Highly Stable Lithium–Sulfur Batteries Based on Laponite Nanosheet‐Coated Celgard Separators

Lithium–sulfur (Li–S) batteries are of great interest due to their high theoretical energy density. However, one of the key issues hindering their real world applications is polysulfide shuttle, which results in severe capacity decay and self‐discharge. Here, a laponite nanosheets/carbon black coated Celgard (LNS/CB‐Celgard) separator to inhibit polysulfide shuttle and to enhance the Li⁺ conductivity simultaneously is reported. The polysulfide shuttle is efficiently inhibited through strong interactions between the O active sites of the LNS and polysulfides by forming the Li···O and O? S bonds. Moreover, the separator features high Li⁺ conductivity, fast Li⁺ diffusion, excellent electrolyte wettability, and high thermal stability. Consequently, the Li–S batteries with the LNS/CB‐Celgard separator and the pure S cathode show a high initial reversible capacity of 1387 mA h g^?1 at 0.1 C, high rate performance, superior cycling stability (with a capacity decay rate of 0.06% cycle^?1 at 0.2 C and 0.028% cycle^?1 at 1.0 C over 500 cycles), and ultralow self‐discharge. The separator could also enhance the performance of other batteries such as the LiFePO₄/separator/Li battery. This work sheds a new light on the design and preparation of novel separators for highly stable Li–S batteries via a “green” and cost‐effective approach.     

Dual‐Confined Flexible Sulfur Cathodes Encapsulated in Nitrogen‐Doped Double‐Shelled Hollow Carbon Spheres and Wrapped with Graphene for Li–S Batteries

Batteries with high energy and power densities along with long cycle life and acceptable safety at an affordable cost are critical for large‐scale applications such as electric vehicles and smart grids, but is challenging. Lithium–sulfur (Li‐S) batteries are attractive in this regard due to their high energy density and the abundance of sulfur, but several hurdles such as poor cycle life and inferior sulfur utilization need to be overcome for them to be commercially viable. Li–S cells with high capacity and long cycle life with a dual‐confined flexible cathode configuration by encapsulating sulfur in nitrogen‐doped double‐shelled hollow carbon spheres followed by graphene wrapping are presented here. Sulfur/polysulfides are effectively immobilized in the cathode through physical confinement by the hollow spheres with porous shells and graphene wrapping as well as chemical binding between heteronitrogen atoms and polysulfides. This rationally designed free‐standing nanostructured sulfur cathode provides a well‐built 3D carbon conductive network without requiring binders, enabling a high initial discharge capacity of 1360 mA h g^?1 at a current rate of C/5, excellent rate capability of 600 mA h g^?1 at 2 C rate, and sustainable cycling stability for 200 cycles with nearly 100% Coulombic efficiency, suggesting its great promise for advanced Li–S batteries.     

Polysulfide Confinement and Highly Efficient Conversion on Hierarchical Mesoporous Carbon Nanosheets for Li–S Batteries

Lithium–sulfur (Li–S) batteries have attracted increasing attention due to their extremely high theoretical specific capacity and a promising power density. However, practical applications of Li–S batteries are still limited by the relatively low performance, owing to poor conductivity of sulfur itself and discharge products (Li₂S/Li₂S₂) as well as the shuttle effect of the intermediate polysulfide. Herein, honeycomb‐like mesoporous Co, N‐doped carbon nanosheets (MC‐NS) with a high specific surface area and abundant defects are developed which, simultaneously enable polysulfide confinement and highly efficient conversion. Moreover, density functional theory calculations and experiments show that the Co‐N‐C catalytic site as well as defects on the carbon skeleton of the MC‐NS facilitate high efficiency in suppressing the shuttle effect of polysulfides. In situ Raman spectra further demonstrate the enhancement of adsorption ability and conversion efficiency of polysulfides on this host. As a result, the MC‐NS enables much increased specific capacity and cycling stability of Li–S batteries. This work provides a useful strategy for realizing practical applications of high‐performance Li–S batteries.     

