Electrolyte Regulation towards Stable Lithium‐Metal Anodes in Lithium–Sulfur Batteries with Sulfurized Polyacrylonitrile Cathodes

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.     

Functional Organosulfide Electrolyte Promotes an Alternate Reaction Pathway to Achieve High Performance in Lithium–Sulfur Batteries

Lithium–sulfur (Li‐S) batteries have recently received great attention because they promise to provide energy density far beyond current lithium ion batteries. Typically, Li‐S batteries operate by conversion of sulfur to reversibly form different soluble lithium polysulfide intermediates and insoluble lithium sulfides through multistep redox reactions. Herein, we report a functional electrolyte system incorporating dimethyl disulfide as a co‐solvent that enables a new electrochemical reduction pathway for sulfur cathodes. This pathway uses soluble dimethyl polysulfides and lithium organosulfides as intermediates and products, which can boost cell capacity and lead to improved discharge–charge reversibility and cycling performance of sulfur cathodes. This electrolyte system can potentially enable Li‐S batteries to achieve high energy density.     

Electrolyte Regulation towards Stable Lithium-Metal Anodes in Lithium–Sulfur Batteries with Sulfurized Polyacrylonitrile Cathodes

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.     

An Organodiselenide Comediator to Facilitate Sulfur Redox Kinetics in Lithium–Sulfur Batteries with Encapsulating Lithium Polysulfide Electrolyte

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.     

An odyssey of lithium metal anode in liquid lithium–sulfur batteries

Lithium–sulfur (Li–S) batteries exhibit outstanding energy density and material sustainability. Enormous effects have been devoted to the sulfur cathode to address redox kinetics and polysulfide intermediates shuttle. Recent attentions are gradually turning to the protection of the lithium metal anodes, since electrochemical performances of Li–S batteries are closely linked to the working efficiency of the anode side, especially in pouch cells that adopt stringent test protocols. This Perspective article summarizes critical issues encountered in the lithium metal anode, and outlines possible solutions to achieve efficient working lithium anode in Li–S batteries. The lithium metal anode in Li–S batteries shares the common failure mechanisms of volume fluctuation, nonuniform lithium flux, electrolyte corrosion and lithium pulverization occurring in lithium metal batteries with oxide cathodes, and also experiences unique polysulfide corrosion and massive lithium accumulation. These issues can be partially addressed by developing three-dimensional scaffold, exerting quasi-solid reaction, tailoring native solid electrolyte interphase (SEI) and designing artificial SEI. The practical evaluation of Li–S batteries highlights the importance of pouch cell platform, which is distinguished from coin-type cells in terms of lean electrolyte-to-sulfur ratio, thin lithium foil, as well as sizable total capacity and current that are loaded on pouch cells. This Perspective underlines the development of practically efficient working lithium metal anode in Li–S batteries.     

Double‐Shelled Nanocages with Cobalt Hydroxide Inner Shell and Layered Double Hydroxides Outer Shell as High‐Efficiency Polysulfide Mediator for Lithium–Sulfur Batteries

Lithium–sulfur (Li‐S) batteries have been considered as a promising candidate for next‐generation electrochemical energy‐storage technologies because of their overwhelming advantages in energy density. Suppression of the polysulfide dissolution while maintaining a high sulfur utilization is the main challenge for Li–S batteries. Here, we have designed and synthesized double‐shelled nanocages with two shells of cobalt hydroxide and layered double hydroxides (CH@LDH) as a conceptually new sulfur host for Li–S batteries. Specifically, the hollow CH@LDH polyhedra with complex shell structures not only maximize the advantages of hollow nanostructures for encapsulating a high content of sulfur (75 wt %), but also provide sufficient self‐functionalized surfaces for chemically bonding with polysulfides to suppress their outward dissolution. When evaluated as cathode material for Li–S batteries, the CH@LDH/S composite shows a significantly improved electrochemical performance.     

