A High‐Volumetric‐Capacity Cathode Based on Interconnected Close‐Packed N‐Doped Porous Carbon Nanospheres for Long‐Life Lithium–Sulfur Batteries

This study reports a Li–S battery cathode of high volumetric capacity enabled by novel micro‐ and mesostructuring. The cathode is based on monodisperse highly porous carbon nanospheres derived from a facile template‐ and surfactant‐free method. At the mesoscale, the nanospheres structure into interconnected close‐packed clusters of a few microns in extent, thus facilitating the fabrication of dense crack‐free high areal sulfur loading (5 mg cm^?2) cathodes with high electrical conductivity and low cathode impedance. A combination of the nitrogen doping (5 wt%), high porosity (2.3 cm³ g^?1), and surface area (2900 m² g^?1) at the microscale enables high sulfur immobilization and utilization. The cathode delivers among the best reported volumetric capacity to date, above typical Li‐ion areal capacity at 0.2 C over 200 cycles and low capacity fading of 0.1% per cycle at 0.5 C over 500 cycles. The compact cathode structure also ensures a low electrolyte requirement (6 µL mg^?1), which aids a low overall cell weight, and further, among the best gravimetric capacities published to date as well.     

Breathable Carbon‐Free Electrode: Black TiO2 with Hierarchically Ordered Porous Structure for Stable Li–O2 Battery

This paper introduces oxygen‐deficient black TiO₂ with hierarchically ordered porous structure fabricated by a simple hydrogen reduction as a carbon‐ and binder‐free cathode, demonstrating superior energy density and stability. With the high electrical conductivity derived from oxygen vacancies or Ti³⁺ ions, this unique electrode features micrometer‐sized voids with mesoporous walls for the effective accommodation of Li₂O₂ toroid and for the rapid transport of reaction molecules without the electrode being clogged. In the highly ordered architecture, toroidal Li₂O₂ particles are guided to form with a regular size and separation, which induces the most of Li₂O₂ external surface to be directly exposed to the electrolyte. Therefore, large Li₂O₂ toroids (≈300 nm) grown from solution can be effectively charged by incorporating a soluble catalyst, resulting in a very small polarization (≈0.37 V). Furthermore, disordered nanoshell in black TiO₂ is suggested to protect the oxygen‐deficient crystalline core, by which oxidation of Ti³⁺ is kinetically impeded during battery operation, leading to the enhanced electrode stability even in a highly oxidizing environment under high voltage (≈4 V).     

Double‐Shelled NiO‐NiCo2O4 Heterostructure@Carbon Hollow Nanocages as an Efficient Sulfur Host for Advanced Lithium–Sulfur Batteries

Double‐shelled NiO‐NiCo₂O₄ heterostructure@carbon hollow nanocages as efficient sulfur hosts are synthesized to overcome the barriers of lithium–sulfur (Li–S) batteries simultaneously. The double‐shelled nanocages can prevent the diffusion of lithium polysulfides (LiPSs) effectively. NiO‐NiCo₂O₄ heterostructure is able to promote polysulfide conversion reactions. Furthermore, the thin carbon layer outside can improve the electrical conductivity during cycling. Besides, such unique double‐shelled hollow nanocage architecture can also accommodate the volumetric effect of sulfur upon cycling. As a result, the prepared S/NiO‐NiCo₂O₄@carbon (C) electrode exhibits good rate capacities and stable cycling life up to 500 cycles at 0.5 C with a very low capacity decay rate of only ≈0.059% per cycle.     

3D Ferroconcrete‐Like Aminated Carbon Nanotubes Network Anchoring Sulfur for Advanced Lithium–Sulfur Battery

To address the serious capacity fading in lithium–sulfur batteries, a 3D ferroconcrete‐like aminated carbon nanotubes network with polyaniline coating as an effective sulfur host to contain polysulfide dissolution is presented here. In this composite, the cross‐linked aminated carbon nanotubes framework provides a fast charge transport pathway and enhancement in the reaction kinetics of the active material to greatly improve the rate capability and sulfur utilization. The ethylenediamine moieties provide strong adhesion of polar discharge products to nonpolar carbon surfaces and thus efficiently prevent polysulfide dissolution to improve the cycle stability, confirmed by density functional theory calculations. The outside polyaniline layers structurally restrain polysulfides to prevent the shuttle effect and active material loss. Benefiting from these advantages, the synthesized composite exhibits a high initial capacity of 1215 mAh g^?1 and a capacity of 975 mAh g^?1 after 200 cycles at 0.2 C. Even after 200 cycles at 0.5 C, a capacity of 735 mAh g^?1 can be maintained, among the best performance reported. The strategy in this work can shed some light on modifying nonpolar carbon surfaces via the amination process to chemically attach sulfur species for high‐performance lithium–sulfur batteries.     

