Functional Mesoporous Carbon‐Coated Separator for Long‐Life,High‐Energy Lithium–Sulfur Batteries

The lithium–sulfur (Li–S) battery is regarded as the most promising rechargeable energy storage technology for the increasing applications of clean energy transportation systems due to its remarkable high theoretical energy density of 2.6 kWh kg^?1, considerably outperforming today's lithium‐ion batteries. Additionally, the use of sulfur as active cathode material has the advantages of being inexpensive, environmentally benign, and naturally abundant. However, the insulating nature of sulfur, the fast capacity fading, and the short lifespan of Li–S batteries have been hampered their commercialization. In this paper, a functional mesoporous carbon‐coated separator is presented for improving the overall performance of Li–S batteries. A straightforward coating modification of the commercial polypropylene separator allows the integration of a conductive mesoporous carbon layer which offers a physical place to localize dissolved polysulfide intermediates and retain them as active material within the cathode side. Despite the use of a simple sulfur–carbon black mixture as cathode, the Li–S cell with a mesoporous carbon‐coated separator offers outstanding performance with an initial capacity of 1378 mAh g^?1 at 0.2 C, and high reversible capacity of 723 mAh g^?1, and degradation rate of only 0.081% per cycle, after 500 cycles at 0.5 C.     

Enhanced Interfacial Stability of Hybrid‐Electrolyte Lithium‐Sulfur Batteries with a Layer of Multifunctional Polymer with Intrinsic Nanoporosity

The use of lithium‐ion conductive solid electrolytes offers a promising approach to address the polysulfide shuttle and the lithium‐dendrite problems in lithium‐sulfur (Li‐S) batteries. One critical issue with the development of solid‐electrolyte Li‐S batteries is the electrode–electrolyte interfaces. Herein, a strategic approach is presented by employing a thin layer of a polymer with intrinsic nanoporosity (PIN) on a Li⁺‐ion conductive solid electrolyte, which significantly enhances the ionic interfaces between the electrodes and the solid electrolyte. Among the various types of Li⁺‐ion solid electrolytes, NASICON‐type Li_1+xAl_xTi_2‐x(PO₄)₃ (LATP) offers advantages in terms of Li⁺‐ion conductivity, stability in ambient environment, and practical viability. However, LATP is susceptible to reaction with both the Li‐metal anode and polysulfides in Li‐S batteries due to the presence of easily reducible Ti⁴⁺ ions in it. The coating with a thin layer of PIN presented in this study overcomes the above issues. At the negative‐electrode side, the PIN layer prevents the direct contact of Li‐metal with the LATP solid electrolyte, circumventing the reduction of LATP by Li metal. At the positive electrode side, the PIN layer prevents the migration of polysulfides to the surface of LATP, preventing the reduction of LATP by polysulfides.     

A Review: Electrospun Nanofiber Materials for Lithium‐Sulfur Batteries

Lithium‐sulfur (Li‐S) batteries are in the spotlight because their outstanding theoretical specific energy is much higher than those of the commercial lithium ion (Li‐ion) batteries. Li‐S batteries are tough competitors for future‐developing energy storage in the fields of portable electronics and electric vehicles. However, the severe “shuttle effect” of the polysulfides and the serious damage of lithium dendrites are main factors blocking commercial production of Li‐S batteries. Owing to their superior nanostructure, electrospun nanofiber materials commonly show some unique characteristics that can simultaneously resolve these issues. So far, various novel cathodes, separators, and interlayers of electrospun nanofiber materials which are applied to resolve these challenges are researched. This review presents the fundamental research and technological development of multifarious electrospun nanofiber materials for Li‐S cells, including their processing methods, structures, morphology engineering, and electrochemical performance. Not only does the review article contain a summary of electrospun nanofiber materials in Li‐S batteries but also a proposal for designing electrospun nanofiber materials for Li‐S cells. These systematic discussions and proposed directions can enlighten thoughts and offer ways in the reasonable design of electrospun nanofiber materials for excellent Li‐S batteries in the near future.     

