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.     

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.     

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.     

Magnesium Anodes with Extended Cycling Stability for Lithium‐Ion Batteries

Magnesium as a promising alloy‐type anode material for lithium‐ion batteries features both high theoretical specific capacity (2150 mAh g^?1) and stack energy density (1032 Wh L^?1). However, the poor cycling performance of Mg‐based anodes severely limits their application, mainly because high‐impedance films can grow easily on the surface of Mg and cause diminished electrochemical activity. As a result, the capacities of reported Mg anodes fade quickly in less than 100 cycles. To improve the stability of Mg anodes, 3D Cu@Mg@C structures are prepared by depositing Mg/C composite on 3D Cu current collectors. The resulting 3D Cu@Mg@C anodes can deliver an initial capacity of 1392 mAh g^?1. With a second‐cycle capacity of 1255 mAh g^?1, 91% can be retained after 1000 cycles at 0.5 C. When cycled at 2 C, the initial capacity can be maintained for 4000 cycles. This remarkably improved cycling performance can be attributed to both the 3D structure and the embedded carbon layers of the 3D Cu@Mg@C electrodes that facilitate electrical contact and prevent the growth of high‐impedance films during cycling. With 3D Cu@Mg@C anodes and LiFePO₄ cathodes, full cells are assembled and charging by a rotating triboelectric nanogenerator that can harvest mechanical energy is demonstrated.     

Facile Solid‐State Growth of 3D Well‐Interconnected Nitrogen‐Rich Carbon Nanotube–Graphene Hybrid Architectures for Lithium–Sulfur Batteries

Constructing 3D carbon structures built from carbon nanotubes (CNTs) and graphene has been considered as an effective approach to achieve superior properties in energy conversion and storage because of the synergistic combination of the advantages of each building block. Herein, a facile solid‐state growth strategy is reported for the first time to fabricate highly nitrogen doped CNT–graphene 3D nanostructures without the necessity to use chemical vapor deposition. As cathode hosts for lithium–sulfur batteries, the hybrid architectures exhibit reversible capacities of 1314 and 922 mAh g^?1 at 0.2 and 1 C, respectively, and a capacity retention of 97% after 200 cycles at a high rate of 2 C, revealing their great potential for energy storage application.     

3D Carbonaceous Current Collectors: The Origin of Enhanced Cycling Stability for High‐Sulfur‐Loading Lithium–Sulfur Batteries

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.     

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.     

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.     

Gas Pickering Emulsion Templated Hollow Carbon for High Rate Performance Lithium Sulfur Batteries

A CO₂ in water nanoparticle stabilized Pickering emulsion is used to template micrometer sized hollow porous nitrogen doped carbon particles for high rate performance lithium sulfur battery. For the first time, nanoparticles serve the dual role of an emulsion stabilizer and a pore template for the shell, directly utilizing in situ generated CO₂ bubbles as template for the core. The minimalistic nature of this method does not require expensive surfactants or additional core templates. Upon polymerization of melamine formaldehyde onto CO₂, a robust polymer/silica composite shell is formed and transformed into a porous shell upon washing. The micrometer‐sized hollow morphology in combination with its nitrogen rich porous shell demonstrates impressive rate capabilities of 670 and 500 mAh g^?1 even at a high rate of 7C and 9C, respectively. This material also possesses excellent cycle durability, exhibiting a low capacity decay of 0.088%/cycle over 300 cycles. Measurement of the shuttle current and impedance provides interesting insight into the polysulfide mass transfer mechanism of hollow structured sulfur hosts.     

Bifunctional Separator with a Light‐Weight Carbon‐Coating for Dynamically and Statically Stable Lithium‐Sulfur Batteries

Sulfur is appealing as a high‐capacity cathode for rechargeable lithium batteries as it offers a high theoretical capacity of 1672 mA h g^?1 and is abundant. However, the commercialization of Li‐S batteries is hampered by fast capacity fade during both dynamic cell cycling and static cell resting. The poor electrochemical stability is due to polysulfide diffusion, leading to a short cycle life and severe self‐discharge. Here, we present the design of a bifunctional separator with a light‐weight carbon‐coating that integrates the two necessary components already inside the cell: the conductive carbon and the separator. With no extra additives, this bifunctional carbon‐coated separator allows the use of pure sulfur cathodes involving no complex composite synthesis process, provides a high initial discharge capacity of 1389 mA h g^?1 with excellent dynamic stability, and facilitates a high reversible capacity of 828 mA h g^?1 after 200 cycles. In addition, the static stability is evidenced by low self‐discharge and excellent capacity retention after a 3 month rest period.     