Electrochemically Stable Rechargeable Lithium–Sulfur Batteries with a Microporous Carbon Nanofiber Filter for Polysulfide

As a primary component in lithium–sulfur (Li–S) batteries, the separator may require a custom design in order to facilitate electrochemical stability and reversibility. Here, a custom separator with an activated carbon nanofiber (ACNF)‐filter coated onto a polypropylene membrane is presented. The entire configuration is comprised of the ACNF filter arranged adjacent to the sulfur cathode so that it can filter out the freely migrating polysulfides and suppress the severe polysulfide diffusion. Four differently optimized ACNF‐filter‐coated separators have been developed with tunable micropores as an investigation into the electrochemical and engineering design parameters of functionalized separators. The optimized parameters that are verified by electrochemical and microstructural analyses require the coated ACNF filter to possess the following: (i) a porous architecture with abundant micropores, (ii) small micropore sizes, and (iii) high electrical conductivity and effective electrolyte immersion. It is found that the ACNF20‐filter‐coated separator demonstrates an overall superior boost in the electrochemical utilization (discharge capacity: 1270 mA h g^?1) and polysulfide retention (capacity fade rate: 0.13% cycle^?1 after 200 cycles). These results show that the modified thin‐film‐coating technique is a viable approach to designing ultratough ACNF‐filter‐coated separators with outstanding mechanical strength and flexibility as an advanced component in Li–S cells.     

Dense Graphene Monolith for High Volumetric Energy Density Li–S Batteries

Despite the outstanding gravimetric performance of lithium–sulfur (Li–S) batteries, their practical volumetric energy density is normally lower than that of lithium‐ion batteries, mainly due to the low density of nanostructured sulfur as well as the porous carbon hosts. Here, a novel approach is developed to fabricate high‐density graphene bulk materials with “ink‐bottle‐like” mesopores by phosphoric acid (H₃PO₄) activation. These pores can effectively confine the polysulfides due to their unique structure with a wide body and narrow neck, which shows only a 0.05% capacity fade per cycle for 500 cycles (75% capacity retention) for accommodating polysulfides. With a density of 1.16 g cm^?3, a hybrid cathode containing 54 wt% sulfur delivers a high volumetric capacity of 653 mA h cm^?3. As a result, a device‐level volumetric energy density as high as 408 W h L^?1 is achieved with a cathode thickness of 100 µm. This is a periodic yet practical advance to improve the volumetric performance of Li–S batteries from a device perspective. This work suggests a design principle for the real use Li–S batteries although there is a long way ahead to bridge the gap between Li–S batteries and Li–ion batteries in volumetric performance.     

An Efficient Separator with Low Li‐Ion Diffusion Energy Barrier Resolving Feeble Conductivity for Practical Lithium–Sulfur Batteries

Due to unprecedented features including high‐energy density, low cost, and light weight, lithium–sulfur batteries have been proposed as a promising successor of lithium‐ion batteries. However, unresolved detrimental low Li‐ion transport rates in traditional carbon materials lead to large energy barrier in high sulfur loading batteries, which prevents the lithium–sulfur batteries from commercialization. In this report, to overcome the challenge of increasing both the cycling stability and areal capacity, a metallic oxide composite (NiCo₂O₄@rGO) is designed to enable a robust separator with low energy barrier for Li‐ion diffusion and simultaneously provide abundant active sites for the catalytic conversion of the polar polysulfides. With a high sulfur‐loading of 6 mg cm^?2 and low sulfur/electrolyte ratio of 10, the assembled batteries deliver an initial capacity of 5.04 mAh cm^?2 as well as capacity retention of 92% after 400 cycles. The metallic oxide composite NiCo₂O₄@rGO/PP separator with low Li‐ion diffusion energy barrier opens up the opportunity for lithium–sulfur batteries to achieve long‐cycle, cost‐effective operation toward wide applications in electric vehicles and electronic devices.     

Separator Modified by Cobalt‐Embedded Carbon Nanosheets Enabling Chemisorption and Catalytic Effects of Polysulfides for High‐Energy‐Density Lithium‐Sulfur Batteries

Lithium‐sulfur (Li‐S) batteries are considered to be one of the promising next‐generation energy storage systems. Considerable progress has been achieved in sulfur composite cathodes, but high cycling stability and discharging capacity at the expense of volumetric capacity have offset their advantages. Herein, a functional separator is presented by coating cobalt‐embedded nitrogen‐doped porous carbon nanosheets and graphene on one surface of a commercial polypropylene separator. The coating layer not only suppresses the polysulfide shuttle effect through chemical affinity, but also functions as an electrocatalyst to propel catalytic conversion of intercepted polysulfides. The slurry‐bladed carbon nanotubes/sulfur cathode with 90 wt% sulfur deliver high reversible capacity of 1103 mA h g^?1 and volumetric capacity of 1062 mA h cm^?3 at 0.2 C, and the freestanding carbon nanofibers/sulfur cathode provides a high discharging capacity of 1190 mA h g^?1 and volumetric capacity of 1136 mA h cm^?3 at high sulfur content of 78 wt% and sulfur loading of 10.5 mg cm^?2. The electrochemical performance is comparable with or even superior to those in the state‐of‐the‐art carbon‐based sulfur cathodes. The separator reported in this work holds great promise for the development of high‐energy‐density Li‐S batteries.     