Hierarchical Free‐Standing Carbon‐Nanotube Paper Electrodes with Ultrahigh Sulfur‐Loading for Lithium–Sulfur Batteries

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.     

Effective Polysulfide Rejection by Dipole‐Aligned BaTiO3 Coated Separator in Lithium–Sulfur Batteries

Although the exceptional theoretical specific capacity (1672 mAh g^?1) of elemental sulfur makes lithium–sulfur (Li–S) batteries attractive for upcoming rechargeable battery applications (e.g., electrical vehicles, drones, unmanned aerial vehicles, etc.), insufficient cycle lives of Li–S cells leave a substantial gap before their wide penetration into commercial markets. Among the key features that affect the cyclability, the shuttling process involving polysulfides (PS) dissolution is most fatal. In an effort to suppress this chronic PS shuttling, herein, a separator coated with poled BaTiO₃ or BTO particles is introduced. Permanent dipoles that are formed in the BTO particles upon the application of an electric field can effectively reject PS from passing through the separator via electrostatic repulsion, resulting in significantly improved cyclability, even when a simple mixture of elemental sulfur and conductive carbon is used as a sulfur cathode. The coating of BTO particles also considerably suppresses thermal shrinkage of the poly(ethylene) separator at high temperatures and thus enhances the safety of the cell adopting the given separator. The incorporation of poled particles can be universally applied to a wide range of rechargeable batteries (i.e., metal‐air batteries) that suffer from cross‐contamination of charged species between both electrodes.     

3D Interconnected Porous Carbon Aerogels as Sulfur Immobilizers for Sulfur Impregnation for Lithium‐Sulfur Batteries with High Rate Capability and Cycling Stability

To eliminate capacity‐fading effects due to the loss of sulfur cathode materials as a result of polysulfide dissolution in lithium–sulfur (Li–S) cells, 3D carbon aerogel (CA) materials with abundant narrow micropores can be utilized as an immobilizer host for sulfur impregnation. The effects of S incorporation on microstructure, surface area, pore size distribution, and pore volume of the S/CA hybrids are studied. The electrochemical performance of the S/CA hybrids is investigated using electrochemical impedance spectroscopy, galvanostatical charge–discharge, and cyclic voltammetry techniques. The 3D porous S/CA hybrids exhibit significantly improved reversible capacity, high‐rate capability, and excellent cycling performance as a cathode electrode for Li–S batteries. The S/CA hybrid with an optimal incorporating content of 27% S shows an excellent reversible capacity of 820 mAhg^?1 after 50 cycles at a current density of 100 mAg^?1. Even at a current density of 3.2C (5280 mAg^?1), the reversible capacity of 27%S/CA hybrid can still maintain at 521 mAhg^?1 after 50 cycles. This strategy for the S/CA hybrids as cathode materials to utilize the abundant micropores for sulfur immobilizers for sulfur impregnation for Li–S battery offers a new way to solve the long‐term reversibility obstacle and provides guidelines for designing cathode electrode architectures.     

Conductive Nanocrystalline Niobium Carbide as High‐Efficiency Polysulfides Tamer for Lithium‐Sulfur Batteries

Rational design of functional interlayer is highly significant in pursuit of high‐performance Li‐S batteries. Herein, a nanocrystalline niobium carbide (NbC) is developed via a facile and scalable autoclave technology, which is, for the first time, employed as the advanced interlayer material for Li‐S batteries. Combining the merits of strong polysulfides (PS) anchoring with high electric conductivity, the NbC‐coated membrane enables efficiently tamed PS shuttling and fast sulfur electrochemistry, achieving outstanding cyclability with negligible capacity fading rate of 0.037% cycle^?1 over 1500 cycles, superb rate capability up to 5 C, high areal capacity of 3.6 mA h cm^?2 under raised sulfur loading, and reliable operation even in soft‐package cells. This work offers a facile and effective method of promoting Li‐S batteries for practical application.     