Nitrogen‐Doped Graphene‐Supported Mixed Transition‐Metal Oxide Porous Particles to Confine Polysulfides for Lithium–Sulfur Batteries

The intricate charge–discharge reactions and bad conductivity nature of sulfur determine the extreme importance of cathode engineering for Li–S batteries. Herein, spinel ZnCo₂O₄ porous particles@N‐doped reduced graphene oxide (ZnCo₂O₄@N‐RGO) are prepared via the combined procedures of refluxing and hydrothermal treatment, consisting of interconnected uniform ZnCo₂O₄ nanocubes with an average size of 5 nm anchored on graphene nanosheets. The as‐obtained composite can act as an inimitable cathode scaffold to suppress the shuttling of polysulfides by chemical confinement of ZnCo₂O₄ and N‐RGO for the first time, as demonstrated by the adsorption energy of ZnCo₂O₄ to Li₂S₄ via the strong chemical bonding between Zn or Co and S. The RGO nanosheets with a relatively high specific surface area provide a good conductive network and structural stability. The introduction of doped N atoms and numerous ZnCo₂O₄ porous nanoparticles can inhibit the transfer of lithium polysulfides between the cathode and anode. Due to the unique structural and compositional features, the as‐obtained hybrid materials with the high sulfur loading of 71% and even 82% still deliver high specific capacity, good rate capability, and enhanced cycling stability with exceptionally high initial Coulombic efficiency, which displays a high utilization of sulfur.     

A High‐Efficiency Sulfur/Carbon Composite Based on 3D Graphene Nanosheet@Carbon Nanotube Matrix as Cathode for Lithium–Sulfur Battery

Carbon materials have attracted extensive attention as the host materials of sulfur for lithium–sulfur battery, especially those with 3D architectural structure. Here, a novel 3D graphene nanosheet–carbon nanotube (GN–CNT) matrix is obtained through a simple one‐pot pyrolysis process. The length and density of CNTs can be readily tuned by altering the additive amount of carbon source (urea). Specifically, CNTs are in situ introduced onto the surface of the graphene nanosheets (GN) and show a stable covalent interaction with GN. Besides, in the GN–CNT matrix, cobalt nanoparticles with different diameters exist as being wrapped in the top of CNTs or scattering on the GN surface, and abundant heteroatoms (N, O) are detected, both of which can help in immobilizing sulfur species. Such a rationally designed 3D GN–CNT matrix makes much more sense in enhancing the electrochemical performance of the sulfur cathode for rapid charge transfer and favorable electrolyte infiltration. Moreover, the presence of dispersed cobalt nanoparticles is beneficial for trapping lithium polysulfides by strong chemical interaction, and facilitating the mutual transformation between the high‐order polysulfides and low‐order ones. As a result, the S/GN–CNT composite presents a high sulfur utilization and large capacity on the basis of the S/GN–CNT composite as active material.     

Affinity Laminated Chromatography Membrane Built‐in Electrodes for Suppressing Polysulfide Shuttling in Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries are promising candidates for energy storage, but suffer from capacity and cycling challenges caused by the serious shuttling effect of polysulfide (PS) ions. To address these issues, a sodium alginate (SA)‐derived affinity laminated chromatography membrane built‐in electrode is designed. This is the first attempt to utilize this type of membrane, which is widely used for the selective adsorption of proteins, in the battery field. An ordered multilayer structure throughout the electrode can easily be obtained, and the number of membrane layers can be also conveniently controlled by varying the cross‐linking time of SA. The PS shuttling effect is efficiently suppressed and the permeability of PSs is reduced by enveloping the carbon/sulfur powder in ultrathin laminated chromatography membranes. As a result, these designed electrodes deliver a superhigh initial capacity of 1492 mA h g^?1, with a capacity retention almost 20% higher than the contrast. This low‐cost and easily mass‐producible strategy inspired by affinity chromatography is expected to effectively solve the PS shuttling problem toward high‐loading and long‐lifetime Li–S batteries in practice.     

