTHOR]

The sp2-hybridized nanocarbon (e.g., carbon nanotubes (CNTs) and graphene) exhibits extraordinary mechanical strength and electrical conductivity but limited external accessible surface area and a small amount of pores, while nanostructured porous carbon affords a huge surface area and abundant pore structures but very poor electrical conductance. Herein the rational hybridization of the sp2 nanocarbon and nanostructured porous carbon into hierarchical all-carbon nanoarchitectures is demonstrated, with full inherited advantages of the component materials. The sp2 graphene/CNT interlinked networks give the composites good electrical conductivity and a robust framework, while the meso-/microporous carbon and the interlamellar compartment between the opposite graphene accommodate sulfur and polysulfides. The strong confinement induced by micro-/mesopores of all-carbon nanoarchitectures renders the transformation of S8 crystal into amorphous cyclo-S8 molecular clusters, restraining the shuttle phenomenon for high capacity retention of a lithium-sulfur cell. Therefore, the composite cathode with an ultrahigh specific capacity of 1121 mAh g−1 at 0.5 C, a favorable high-rate capability of 809 mAh g−1 at 10 C, a very low capacity decay of 0.12% per cycle, and an impressive cycling stability of 877 mAh g−1 after 150 cycles at 1 C. As sulfur loading increases from 50 wt% to 77 wt%, high capacities of 970, 914, and 613 mAh g−1 are still available at current densities of 0.5, 1, and 5 C, respectively. Based on the total mass of packaged devices, gravimetric energy density of GSH@APC-S//Li cell is expected to be 400 Wh kg−1 at a power density of 10 000 W kg−1, matching the level of engine driven systems. [ABSTRACT FROM AUTHOR]

Abstract: Lithium-sulfur battery is one of the most promising alternative power sources, but the polysulfide shuttle between the anode and cathode induces low Coulombic efficiency, low utilization of the sulfur cathode, and severe degradation of cycle life. Herein, the polysulfide shuttle was tuned by the loading of sulfur and electrolyte in a Li-S cell. A lithium-sulfur cell with a high initial discharge capacity of 1053 mAh g−1 at a high rate of 1 C and an ultralow decay rate of 0.049%/per cycle during 1000 cycles was obtained by using carbon nanotube@sulfur cathode and suppressing polysulfide shuttle to a shuttle factor of 0.02 by matching the sulfur/electrolyte loading. The use of matching the sulfur/electrolyte loading is a facile way to tune the shuttle of polysulfide, which provides not only new insights to the energy chemistry of Li/S batteries, but also important principle to assemble a Li/S cell with recommend loading for their commercialization application in portable mobile devices and electric vehicles. [Copyright &y& Elsevier]

Keywords: Disulfide; Lithium-Sulfur Batteries; Polysulfide Electrocatalysts; Sulfur Redox Kinetics; Surface Gelation EN Disulfide Lithium-Sulfur Batteries Polysulfide Electrocatalysts Sulfur Redox Kinetics Surface Gelation 1 1 1 02/03/22 20220207 NES 220207 B Li-S-Batterien b In ihrem Forschungsartikel (e202114671) identifizieren Bo-Quan Li, Qiang Zhang et al. erstmals die Oberflächengelbildung auf Elektrokatalysatoren in Li-S-Batterien. Frontispiz: Surface Gelation on Disulfide Electrocatalysts in Lithium-Sulfur Batteries Disulfide, Lithium-Sulfur Batteries, Polysulfide Electrocatalysts, Sulfur Redox Kinetics, Surface Gelation. [Extracted from the article]

Abstract: High efficient sulfur cathode materials were constructed by the incorporation of aligned sulfur-coated carbon nanotubes (CNTs) and a polyethylene glycol (PEG) barrier at one end. During the charge and discharge of lithium sulfur batteries, high Li ion storage performance can be achieved on the composite electrode, which was benefited from both the aligned CNT structure and the polymer barrier. Aligned CNT framework afforded high conductivity for electron transportation and ordered pores for lithium ion transportation. Meanwhile, the PEG barrier layer greatly suppressed the shuttle of polysulfides. Therefore, this aligned sulfur-coated CNTs with a PEG barrier showed a high initial discharge capacity of 920 and 1128mAhg−1 in lithium bis(trifluoromethanesulfonyl)imide/1,3-dioxolane/1,2-dimethoxyethane and electrolyte with LiNO3 additives, respectively. The PEG coated cathode showed high cycle stability that a low degradation with 0.38% per cycle during the 100 cycles at 0.1C was achieved in LiNO3-free electrolytes. These Li storage performance was superior to the aligned sulfur-coated CNT electrode without PEG barrier. [Copyright &y& Elsevier]