Towards a Safe Lithium–Sulfur Battery with a Flame‐Inhibiting Electrolyte and a Sulfur‐Based Composite Cathode

Of the various beyond‐lithium‐ion batteries, lithium–sulfur (Li‐S) batteries were recently reported as possibly being the closest to market. However, its theoretically high energy density makes it potentially hazardous under conditions of abuse. Therefore, addressing the safety issues of Li‐S cells is necessary before they can be used in practical applications. Here, we report a concept to build a safe and highly efficient Li‐S battery with a flame‐inhibiting electrolyte and a sulfur‐based composite cathode. The flame retardant not only makes the carbonates nonflammable but also dramatically enhances the electrochemical performance of the sulfur‐based composite cathode, without an apparent capacity decline over 750 cycles, and with a capacity greater than 800 mA h^?1 g^?1(sulfur) at a rate of 10 C.     

Enhanced Performance of a Lithium–Sulfur Battery Using a Carbonate‐Based Electrolyte

The lithium–sulfur battery is regarded as one of the most promising candidates for lithium–metal batteries with high energy density. However, dendrite Li formation and low cycle efficiency of the Li anode as well as unstable sulfur based cathode still hinder its practical application. Herein a novel electrolyte (1 m LiODFB/EC‐DMC‐FEC) is designed not only to address the above problems of Li anode but also to match sulfur cathode perfectly, leading to extraordinary electrochemical performances. Using this electrolyte, lithium|lithium cells can cycle stably for above 2000 hours and the average Coulumbic efficiency reaches 98.8 %. Moreover, the Li–S battery delivers a reversible capacity of about 1400 mAh g^?1_sulfur with retention of 89 % for 1100 cycles at 1 C, and a capacity above 1100 mAh g^?1_sulfur at 10 C. The more advantages of this cell system are its outstanding cycle stability at 60 °C and no self‐discharge phenomena.     

Enhanced Electrochemical Kinetics on Conductive Polar Mediators for Lithium–Sulfur Batteries

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.     

Electrolytes for Rechargeable Lithium–Air Batteries

Lithium–air batteries are promising devices for electrochemical energy storage because of their ultrahigh energy density. However, it is still challenging to achieve practical Li–air batteries because of their severe capacity fading and poor rate capability. Electrolytes are the prime suspects for cell failure. In this Review, we focus on the opportunities and challenges of electrolytes for rechargeable Li–air batteries. A detailed summary of the reaction mechanisms, internal compositions, instability factors, selection criteria, and design ideas of the considered electrolytes is provided to obtain appropriate strategies to meet the battery requirements. In particular, ionic liquid (IL) electrolytes and solid‐state electrolytes show exciting opportunities to control both the high energy density and safety.     

Beyond the Polysulfide Shuttle and Lithium Dendrite Formation: Addressing the Sluggish Sulfur Redox Kinetics for Practical High‐Energy Li‐S Batteries

Electrolyte modulation simultaneously suppresses polysulfide the shuttle effect and lithium dendrite formation of lithium–sulfur (Li‐S) batteries. However, the sluggish S redox kinetics, especially under high S loading and lean electrolyte operation, has been ignored, which dramatically limits the cycle life and energy density of practical Li‐S pouch cells. Herein, we demonstrate that a rational combination of selenium doping, core–shell hollow host structure, and fluorinated ether electrolytes enables ultrastable Li stripping/plating and essentially no polysulfide shuttle as well as fast redox kinetics. Thus, high areal capacity (>4 mAh cm^?2) with excellent cycle stability and Coulombic efficiency were both demonstrated in Li metal anode and thick S cathode (4.5 mg cm^?2) with a low electrolyte/sulfur ratio (10 μL mg^?1). This research further demonstrates a durable Li‐Se/S pouch cell with high specific capacity, validating the potential practical applications.     