Revisiting the Role of Conductivity and Polarity of Host Materials for Long‐Life Lithium–Sulfur Battery

Despite their high theoretical energy density and low cost, lithium–sulfur batteries (LSBs) suffer from poor cycle life and low energy efficiency owing to the polysulfides shuttle and the electronic insulating nature of sulfur. Conductivity and polarity are two critical parameters for the search of optimal sulfur host materials. However, their role in immobilizing polysulfides and enhancing redox kinetics for long‐life LSBs are not fully understood. This work has conducted an evaluation on the role of polarity over conductivity by using a polar but nonconductive platelet ordered mesoporous silica (pOMS) and its replica platelet ordered mesoporous carbon (pOMC), which is conductive but nonpolar. It is found that the polar pOMS/S cathode with a sulfur mass fraction of 80 wt% demonstrates outstanding long‐term cycle stability for 2000 cycles even at a high current density of 2C. Furthermore, the pOMS/S cathode with a high sulfur loading of 6.5 mg cm^?2 illustrates high areal and volumetric capacities with high capacity retention. Complementary physical and electrochemical probes clearly show that surface polarity and structure are more dominant factors for sulfur utilization efficiency and long‐life, while the conductivity can be compensated by the conductive agent involved as a required electrode material during electrode preparation. The present findings shed new light on the design principles of sulfur hosts towards long‐life and highly efficient LSBs.     

High‐Capacity Concentration Gradient Li[Ni0.865Co0.120Al0.015]O2 Cathode for Lithium‐Ion Batteries

A Ni‐rich concentration‐gradient Li[Ni_0.865Co_0.120Al_0.015]O₂ (NCA) cathode is prepared with a Ni‐rich core to maximize the discharge capacity and a Co‐rich particle surface to provide structural and chemical stability. Compared to the conventional NCA cathode with a uniform composition, the gradient NCA cathode exhibits improved capacity retention and better thermal stability. Even more remarkably, the gradient NCA cathode maintains 90% of its initial capacity after 100 cycles when cycled at 60 °C, whereas the conventional cathode exhibits poor capacity retention and suffers severe structural deterioration. The superior cycling stability of the gradient NCA cathode largely stemmed from the gradient structure combines with the Co‐rich surface, which provides chemical stability against electrolyte attack and reduces the inherent internal strain observed in all Ni‐rich layered cathodes in their charged state, thus providing structural stability against the repeated anisotropic volume changes during cycling. The high discharge capacity of the proposed gradient NCA cathode extends the driving range of electric vehicles and reduces battery costs. Furthermore, its excellent capacity retention guarantees a long battery life. Therefore, gradient NCA cathodes represent one of the best classes of cathode materials for electric vehicle applications that should satisfy the demands of future electric vehicles.     

Optimized Catalytic WS2–WO3 Heterostructure Design for Accelerated Polysulfide Conversion in Lithium–Sulfur Batteries

The lithium–sulfur (Li–S) battery is a next generation high energy density battery, but its practical application is hindered by the poor cycling stability derived from the severe shuttling of lithium polysulfides (LiPSs). Catalysis is a promising way to solve this problem, but the rational design of relevant catalysts is still hard to achieve. This paper reports the WS₂–WO₃ heterostructures prepared by in situ sulfurization of WO₃, and by controlling the sulfurization degree, the structure is controlled, which balances the trapping ability (by WO₃) and catalytic activity (by WS₂) toward LiPSs. As a result, the WS₂–WO₃ heterostructures effectively accelerate LiPS conversion and improve sulfur utilization. The Li–S battery with 5 wt% WS₂–WO₃ heterostructures as additives in the cathode shows an excellent rate performance and good cycling stability, revealing a 0.06% capacity decay each cycle over 500 cycles at 0.5 C. By building an interlayer with such heterostructure‐added graphenes, the battery with a high sulfur loading of 5 mg cm^?2 still shows a high capacity retention of 86.1% after 300 cycles at 0.5 C. This work provides a rational way to prepare the metal oxide–sulfide heterostructures with an optimized structure to enhance the performance of Li–S batteries.     