Long Cycle Life,Low Self‐Discharge Sodium–Selenium Batteries with High Selenium Loading and Suppressed Polyselenide Shuttling

The use of selenium as a cathode in rechargeable sodium–selenium batteries is hampered by low Se loading, inferior electrode kinetics, and polyselenide shuttling between the cathode and anode. Here a high‐performance sodium–selenium cell is presented by coupling a binder‐free, self‐interwoven carbon nanofiber–selenium cathode with a light‐weight carbon‐coated bifunctional separator. With this strategy, electrodes with a high Se mass loading (4.4 mg cm^?2) render high reversible capacities of 599 mA h g^?1 at 0.1C rate and 382 mA h g^?1 at 5C rate. In addition, this novel cell offers good shelf‐life with a low self‐discharge, retaining 93.4% of its initial capacity even after resting for six months. As evidenced by experimental and density functional theory analysis, the remarkable dynamic (cycle life) and static (shelf‐life) stabilities originate from the high electrical conductivity, improved Na‐ion accessibility through the 3D interconnected open channels, and highly restrained polyselenide shuttle. The results demonstrate the viability of high‐performance sodium–selenium batteries with high selenium loading.     

Tailored Reaction Route by Micropore Confinement for Li–S Batteries Operating under Lean Electrolyte Conditions

Lithium‐sulfur (Li–S) batteries are one of the most promising alternative energy storage systems beyond Li‐ion batteries. However, the sluggish kinetics of the nucleation and growth of the solid discharge product of Li₂S/Li₂S₂ in the lower discharge plateau has been recently identified as a critical hurdle for attaining high specific capacity in Li–S batteries with high sulfur loadings under lean electrolyte conditions. Herein, a new strategy of breaking the charge‐transport bottleneck by successful generation of experimentally verified stable Li₂S₂ and a reservoir of quasi‐solid lithium polysulfides within the micropores of activated carbon fiber cloth as a high‐sulfur‐loading host is proposed. The developed Li–S cell is capable of delivering a highly sustainable areal capacity of 6.0 mAh cm^?2 under lower electrolyte to sulfur ratios (<3.0 mL_E g_S^?1). Micropore confinement leads to generation of solid Li₂S₂ that enables high utilization of the entire electroactive area by its inherent self‐healing capacity. This strategy opens a new avenue for rational material designs for Li–S batteries under lean electrolyte condition.     

Carbon Quantum Dots–Modified Interfacial Interactions and Ion Conductivity for Enhanced High Current Density Performance in Lithium–Sulfur Batteries

Significant progress has achieved for developing lithium–sulfur (Li–S) batteries with high specific capacities and excellent cyclic stability. However, some critical issues emerge when attempts are made to raise the areal sulfur loading and increase the operation current density to meet the standards for various industrial applications. In this work, polyethylenimine‐functionalized carbon dots (PEI‐CDots) are designed and prepared for enhancing performance of the Li–S batteries with high sulfur loadings and operation under high current density situations. Strong chemical binding effects towards polysulfides and fast ion transport property are achieved in the PEI‐CDots‐modified cathodes. At a high current density of 8 mA cm^?2, the PEI‐CDots‐modified Li–S battery delivers a reversible areal capacity of 3.3 mAh cm^?2 with only 0.07% capacity decay per cycle over 400 cycles at 6.6 mg sulfur loading. Detailed analysis, involving electrochemical impedance spectroscopy, cyclic voltammetry, and density functional theory calculations, is done for the elucidation of the underlying enhancement mechanism by the PEI‐CDots. The strongly localized sulfur species and the promoted Li⁺ ion conductivity at the cathode–electrolyte interface are revealed to enable high‐performance Li–S batteries with high sulfur loading and large operational current.     

Boosting Polysulfide Redox Kinetics by Graphene‐Supported Ni Nanoparticles with Carbon Coating

Lithium–sulfur batteries have attracted extensive attention because of their high energy density. However, their application is still impeded by the inherent sluggish kinetics and solubility of intermediate products (i.e., polysulfides) of the sulfur cathode. Herein, graphene‐supported Ni nanoparticles with a carbon coating are fabricated by directly carbonizing a metal–organic framework/graphene oxide composite, which is then dispersed on a commercial glass fiber membrane to form a separator with electrocatalytic activity. In situ analysis and electrochemical investigation demonstrate that this modified separator can effectively suppress the shuttle effect and regulate the catalytic conversion of intercepted polysulfides, which is also confirmed by density functional theory calculations. It is found that Ni–C sites can chemically interact with polysulfides and stabilize the radical S₃^?? through Ni? S bonds to enable fast dynamic equilibrium with S₆^2?, while Ni nanoparticles reduce the oxidation barrier of Li₂S and accelerate ion/electron transport. As a result, the corresponding lithium–sulfur battery shows a high cycle stability (88% capacity retention over 100 cycles) even with a high sulfur mass loading of 8 mg cm^?2 and lean electrolyte (6.25 µ L mg^?1). Surprisingly, benefitting from the improved kinetics, the battery can work well at ?50 °C, which is rarely achieved by conventional Li–S batteries.     