Multifunctional Metal Phosphides as Superior Host Materials for Advanced Lithium-Sulfur Batteries

For the past few years, a new generation of energy storage systems with large theoretical specific capacity has been urgently needed because of the rapid development of society. Lithium–sulfur (Li−S) batteries are regarded as one of the most promising candidates for novel battery systems, since their resurgence at the end of the 20th century Li−S batteries have attracted ever more attention, attributed to their notably high theoretical energy density of 2600 W h kg⁻¹, which is almost five times larger than that of commercial lithium-ion batteries (LIBs). One of the determining factors in Li−S batteries is how to design/prepare the sulfur cathode. For the sulfur host, the major technical challenge is avoiding the shuttling effect that is caused by soluble polysulfides during the reaction. In past decades, though the sulfur cathode has developed greatly, there are still some enormous challenges to be conquered, such as low utilization of S, rapid decay of capacity, and poor cycle life. This article spotlights the recent progress and foremost findings in improving the performance of Li−S batteries by employing multifunctional metal phosphides as host materials. The current state of development of the sulfur electrode of Li−S batteries is summarized by emphasizing the relationship between the essential properties of metal phosphide-based hybrid nanomaterials, the chemical reaction with lithium polysulfides and the latter′s influence on electrochemical performance. Finally, trends in the development and practical application of Li−S batteries are also pointed out.     

Prospect of Sulfurized Pyrolyzed Poly(acrylonitrile) (S@pPAN) Cathode Materials for Rechargeable Lithium Batteries

Lithium–sulfur (Li–S) batteries are one of the most promising next‐generation batteries owing to their ultra‐high theoretical energy density and that sulfur is an abundant resource. During the past 20 years, various sulfur materials have been reported. As a molecular‐scale sulfur‐composite cathode, sulfurized pyrolyzed poly(acrylonitrile) (S@pPAN) exhibits several competitive advantages in terms of its electrochemical behavior. Although it was first reported in 2002 S@pPAN is currently attracting increasing attention. In this Minireview, we summarize its molecular model and explore the correlation between its structure and its exceptional electrochemical performance. We classify the modification strategies into three types, including material improvement, binder, and electrolyte screening. Several research and development directions are also suggested.     

Activating Inert Metallic Compounds for High‐Rate Lithium–Sulfur Batteries Through In Situ Etching of Extrinsic Metal

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.     

Pomegranate‐Structured Silica/Sulfur Composite Cathodes for High‐Performance Lithium–Sulfur Batteries

Porous materials have many structural advantages for energy storage and conversion devices such as rechargeable batteries, supercapacitors, and fuel cells. When applied as a host material in lithium‐sulfur batteries, porous silica materials with a pomegranate‐like architecture can not only act as a buffer matrix for accommodating a large volume change of sulfur, but also suppress the polysulfide shuttle effect. The porous silica/sulfur composite cathodes exhibit excellent electrochemical performances including a high specific capacity of 1450 mA h g^?1, a reversible capacity of 82.9 % after 100 cycles at a rate of C/2 (1 C=1672 mA g^?1) and an extended cyclability over 300 cycles at 1 C‐rate. Furthermore, the high polysulfide adsorption property of porous silica has been proven by ex‐situ analyses, showing a relationship between the surface area of silica and polysulfide adsorption ability. In particular, the modified porous silica/sulfur composite cathode, which is treated by a deep‐lithiation process in the first discharge step, exhibits a highly reversible capacity of 94.5 % at 1C‐rate after 300 cycles owing to a formation of lithiated‐silica frames and stable solid‐electrolyte‐interphase layers.     

Beyond the Polysulfide Shuttle and Lithium Dendrite Formation: Addressing the Sluggish Sulfur Redox Kinetics for Practical High-Energy Li-S Batteries

Electrolyte modulation simultaneously suppresses polysulfide the shuttle effect and lithium dendrite formation of lithium–sulfur (Li-S) batteries. However, the sluggish S redox kinetics, especially under high S loading and lean electrolyte operation, has been ignored, which dramatically limits the cycle life and energy density of practical Li-S pouch cells. Herein, we demonstrate that a rational combination of selenium doping, core–shell hollow host structure, and fluorinated ether electrolytes enables ultrastable Li stripping/plating and essentially no polysulfide shuttle as well as fast redox kinetics. Thus, high areal capacity (>4 mAh cm⁻²) with excellent cycle stability and Coulombic efficiency were both demonstrated in Li metal anode and thick S cathode (4.5 mg cm⁻²) with a low electrolyte/sulfur ratio (10 μL mg⁻¹). This research further demonstrates a durable Li-Se/S pouch cell with high specific capacity, validating the potential practical applications.     

