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.     

Sulfur Cathodes Based on Conductive MXene Nanosheets for High‐Performance Lithium–Sulfur Batteries

Lithium–sulfur batteries are amongst the most promising candidates to satisfy emerging energy‐storage demands. Suppression of the polysulfide shuttle while maintaining high sulfur content is the main challenge that faces their practical development. Here, we report that 2D early‐transition‐metal carbide conductive MXene phases—reported to be impressive supercapacitor materials—also perform as excellent sulfur battery hosts owing to their inherently high underlying metallic conductivity and self‐functionalized surfaces. We show that 70 wt % S/Ti₂C composites exhibit stable long‐term cycling performance because of strong interaction of the polysulfide species with the surface Ti atoms, demonstrated by X‐ray photoelectron spectroscopy studies. The cathodes show excellent cycling performance with specific capacity close to 1200 mA h g^?1 at a five‐hour charge/discharge (C/5) current rate. Capacity retention of 80 % is achieved over 400 cycles at a two‐hour charge/discharge (C/2) current rate.     

Lithium–Sulfur Batteries under Lean Electrolyte Conditions: Challenges and Opportunities

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.     

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.     

Encapsulating Sulfur into Hierarchically Ordered Porous Carbon as a High‐Performance Cathode for Lithium–Sulfur Batteries

A three‐dimensional (3D) hierarchical carbon–sulfur nanocomposite that is useful as a high‐performance cathode for rechargeable lithium–sulfur batteries is reported. The 3D hierarchically ordered porous carbon (HOPC) with mesoporous walls and interconnected macropores was prepared by in situ self‐assembly of colloidal polymer and silica spheres with sucrose as the carbon source. The obtained porous carbon possesses a large specific surface area and pore volume with narrow mesopore size distribution, and acts as a host and conducting framework to contain highly dispersed elemental sulfur. Electrochemical tests reveal that the HOPC/S nanocomposite with well‐defined nanostructure delivers a high initial specific capacity up to 1193 mAh g^?1 and a stable capacity of 884 mAh g^?1 after 50 cycles at 0.1 C. In addition, the HOPC/S nanocomposite exhibits high reversible capacity at high rates. The excellent electrochemical performance is attributed exclusively to the beneficial integration of the mesopores for the electrochemical reaction and macropores for ion transport. The mesoporous walls of the HOPC act as solvent‐restricted reactors for the redox reaction of sulfur and aid in suppressing the diffusion of polysulfide species into the electrolyte. The “open” ordered interconnected macropores and windows facilitate transportation of electrolyte and solvated lithium ions during the charge/discharge process. These results show that nanostructured carbon with hierarchical pore distribution could be a promising scaffold for encapsulating sulfur to approach high specific capacity and energy density with long cycling performance.     

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.     

An Aluminum–Sulfur Battery with a Fast Kinetic Response

The electrochemical performance of the aluminum‐sulfur (Al‐S) battery has very poor reversibility and a low charge/discharge current density owing to slow kinetic processes determined by an inevitable dissociation reaction from Al₂Cl₇^? to free Al³⁺. Al₂Cl₆Br^? was used instead of Al₂Cl₇^? as the dissociation reaction reagent. A 15‐fold faster reaction rate of Al₂Cl₆Br^? dissociation than that of Al₂Cl₇^? was confirmed by density function theory calculations and the Arrhenius equation. This accelerated dissociation reaction was experimentally verified by the increase of exchange current density during Al electro‐deposition. Using Al₂Cl₆Br^? instead of Al₂Cl₇^?, a kinetically accelerated Al‐S battery has a sulfur utilization of more than 80 %, with at least four times the sulfur content and five times the current density than that of previous work.     

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.     

Superior Electrochemical Performance of Sulfur/Graphene Nanocomposite Material for High‐Capacity Lithium–Sulfur Batteries

Sulfur/graphene nanocomposite material has been prepared by incorporating sulfur into the graphene frameworks through a melting process. Field‐emission scanning electron microscope analysis shows a homogeneous distribution of sulfur in the graphene nanosheet matrix. The sulfur/graphene nanocomposite exhibits a super‐high lithium‐storage capacity of 1580 mAh g^?1 and a satisfactory cycling performance in lithium–sulfur cells. The enhancement of the reversible capacity and cycle life could be attributed to the flexible graphene nanosheet matrix, which acts as a conducting medium and a physical buffer to cushion the volume change of sulfur during the lithiation and delithiation process. Graphene‐based nanocomposites can significantly improve the electrochemical performance of lithium–sulfur batteries.     