Hierarchical NiCo2S4@NiO Core–Shell Heterostructures as Catalytic Cathode for Long‐Life Li‐O2 Batteries

The critical challenges of Li‐O₂ batteries lie in sluggish oxygen redox kinetics and undesirable parasitic reactions during the oxygen reduction reaction and oxygen evolution reaction processes, inducing large overpotential and inferior cycle stability. Herein, an elaborately designed 3D hierarchical heterostructure comprising NiCo₂S₄@NiO core–shell arrays on conductive carbon paper is first reported as a freestanding cathode for Li‐O₂ batteries. The unique hierarchical array structures can build up multidimensional channels for oxygen diffusion and electrolyte impregnation. A built‐in interfacial potential between NiCo₂S₄ and NiO can drastically enhance interfacial charge transfer kinetics. According to density functional theory calculations, intrinsic LiO₂‐affinity characteristics of NiCo₂S₄ and NiO play an importantly synergistic role in promoting the formation of large peasecod‐like Li₂O₂, conducive to construct a low‐impedance Li₂O₂/cathode contact interface. As expected, Li‐O₂ cells based on NiCo₂S₄@NiO electrode exhibit an improved overpotential of 0.88 V, a high discharge capacity of 10 050 mAh g^?1 at 200 mA g^?1, an excellent rate capability of 6150 mAh g^?1 at 1.0 A g^?1, and a long‐term cycle stability under a restricted capacity of 1000 mAh g^?1 at 200 mA g^?1. Notably, the reported strategy about heterostructure accouplement may pave a new avenue for the effective electrocatalyst design for Li‐O₂ batteries.     

Ultrahigh‐Capacity and Fire‐Resistant LiFePO4‐Based Composite Cathodes for Advanced Lithium‐Ion Batteries

The growing demand for advanced energy storage devices with high energy density and high safety has continuously driven the technical upgrades of cell architectures as well as electroactive materials. Designing thick electrodes with more electroactive materials is a promising strategy to improve the energy density of lithium‐ion batteries (LIBs) without alternating the underlying chemistry. However, the progress toward thick, high areal capacity electrodes is severely limited by the sluggish electronic/ionic transport and easy deformability of conventional electrodes. A self‐supported ultrahigh‐capacity and fire‐resistant LiFePO₄ (UCFR‐LFP)‐based nanocomposite cathode is demonstrated here. Benefiting from the structural and chemical uniqueness, the UCFR‐LFP electrodes demonstrate exceptional improvements in electrochemical performance and mass loading of active materials, and thermal stability. Notably, an ultrathick UCFR‐LFP electrode (1.35 mm) with remarkably high mass loading of active materials (108 mg cm^?2) and areal capacity (16.4 mAh cm^?2) is successfully achieved. Moreover, the 1D inorganic binder‐like ultralong hydroxyapatite nanowires (HAP NWs) enable the UCFR‐LFP electrode with excellent thermal stability (structural integrity up to 1000 °C and electrochemical activity up to 750 °C), fire‐resistance, and wide‐temperature operability. Such a unique UCFR‐LFP electrode offers a promising solution for next‐generation LIBs with high energy density, high safety, and wide operating‐temperature window.     

In Situ Assembly of 2D Conductive Vanadium Disulfide with Graphene as a High‐Sulfur‐Loading Host for Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries are deemed to be one of the most promising energy storage technologies because of their high energy density, low cost, and environmental benignancy. However, existing drawbacks including the shuttling of intermediate polysulfides, the insulating nature of sulfur, and the considerable volume change of sulfur cathode would otherwise result in the capacity fading and unstable cycling. To overcome these challenges, herein an in situ assembly route is presented to fabricate VS₂/reduced graphene oxide nanosheets (G–VS₂) as a sulfur host. Benefiting from the 2D conductive and polar VS₂ interlayered within a graphene framework, the obtained G–VS₂ hybrids can effectively suppress the polysulfide shuttling, facilitate the charge transport, and cushion the volume expansion throughout the synergistic effect of structural confinement and chemical anchoring. With these advantageous features, the obtained sulfur cathode (G–VS₂/S) can deliver an outstanding rate capability (≈950 and 800 mAh g^?1 at 1 and 2 C, respectively) and an impressive cycling stability at high rates (retaining ≈532 mAh g^?1 after 300 cycles at 5 C). More significantly, it enables superior cycling performance of high‐sulfur‐loading cathodes (achieving an areal capacity of 5.1 mAh cm^?2 at 0.2 C with a sulfur loading of 5 mg cm^?2) even at high current densities.     