Polyolefin‐Based Janus Separator for Rechargeable Sodium Batteries

Rechargeable sodium batteries are a promising technology for low‐cost energy storage. However, the undesirable drawbacks originating from the use of glass fiber membrane separators have long been overlooked. A versatile grafting–filtering strategy was developed to controllably tune commercial polyolefin separators for sodium batteries. The as‐developed Janus separators contain a single–ion‐conducting polymer‐grafted side and a functional low‐dimensional material coated side. When employed in room‐temperature sodium–sulfur batteries, the poly(1‐[3‐(methacryloyloxy)propylsulfonyl]‐1‐(trifluoromethanesulfonyl)imide sodium)‐grafted side effectively enhances the electrolyte wettability, and inhibits polysulfide diffusion and sodium dendrite growth. Moreover, a titanium‐deficient nitrogen‐containing MXene‐coated side electrocatalytically improved the polysulfide conversion kinetics. The as‐developed batteries demonstrate high capacity and extended cycling life with lean electrolyte loading.     

A Stable Quasi‐Solid‐State Sodium–Sulfur Battery

Ambient‐temperature sodium–sulfur (Na–S) batteries are considered a promising energy storage system due to their high theoretical energy density and low costs. However, great challenges remain in achieving a high rechargeable capacity and long cycle life. Herein we report a stable quasi‐solid‐state Na‐S battery enabled by a poly(S‐pentaerythritol tetraacrylate (PETEA))‐based cathode and a (PETEA‐tris[2‐(acryloyloxy)ethyl] isocyanurate (THEICTA))‐based gel polymer electrolyte. The polymeric sulfur electrode strongly anchors sulfur through chemical binding and inhibits the shuttle effect. Meanwhile, the in situ formed polymer electrolyte with high ionic conductivity and enhanced safety successfully stabilizes the Na anode/electrolyte interface, and simultaneously immobilizes soluble Na polysulfides. The as‐developed quasi‐solid‐state Na‐S cells exhibit a high reversible capacity of 877 mA h g^?1 at 0.1 C and an extended cycling stability.     

Fast,Reversible Lithium Storage with a Sulfur/Long‐Chain‐Polysulfide Redox Couple

The cathodic reactions in Li–S batteries can be divided into two steps. Firstly, elemental sulfur is transformed into long‐chain polysulfides (S₈?Li₂S₄), which are highly soluble in the electrolyte. Next, long‐chain polysulfides undergo nucleation reaction and convert into solid‐state Li₂S₂ and Li₂S (Li₂S₄?Li₂S) by slow processes. As a result, the second‐step of the electrochemical reaction hinders the high‐rate application of Li–S batteries. In this report, the kinetics of the sulfur/long‐chain‐polysulfide redox couple (theoretical capacity=419 mA h g^?1) are experimentally demonstrated to be very fast in the Li–S system. A Li–S cell with a blended carbon interlayer retains excellent cycle stability and possesses a high percentage of active material utilization over 250 cycles at high C rates. The meso‐/micropores in the interlayer are responsible for accommodating the shuttling polysulfides and offering sufficient electrolyte accessibility. Therefore, utilizing the sulfur/long‐chain polysulfide redox couple with an efficient interlayer configuration in Li–S batteries may be a promising choice for high‐power applications.     

Lithium–Sulfur Batteries: Electrochemistry,Materials, and Prospects

With the increasing demand for efficient and economic energy storage, Li‐S batteries have become attractive candidates for the next‐generation high‐energy rechargeable Li batteries because of their high theoretical energy density and cost effectiveness. Starting from a brief history of Li‐S batteries, this Review introduces the electrochemistry of Li‐S batteries, and discusses issues resulting from the electrochemistry, such as the electroactivity and the polysulfide dissolution. To address these critical issues, recent advances in Li‐S batteries are summarized, including the S cathode, Li anode, electrolyte, and new designs of Li‐S batteries with a metallic Li‐free anode. Constructing S molecules confined in the conductive microporous carbon materials to improve the cyclability of Li‐S batteries serves as a prospective strategy for the industry in the future.