Elemental‐Sulfur‐Mediated Facile Synthesis of a Covalent Triazine Framework for High‐Performance Lithium–Sulfur Batteries

A covalent triazine framework (CTF) with embedded polymeric sulfur and a high sulfur content of 62 wt % was synthesized under catalyst‐ and solvent‐free reaction conditions from 1,4‐dicyanobenzene and elemental sulfur. Our synthetic approach introduces a new way of preparing CTFs under environmentally benign conditions by the direct utilization of elemental sulfur. The homogeneous sulfur distribution is due to the in situ formation of the framework structure, and chemical sulfur impregnation within the micropores of CTF effectively suppresses the dissolution of polysulfides into the electrolyte. Furthermore, the triazine framework facilitates electron and ion transport, which leads to a high‐performance lithium–sulfur battery.     

Strong Lithium Polysulfide Chemisorption on Electroactive Sites of Nitrogen‐Doped Carbon Composites For High‐Performance Lithium–Sulfur Battery Cathodes

Despite the high theoretical capacity of lithium–sulfur batteries, their practical applications are severely hindered by a fast capacity decay, stemming from the dissolution and diffusion of lithium polysulfides in the electrolyte. A novel functional carbon composite (carbon‐nanotube‐interpenetrated mesoporous nitrogen‐doped carbon spheres, MNCS/CNT), which can strongly adsorb lithium polysulfides, is now reported to act as a sulfur host. The nitrogen functional groups of this composite enable the effective trapping of lithium polysulfides on electroactive sites within the cathode, leading to a much improved electrochemical performance (1200 mAh g^?1 after 200 cycles). The enhancement in adsorption can be attributed to the chemical bonding of lithium ions by nitrogen functional groups in the MNCS/CNT framework. Furthermore, the micrometer‐sized spherical structure of the material yields a high areal capacity (ca. 6 mAh cm^?2) with a high sulfur loading of approximately 5 mg cm^?2, which is ideal for practical applications of the lithium–sulfur batteries.     

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.     

Integrating a Photocatalyst into a Hybrid Lithium–Sulfur Battery for Direct Storage of Solar Energy

Direct capture and storage of abundant but intermittent solar energy in electrical energy‐storage devices such as rechargeable lithium batteries is of great importance, and could provide a promising solution to the challenges of energy shortage and environment pollution. Here we report a new prototype of a solar‐driven chargeable lithium–sulfur (Li‐S) battery, in which the capture and storage of solar energy was realized by oxidizing S^2? ions to polysulfide ions in aqueous solution with a Pt‐modified CdS photocatalyst. The battery can deliver a specific capacity of 792 mAh g^?1 during 2 h photocharging process with a discharge potential of around 2.53 V versus Li⁺/Li. A specific capacity of 199 mAh g^?1, reaching the level of conventional lithium‐ion batteries, can be achieved within 10 min photocharging. Moreover, the charging process of the battery can proceed under natural sunlight irradiation.     

Evaluating the Free Energies of Solvation and Electronic Structures of Lithium‐Ion Battery Electrolytes

Adaptive biasing force molecular dynamics simulations and density functional theory calculations were performed to understand the interaction of Li⁺ with pure carbonates and ethylene carbonate (EC)‐based binary mixtures. The most favorable Li carbonate cluster configurations obtained from molecular dynamics simulations were subjected to detailed structural and thermochemistry calculations on the basis of the M06‐2X/6‐311++G(d,p) level of theory. We report the ranking of these electrolytes on the basis of the free energies of Li‐ion solvation in carbonates and EC‐based mixtures. A strong local tetrahedral order involving four carbonates around the Li⁺ was seen in the first solvation shell. Thermochemistry calculations revealed that the enthalpy of solvation and the Gibbs free energy of solvation of the Li⁺ ion with carbonates are negative and suggested the ion–carbonate complexation process to be exothermic and spontaneous. Natural bond orbital analysis indicated that Li⁺ interacts with the lone pairs of electrons on the carbonyl oxygen atom in the primary solvation sphere. These interactions lead to an increase in the carbonyl (C=O) bond lengths, as evidenced by a redshift in the vibrational frequencies [ν(C=O)] and a decrease in the electron density values at the C=O bond critical points in the primary solvation sphere. Quantum theory of atoms in molecules, localized molecular orbital energy decomposition analysis (LMO‐EDA), and noncovalent interaction plots revealed the electrostatic nature of the Li⁺ ion interactions with the carbonyl oxygen atoms in these complexes. On the basis of LMO‐EDA, the strongest attractive interaction in these complexes was found to be the electrostatic interaction followed by polarization, dispersion, and exchange interactions. Overall, our calculations predicted EC and a binary mixture of EC/dimethyl carbonate to be appropriate electrolytes for Li‐ion batteries, which complies with experiments and other theoretical results.     