Carbon Coated Fe3O4 Nanospindles as a Superior Anode Material for Lithium‐Ion Batteries

Carbon‐coated Fe₃O₄ nanospindles are synthesized by partial reduction of monodispersed hematite nanospindles with carbon coatings, and investigated with scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, and electrochemical experiments. The Fe₃O₄? C nanospindles show high reversible capacity (～745 mA h g^?1 at C/5 and ～600 mA h g^?1 at C/2), high coulombic efficiency in the first cycle, as well as significantly enhanced cycling performance and high rate capability compared with bare hematite spindles and commercial magnetite particles. The improvements can be attributed to the uniform and continuous carbon coating layers, which have several functions, including: i) maintaining the integrity of particles, ii) increasing the electronic conductivity of electrodes leading to the formation of uniform and thin solid electrolyte interphase (SEI) films on the surface, and iii) stabilizing the as‐formed SEI films. The results give clear evidence of the utility of carbon coatings to improve the electrochemical performance of nanostructured transition metal oxides as superior anode materials for lithium‐ion batteries.     

In Situ Synthesis of Bipyramidal Sulfur with 3D Carbon Nanotube Framework for Lithium–Sulfur Batteries

A one‐pot synthesis of three‐dimensional carbon nanotube frameworks with bipyramidal sulfur particles and the application of these materials for a cathode in lithium–sulfur (Li–S) battery are reported. By simple mixing of multi‐walled carbon nanotubes (MWCNTs), sulfur powder, and capping agents in water/tetrahydrofuran, micrometer bipyramidal sulfur particles enclosed with MWCNTs are synthesized. The MWCNTs spontaneously form a 3D conducting network inside and outside the sulfur particle. Along the edge of MWCNT framework, a sulfur particle‐free region is present, which comprises ≈35 vol% based on the total volume. These sulfur‐MWCNT bipyramidal particles are mixed with conductive carbon additive to prepare binder‐free cathode for Li–S cells. The Li–S cells deliver a specific discharge capacity of ≈1600 mAh g^?1 at 0.05 C on the first cycle. In particular, these Li–S cells show high rate stability and Coulombic efficiency with deep discharge and charge (1.0–3.0 V vs Li/Li⁺). This resultant performance can arise from 1) homogeneous distribution of the conducting MWCNT framework and the carbon additive coating layer on the sulfur particle, which allow rapid Li⁺ ion/electrolyte diffusion and mitigation of polysulfide shuttle, respectively, and 2) the sulfur‐free buffer space accommodating volume expansion. It is expected that this new cathode design with the simple synthetic process can reduce the number of preparation steps, thus allowing the construction of a low‐cost Li–S battery.     

A 3D Hybrid of Chemically Coupled Nickel Sulfide and Hollow Carbon Spheres for High Performance Lithium–Sulfur Batteries

Lithium–sulfur batteries are a promising next‐generation energy storage device owing to their high theoretical capacity and the low cost and abundance of sulfur. However, the low conductivity and loss of active sulfur material during operation greatly limit the rating capabilities and cycling stability of lithium–sulfur batteries. In this work, a unique sulfur host hybrid material comprising nanosized nickel sulfide (NiS) uniformly distributed on 3D carbon hollow spheres (C‐HS) is fabricated using an in situ thermal reduction and sulfidation method. In the hybrid material, the nanosized NiS provides a high adsorption capability for polysulfides and the C‐HS serves as a physical confinement for polysulfides and also a 3D electron transfer pathway. Moreover, NiS has strong chemical coupling with the C‐HS, favoring fast charge transfer and redox kinetics of the sulfur electrode. With a sulfur loading of up to 2.3 mg cm^?2, the hybrid material‐based lithium–sulfur batteries offer a capacity decay as low as 0.013% per cycle and a capacity of 695 mA h g^?1 at 0.5 C after 300 cycles. This unique 3D hybrid material with strong chemical coupling provides a promising sulfur host for high performance lithium–sulfur batteries.     

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.     

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.