The cycling lifespan of high‐energy‐density lithium–sulfur (Li–S) batteries is dominantly limited by the rapid failure of Li metal anodes. Herein, the evolution of Li metal anode along cycling is systematically investigated in Li–S batteries to clarify the Li plating and stripping behaviors, the generation and accumulation of inactive Li, and the failure mechanism of Li metal anodes. Concretely, plated Li strips preferentially than bulk Li to leave massive stripping Li shells during initial discharge, and the stripping Li shells are refilled by plated Li during the subsequent charge to generate thick Li dendrites. During the following cycles, inactive Li generates and accumulates on top of bulk Li due to solid electrolyte interphase formation and incomplete removal of plated Li. Eventually, the accumulation of inactive Li hinders the diffusion of Li ions through the inactive Li layer to induce cell polarization at the end of the second discharge plateau and rapid decay of discharge capacity. This work elucidates the detailed evolution mechanism of Li metal anode along cycling in working Li–S batteries and highlights the reactivation of inactive Li as an effective strategy to prolong the cycling lifespan of Li–S batteries. [ABSTRACT FROM AUTHOR]

Rücktitelbild: Electrochemical Phase Evolution of Metal-Based Pre-Catalysts for High-Rate Polysulfide Conversion (Angew. Keywords: electrocatalysts; electrochemical phase evolution; lithium-sulfur batteries; polysulfide conversion EN electrocatalysts electrochemical phase evolution lithium-sulfur batteries polysulfide conversion 9278 9278 1 05/27/20 20200602 NES 200602 B Die In-situ-Evolution von Elektrokatalysatoren b ist von größter Bedeutung für die Auslegung katalytischer Reaktionen. Electrocatalysts, electrochemical phase evolution, lithium-sulfur batteries, polysulfide conversion. [Extracted from the article]

Lithium–sulfur (Li–S) batteries have emerged as a promising candidate for the next‐generation high‐energy‐density system for energy‐demanding applications. Despite innovations in concepts and materials that significantly improve the electrochemical performance of coin cells, Li–S pouch cells have the disadvantages of short cycle life and inferior rate capability in comparison with coin cells. Bridging the fundamentals of Li–S chemistry to the hindrance on its practical application is of great importance for the development of Li–S batteries. Herein, the nonuniformity of the distribution of sulfur and lithium upon cycling is probed as one of the origins for the rapid capacity fading in a Li–S pouch cell. In particular, the nonuniform evolution of sulfur/lithium distribution impairs the discharge capacity of a low‐voltage plateau. Lithium polysulfide intermediates produced on discharge tend to diffuse toward the bottom of a pouch cell, leading to agglomeration of sulfur and thus passivating the cathode. The migration of polysulfides also etches lithium away from the central region of the anode and induces nonuniform anode pulverization. Herein, the importance of a rational design of a pouch cell to mitigate the nonuniform redistribution of the active material toward stable Li–S pouch cells is highlighted. [ABSTRACT FROM AUTHOR]

Vacant defects bring activity to multimetallic alloys for cathode redox reactions in lithium–sulfur batteries. In their Communication on page 3779 ff., J.‐Q. Huang et al. show that the introduction and in situ etching of an extrinsic metal to a monometallic compound activates the originally inert phase for kinetic propelling of polysulfide‐involving surface reactions at a high rate. Remarkable cycling stability is found at a high sulfur loading of 4.8 mg cm−2. [ABSTRACT FROM AUTHOR]