Synthesis,Crystal Structure,and Electrochemical Properties of a Simple Magnesium Electrolyte for Magnesium/Sulfur Batteries

Most simple magnesium salts tend to passivate the Mg metal surface too quickly to function as electrolytes for Mg batteries. In the present work, an electroactive salt [Mg(THF)₆][AlCl₄]₂ was synthesized and structurally characterized. The Mg electrolyte based on this simple mononuclear salt showed a high Mg cycling efficiency, good anodic stability (2.5 V vs. Mg), and high ionic conductivity (8.5 mS cm^?1). Magnesium/sulfur cells employing the as‐prepared electrolyte exhibited good cycling performance over 20 cycles in the range of 0.3–2.6 V, thus indicating an electrochemically reversible conversion of S to MgS without severe passivation of the Mg metal electrode surface.     

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.     

Achilles’ Heel of Lithium–Air Batteries: Lithium Carbonate

The lithium–air battery (LAB) is envisaged as an ultimate energy storage device because of its highest theoretical specific energy among all known batteries. However, parasitic reactions bring about vexing issues on the efficiency and longevity of the LAB, among which the formation and decomposition of lithium carbonate Li₂CO₃ is of paramount importance. The discovery of Li₂CO₃ as the main discharge product in carbonate‐based electrolytes once brought researchers to “the end of the idyll“ in the early 2010s. In the past few years, tremendous efforts have been made to understand the formation and decomposition mechanisms of Li₂CO₃, as well as to conceive novel chemical/material strategies to suppress the Li₂CO₃ formation and to facilitate the Li₂CO₃ decomposition. Moreover, the study on Li₂CO₃ in LABs is opening up a new research field in energy technology. Considering the rapid development and innumerous emerging issues, it is timely to recapitulate the current understandings, define the ambiguities and the scientific gaps, and discuss topics of high priority for future research, which is the aim of this Minireview.     

Ionic‐Liquid‐Based Polymer Electrolytes for Battery Applications

The advent of solid‐state polymer electrolytes for application in lithium batteries took place more than four decades ago when the ability of polyethylene oxide (PEO) to dissolve suitable lithium salts was demonstrated. Since then, many modifications of this basic system have been proposed and tested, involving the addition of conventional, carbonate‐based electrolytes, low molecular weight polymers, ceramic fillers, and others. This Review focuses on ternary polymer electrolytes, that is, ion‐conducting systems consisting of a polymer incorporating two salts, one bearing the lithium cation and the other introducing additional anions capable of plasticizing the polymer chains. Assessing the state of the research field of solid‐state, ternary polymer electrolytes, while giving background on the whole field of polymer electrolytes, this Review is expected to stimulate new thoughts and ideas on the challenges and opportunities of lithium‐metal batteries.     

A Sulfur Heterocyclic Quinone Cathode and a Multifunctional Binder for a High‐Performance Rechargeable Lithium‐Ion Battery

We report a rational design of a sulfur heterocyclic quinone (dibenzo[b,i]thianthrene‐5,7,12,14‐tetraone=DTT) used as a cathode (uptake of four lithium ions to form Li₄DTT) and a conductive polymer [poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate)=PEDOT:PSS) used as a binder for a high‐performance rechargeable lithium‐ion battery. Because of the reduced energy level of the lowest unoccupied molecular orbital (LUMO) caused by the introduced S atoms, the initial Li‐ion intercalation potential of DTT is 2.89 V, which is 0.3 V higher than that of its carbon analog. Meanwhile, there is a noncovalent interaction between DTT and PEDOT:PSS, which remarkably suppressed the dissolution and enhanced the conductivity of DTT, thus leading to the great improvement of the electrochemical performance. The DTT cathode with the PEDOT:PSS binder displays a long‐term cycling stability (292 mAh g^?1 for the first cycle, 266 mAh g^?1 after 200 cycles at 0.1 C) and a high rate capability (220 mAh g^?1 at 1 C). This design strategy based on a noncovalent interaction is very effective for the application of small organic molecules as the cathode of rechargeable lithium‐ion batteries.