Carbonized‐MOF as a Sulfur Host for Aluminum–Sulfur Batteries with Enhanced Capacity and Cycling Life

The rechargeable aluminum–sulfur (Al–S) battery is a promising next generation electrochemical energy storage system owing to its high theoretical capacity of 1672 mAh g^?1 and in combining low‐cost and naturally abundant elements, Al and S. However, to date, its poor reversibility and low lifespan have limited its practical application. In this paper, a composite cathode is reported for Al–S batteries based on S anchored on a carbonized HKUST‐1 matrix (S@HKUST‐1‐C). The S@HKUST‐1‐C composite maintains a reversible capacity of 600 mAh g^?1 at the 75th cycle and a reversible capacity of 460 mAh g^?1 at the 500th cycle under a current density of 1 A g^?1, with a Coulombic efficiency of around 95%. X‐ray diffraction and Auger spectrum results reveal that the Cu in HKUST‐1 forms S–Cu ionic clusters. This serves to facilitate the electrochemical reaction and improve the reversibility of S during charge/discharge. Additionally, Cu increases the electron conductivity at the carbon matrix/S interface to significantly decrease the kinetic barrier for the conversion of sulfur species during battery operation.     

3D Metal Carbide@Mesoporous Carbon Hybrid Architecture as a New Polysulfide Reservoir for Lithium‐Sulfur Batteries

3D metal carbide@mesoporous carbon hybrid architecture (Ti₃C₂T_x@Meso‐C, T_X ≈ F_xO_y) is synthesised and applied as cathode material hosts for lithium‐sulfur batteries. Exfoliated‐metal carbide (Ti₃C₂T_x) nanosheets have high electronic conductivity and contain rich functional groups for effective trapping of polysulfides. Mesoporous carbon with a robust porous structure provides sufficient spaces for loading sulfur and effectively cushion the volumetric expansion of sulfur cathodes. Theoretical calculations have confirmed that metal carbide can absorb sulfur and polysulfides, therefore extending the cycling performance. The Ti₃C₂T_x@Meso‐C/S cathodes have achieved a high capacity of 1225.8 mAh g^?1 and more than 300 cycles at the C/2 current rate. The Ti₃C₂T_x@Meso‐C hybrid architecture is a promising cathode host material for lithium‐sulfur batteries.     

A Flexible 3D Multifunctional MgO‐Decorated Carbon Foam@CNTs Hybrid as Self‐Supported Cathode for High‐Performance Lithium‐Sulfur Batteries

One of the critical challenges to develop advanced lithium‐sulfur (Li‐S) batteries lies in exploring a high efficient stable sulfur cathode with robust conductive framework and high sulfur loading. Herein, a 3D flexible multifunctional hybrid is rationally constructed consisting of nitrogen‐doped carbon foam@CNTs decorated with ultrafine MgO nanoparticles for the use as advanced current collector. The dense carbon nanotubes uniformly wrapped on the carbon foam skeletons enhance the flexibility and build an interconnected conductive network for rapid ionic/electronic transport. In particular, a synergistic action of MgO nanoparticles and in situ N‐doping significantly suppresses the shuttling effect via enhanced chemisorption of lithium polysulfides. Owing to these merits, the as‐built electrode with an ultrahigh sulfur loading of 14.4 mg cm^?2 manifests a high initial areal capacity of 10.4 mAh cm^?2, still retains 8.8 mAh cm^?2 (612 mAh g^?1 in gravimetric capacity) over 50 cycles. The best cycling performance is achieved upon 800 cycles with an extremely low decay rate of 0.06% at 2 C. Furthermore, a flexible soft‐packaged Li‐S battery is readily assembled, which highlights stable electrochemical characteristics under bending and even folding. This cathode structural design may open up a potential avenue for practical application of high‐sulfur‐loading Li‐S batteries toward flexible energy‐storage devices.     

Nanoarchitectured Graphene/CNT@Porous Carbon with Extraordinary Electrical Conductivity and Interconnected Micro/Mesopores for Lithium‐Sulfur Batteries

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.     