Lithium–sulfur (Li–S) batteries have been strongly considered as one of the most promising future energy storage systems because of ultrahigh theoretical energy density of 2600 Wh kg−1. The natural abundance, affordable cost, and environmental benignity of elemental sulfur constitute additional advantages. However, complicated reaction behaviors at working electrode/electrolyte interfaces that involve multiphase conversion and multistep ion/electron diffusion during sulfur redox reactions have impeded the thorough understanding of Li–S chemistry and its practical applications. This perspective article highlights the influence of the ion/electron transport and reaction regulation through electrocatalysis or redox mediation at electrode/electrolyte interfaces on various interfacial sulfur redox reactions (liquid–liquid–solid interconversion between soluble lithium polysulfide with different chain lengths and insoluble lithium sulfides in liquid‐electrolyte Li–S batteries and direct solid–solid conversion between sulfur and Li2S in all‐solid‐state Li–S batteries). The current status, existing challenges, and future directions are discussed and prospected, aiming at shedding fresh light on fundamental understanding of interfacial sulfur redox reactions and guiding the rational design of electrode/electrolyte interfaces for next‐generation Li–S batteries with high energy density and long cycle life. Sulfur redox reactions at working interfaces are very crucial for efficiently operating lithium–sulfur batteries. In this perspective article, focusing on the interfacial conversion processes of sulfur, current status and future directions are included to shed light on an in‐depth fundamental understanding of interfacial behavior for sulfur electrochemistry toward better lithium–sulfur batteries. [ABSTRACT FROM AUTHOR]

Similar to the mermaids at the complex coast between sea and land, the working interfaces between liquid and solid phase is very crucial for efficient energy storage based on multiphase electrochemistry. In article number 1802046, Qiang Zhang and co‐workers summarize the recent advances in sulfur redox reactions at working interfaces. Future directions are also included to promote the insightful research in lithium–sulfur electrochemistry. [ABSTRACT FROM AUTHOR]

Rechargeable lithium–sulfur batteries have attracted tremendous scientific attention owing to their superior energy density. However, the sulfur electrochemistry involves multielectron redox reactions and complicated phase transformations, while the final morphology of solid‐phase Li2S precipitates largely dominate the battery's performance. Herein, a triple‐phase interface among electrolyte/CoSe2/G is proposed to afford strong chemisorption, high electrical conductivity, and superb electrocatalysis of polysulfide redox reactions in a working lithium–sulfur battery. The triple‐phase interface effectively enhances the kinetic behaviors of soluble lithium polysulfides and regulates the uniform nucleation and controllable growth of solid Li2S precipitates at large current density. Therefore, the cell with the CoSe2/G functional separator delivers an ultrahigh rate cycle at 6.0 C with an initial capacity of 916 mAh g−1 and a capacity retention of 459 mAh g−1 after 500 cycles, and a stable operation of high sulfur loading electrode (2.69–4.35 mg cm−2). This work opens up a new insight into the energy chemistry at interfaces to rationally regulate the electrochemical redox reactions, and also inspires the exploration of related energy storage and conversion systems based on multielectron redox reactions. A unique triple‐phase interface with synergistic properties of strong chemisorption, large electrical conductivity, and highly active electrocatalysis sites is proposed, which can effectively regulate the electrochemical redox reaction of soluble lithium polysulfides and tune Li2S nucleation and growth, enabling controllable Li2S precipitates on reactive interfaces at high current rates in a working Li–S battery. [ABSTRACT FROM AUTHOR]

Lithium–sulfur (Li–S) batteries have received tremendous attention due to their superior theoretical energy density of 2600 Wh kg−1, as well as the abundance of sulfur resources and its environmental friendliness. Polymer binders as an indispensable component in cathodes play a critical role in maintaining the structural integrity and stability of electrodes. Additionally, multifunctional polymer binders have been involved in Li–S batteries to benefit electrochemical performance by mitigating the shuttle effect, facilitating the electron/ion transportation, and propelling the redox kinetics. In the context of the significant impact of binders on the performance of Li–S batteries, recent progress in research on polymer binders in sulfur cathodes is herein summarized. Focusing on the functions and effects of the polymer binders, the authors hope to shed light on the rational construction of robust and stable sulfur cathode for high‐energy‐density Li–S batteries. Perspectives regarding the future research opportunities in Li–S batteries are also discussed. Polymer binders in lithium–sulfur batteries play a critical role in maintaining the structural integrity and stability of the electrode as an indispensable component. In this review, recent progress in research on polymer binders in sulfur cathodes is summarized, focusing on the rational design strategies of multifunctional polymer binders toward better lithium–sulfur batteries. [ABSTRACT FROM AUTHOR]

In article number 1700260, Qiang Zhang and co‐workers review high‐sulfur‐loading Li–S batteries enabled by multiscale hierarchical design principles. How to bridge the ‘sulfur cathode’ and ‘lithium anode’ is the key to fill the gaps for better Li‐S batteries. The authors provide new insights into the interfacial reactions, strategies for mesoscale assembly, unique architectures, and configurational innovation in the cathode, anode, and separator in advanced Li‐S batteries. [ABSTRACT FROM AUTHOR]