Long‐Life,High‐Rate Lithium–Sulfur Cells with a Carbon‐Free VN Host as an Efficient Polysulfide Adsorbent and Lithium Dendrite Inhibitor

Lithium–sulfur (Li‐S) batteries are a promising next‐generation energy‐storage system, but the polysulfide shuttle and dendritic Li growth seriously hinder their commercial viability. Most of the previous studies have focused on only one of these two issues at a time. To address both the issues simultaneously, presented here is a highly conductive, noncarbon, 3D vanadium nitride (VN) nanowire array as an efficient host for both sulfur cathodes and lithium‐metal anodes. With fast electron and ion transport and high porosity and surface area, VN traps the soluble polysulfides, promotes the redox kinetics of sulfur cathodes, facilitates uniform nucleation/growth of lithium metal, and inhibits lithium dendrite growth at an unprecedented high current density of 10 mA cm^?2 over 200 h of repeated plating/stripping. As a result, VN‐Li||VN‐S full cells constructed with VN as both an anode and cathode host with a negative to positive electrode capacity ratio of only ≈2 deliver remarkable electrochemical performance with a high Coulombic efficiency of ≈99.6% over 850 cycles at a high 4 C rate and a high areal capacity of 4.6 mA h cm^?2. The strategy presented here offers a viable approach to realize high‐energy‐density, safe Li‐metal‐based batteries.     

A Li2S‐TiS2‐Electrolyte Composite for Stable Li2S‐Based Lithium–Sulfur Batteries

Li₂S is a fully lithiated sulfur‐based cathode with a high theoretical capacity of 1166 mAh g^?1 that can be coupled with lithium‐free anodes to develop high‐energy‐density lithium–sulfur batteries. Although various approaches have been pursued to obtain a high‐performance Li₂S cathode, there are still formidable challenges with it (e.g., low conductivity, high overpotential, and irreversible polysulfide diffusion) and associated fabrication processes (e.g., insufficient Li₂S, excess electrolyte, and low reversible capacity), which have prevented the realization of high electrochemical utilization and stability. Here, a new cathode design composed of a homogeneous Li₂S‐TiS₂‐electrolyte composite that is prepared by a simple two‐step dry/wet‐mixing process is demonstrated, allowing the liquid electrolyte to wet the powder mixture consisting of insulating Li₂S and conductive TiS₂. The close‐contact, three‐phase boundary of this system improves the Li₂S‐activation efficiency and provides fast redox‐reaction kinetics, enabling the Li₂S‐TiS₂‐electrolyte cathode to attain stable cyclability at C/7 to C/3 rates, superior long‐term cyclability over 500 cycles, and promising high‐rate performance up to 1C rate. More importantly, this improved performance results from a cell design attaining a high Li₂S loading of 6 mg cm^?2, a high Li₂S content of 75 wt%, and a low electrolyte/Li₂S ratio of 6.     

Elastic Sandwich‐Type rGO–VS2/S Composites with High Tap Density: Structural and Chemical Cooperativity Enabling Lithium–Sulfur Batteries with High Energy Density

Driven by increasing demand for high‐energy‐density batteries for consumer electronics and electric vehicles, substantial progress is achieved in the development of long‐life lithium–sulfur (Li–S) batteries. Less attention is given to Li–S batteries with high volume energy density, which is crucial for applications in compact space. Here, a series of elastic sandwich‐structured cathode materials consisting of alternating VS₂‐attached reduced graphene oxide (rGO) sheets and active sulfur layers are reported. Due to the high polarity and conductivity of VS₂, a small amount of VS₂ can suppress the shuttle effect of polysulfides and improve the redox kinetics of sulfur species in the whole sulfur layer. Sandwich‐structured rGO–VS₂/S composites exhibit significantly improved electrochemical performance, with high discharge capacities, low polarization, and excellent cycling stability compared with their bare rGO/S counterparts. Impressively, the tap density of rGO–VS₂/S with 89 wt% sulfur loading is 1.84 g cm^?3, which is almost three times higher than that of rGO/S with the same sulfur content (0.63 g cm^?3), and the volumetric specific capacity of the whole cell is as high as 1182.1 mA h cm^?3, comparable with the state‐of‐the‐art reported for energy storage devices, demonstrating the potential for application of these composites in long‐life and high‐energy‐density Li–S batteries.