Nitrogen‐Doped Mesoporous Carbon Promoted Chemical Adsorption of Sulfur and Fabrication of High‐Areal‐Capacity Sulfur Cathode with Exceptional Cycling Stability for Lithium‐Sulfur Batteries

As one important component of sulfur cathodes, the carbon host plays a key role in the electrochemical performance of lithium‐sulfur (Li‐S) batteries. In this paper, a mesoporous nitrogen‐doped carbon (MPNC)‐sulfur nanocomposite is reported as a novel cathode for advanced Li‐S batteries. The nitrogen doping in the MPNC material can effectively promote chemical adsorption between sulfur atoms and oxygen functional groups on the carbon, as verified by X‐ray absorption near edge structure spectroscopy, and the mechanism by which nitrogen enables the behavior is further revealed by density functional theory calculations. Based on the advantages of the porous structure and nitrogen doping, the MPNC‐sulfur cathodes show excellent cycling stability (95% retention within 100 cycles) at a high current density of 0.7 mAh cm^‐2 with a high sulfur loading (4.2 mg S cm^‐2) and a sulfur content (70 wt%). A high areal capacity (≈3.3 mAh cm^‐2) is demonstrated by using the novel cathode, which is crucial for the practical application of Li‐S batteries. It is believed that the important role of nitrogen doping promoted chemical adsorption can be extended for development of other high performance carbon‐sulfur composite cathodes for Li‐S batteries.     

Electrode Design for Lithium–Sulfur Batteries: Problems and Solutions

Pursuit of advanced batteries with high‐energy density is one of the eternal goals for electrochemists. Over the past decades, lithium–sulfur batteries (LSBs) have gained world‐wide popularity due to their high theoretical energy density and cost effectiveness. However, their road to the market is still full of thorns. Apart from the poor electronic conductivity of sulfur‐based cathodes, LSBs involve special multielectron reaction mechanisms associated with active soluble lithium polysulfides intermediates. Accordingly, the electrode design and fabrication protocols of LSBs are different from those of traditional lithium ion batteries. This review is aimed at discussing the electrode design/fabrication protocols of LSBs, especially the current problems on various sulfur‐based cathodes (such as S, Li₂S, Li₂S_x catholyte, organopolysulfides) and corresponding solutions. Different fabrication methods of sulfur‐based cathodes are introduced and their corresponding bullet points to achieve high‐quality cathodes are highlighted. In addition, the challenges and solutions of sulfur‐based cathodes including active material content, mass loading, conductive agent/binder, compaction density, electrolyte/sulfur ratio, and current collector are summarized and rational strategies are refined to address these issues. Finally, the future prospects on sulfur‐based cathodes and LSBs are proposed.     

Activation of Oxygen‐Stabilized Sulfur for Li and Na Batteries

The sulfur‐based cathode materials suffer severely from poor cycling stability and low utilization, incurred by their stepwise reaction mechanism that generates polysulfide intermediates and the subsequent irreversible losses. In this work, those issues are significantly relieved by entrapping sulfur species in carbon host rich in oxygen functionalities. Sulfur species in such C/S composite are highly stabilized by their interaction with oxygen, and can deliver a reversible capacity of 508 mAh/(g of S) for 2000 cycles when coupled with Li, representing the best cycling stability up to date. More interestingly, extra capacity can be accessed by simply prelithiating the oxygen‐stabilized C/S composites down to 0.6 V for a few cycles, which enables a high capacity of 1621 mAh/(g of S) that eventually stabilizes at 820 mAh/(g of S) for 600 cycles. The mechanism for this electrochemical activation process is investigated with both spectroscopic and electrochemical techniques, which reveal that the inactive sulfur bonded to oxygen is liberated in the initial deep lithiation precycles and becomes electrochemically active. The oxygen‐stabilized sulfur can also be coupled with Na anode to form Na/S cell, confirming that the formation of S?O interaction in C/S composite generates promising sulfur‐based cathode materials for Li–S and Na–S batteries.     

Nanoflake Arrays of Lithiophilic Metal Oxides for the Ultra‐Stable Anodes of Lithium‐Metal Batteries

A molten lithium infusion strategy has been proposed to prepare stable Li‐metal anodes to overcome the serious issues associated with dendrite formation and infinite volume change during cycling of lithium‐metal batteries. Stable host materials with superior wettability of molten Li are the prerequisite. Here, it is demonstrated that a series of strong oxidizing metal oxides, including MnO₂, Co₃O₄, and SnO₂, show superior lithiophilicity due to their high chemical reactivity with Li. Composite lithium‐metal anodes fabricated via melt infusion of lithium into graphene foams decorated by these metal oxide nanoflake arrays successfully control the formation and growth of Li dendrites and alleviate volume change during cycling. A resulting Li‐Mn/graphene composite anode demonstrates a super‐long and stable lifetime for repeated Li plating/stripping of 800 cycles at 1 mA cm^?2 without voltage fluctuation, which is eight times longer than the normal lifespan of a bare Li foil under the same conditions. Furthermore, excellent rate capability and cyclability are realized in full‐cell batteries with Li‐Mn/graphene composite anodes and LiCoO₂ cathodes. These results show a major advancement in developing a stable Li anode for lithium‐metal batteries.     

Liquid‐Crystalline Electrolytes for Lithium‐Ion Batteries: Ordered Assemblies of a Mesogen‐Containing Carbonate and a Lithium Salt

Thermotropic liquid‐crystalline (LC) electrolytes for lithium‐ion batteries are developed for the first time. A rod‐like LC molecule having a cyclic carbonate moiety is used to form self‐assembled two‐dimensional ion‐conductive pathways with lithium salts. Electrochemical and thermal stability, and efficient ionic conduction is achieved for the liquid crystal. The mixture of the carbonate derivative and lithium bis(trifluoromethylsulfonyl)imide is successfully applied as an electrolyte in lithium‐ion batteries. Reversible charge–discharge for both positive and negative electrodes is observed for the lithium‐ion batteries composed of the LC electrolyte.     

Hierarchical Defective Fe3‐xC@C Hollow Microsphere Enables Fast and Long‐Lasting Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries present one of the most promising energy storage systems owing to their high energy density and low cost. However, the commercialization of Li–S batteries is still hindered by several technical issues; the notorious polysulfide shuttling and sluggish sulfur conversion kinetics. In this work, unique hierarchical Fe_3‐xC@C hollow microspheres as an advanced sulfur immobilizer and promoter for enabling high‐efficiency Li–S batteries is developed. The porous hollow architecture not only accommodates the volume variation upon the lithiation–delithiation processes, but also exposes vast active interfaces for facilitated sulfur redox reactions. Meanwhile, the mesoporous carbon coating establishes a highly conductive network for fast electron transportation. More importantly, the defective Fe_3‐xC nanosized subunits impose strong LiPS adsorption and catalyzation, enabling fast and durable sulfur electrochemistry. Attributed to these structural superiorities, the obtained sulfur electrodes exhibit excellent electrochemical performance, i.e., high areal capacity of 5.6 mAh cm^?2, rate capability up to 5 C, and stable cycling over 1000 cycles with a low capacity fading rate of 0.04% per cycle at 1 C, demonstrating great promise in the development of practical Li–S batteries.     

Carbon‐Based Anodes for Lithium Sulfur Full Cells with High Cycle Stability

The lithium sulfur battery system has been studied since the late 1970s and has seen renewed interest in recent years. However, even after three decades of intensive research, prolonged cycling can only be achieved when a large excess of electrolyte and lithium is used. Here, for the first time, a balanced and stable lithium sulfur full cell is demonstrated with silicon–carbon as well as all‐carbon anodes. More than 1000 cycles, a specific capacity up to 1470 mAh g^?1 _sulfur (720 mAh g^?1 _cathode), and a high coulombic efficiency of over 99% even with a low amount of electrolyte are achieved. The alternative anodes do not suffer from electrolyte depletion, which is found to be the main cause of cell failure when using metallic lithium anodes.