3D Hyperbranched Hollow Carbon Nanorod Architectures for High‐Performance Lithium‐Sulfur Batteries

Lithium‐sulfur batteries have been plagued for a long time by low Coulombic efficiency, fast capacity loss, and poor high rate performance. Here, the synthesis of 3D hyperbranched hollow carbon nanorod encapsulated sulfur nanocomposites as cathode materials for lithium‐sulfur batteries is reported. The sulfur nanocomposite cathodes deliver a high specific capacity of 1378 mAh g^‐1 at a 0.1C current rate and exhibit stable cycling performance. The as‐prepared sulfur nanocomposites also achieve excellent high rate capacities and cyclability, such as 990 mAh g^‐1 at 1C, 861 mAh g^‐1 at 5C, and 663 mAh g^‐1 at 10C, extending to more than 500 cycles. The superior electrochemical performance are ascribed to the unique 3D hyperbranched hollow carbon nanorod architectures and high length/radius aspect ratio of the carbon nanorods, which can effectively prevent the dissolution of polysulfides, decrease self‐discharge, and confine the volume expansion on cycling. High capacity, excellent high‐rate performance, and long cycle life render the as‐developed sulfur/carbon nanorod nanocomposites a promising cathode material for lithium‐sulfur batteries.     

Functionalized Boron Nitride Nanosheets/Graphene Interlayer for Fast and Long‐Life Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries have a much higher energy density than Li ion batteries and thus are considered as next generation batteries for electric vehicle applications. However, the problem of rapid capacity fading due to the shuttling of soluble polysulfides between electrodes remains the main obstacle for practical applications. Here, a thin and selective interlayer structure has been designed and produced to decrease the charge transfer resistance and mitigate the shuttling problem, simply by coating the surface of cathode with a thin film of functionalized boron nitride nanosheets/graphene. Due to this thin and ultralight interlayer, the specific capacity and cycling stability of the Li–S batteries with a cathode of sulfur‐containing porous carbon nanotubes (≈60 wt% sulfur content) have been improved significantly with a life of over 1000 cycles, an initial specific capacity of 1100 mA h g^?1 at 3 C, and a cycle decay as low as 0.0037% per cycle. This new interlayer provides a promising approach to significantly enhance the performance of Li–S batteries.     

Suppressed Shuttle via Inhibiting the Formation of Long‐Chain Lithium Polysulfides and Functional Separator for Greatly Improved Lithium–Organosulfur Batteries Performance

The development of lithium–sulfur batteries is limited by the poor conductivity of sulfur cathodes and soluble long‐chain lithium polysulfides (LPSs), which cause the low utilization of sulfur and the aversive shuttle effect, and further, give rise to self‐discharge, rapid reversible capacity fading, and low Coulombic efficiency. In this work, a novel configuration is built for high‐performance lithium–organosulfur batteries, in which the organosulfur hybrid material and lithium metal are used as the cathode and the anode, respectively, and are separated by a functional separator decorated with nitrogen and sulfur co‐doped reduced graphite oxide. The organosulfur in the cathode prevents the shuttle effect by inhibiting the formation of long‐chain LPSs. In addition, the functional separator effectively adsorbs LPSs escaping from the cathode by electrostatic interactions and further restrains the shuttle effect. These effects are confirmed by density‐functional theory calculations. As a result, this novel configuration provides a high initial discharge capacity of 1364 mAh g^?1 at 0.2 C and a high discharge capacity of 750 mAh g^?1 at 1 C after 700 cycles with a very low capacity decay rate of 0.037% per cycle.     

Highly Dispersed Cobalt Clusters in Nitrogen‐Doped Porous Carbon Enable Multiple Effects for High‐Performance Li–S Battery

The lithium–sulfur (Li–S) battery is considered a promising candidate for the next generation of energy storage system due to its high specific energy density and low cost of raw materials. However, the practical application of Li–S batteries is severely limited by several weaknesses such as the shuttle effect of polysulfides and the insulation of the electrochemical products of sulfur and Li₂S/Li₂S₂. Here, by doping nitrogen and integrating highly dispersed cobalt catalysts, a porous carbon nanocage derived from glucose adsorbed metal–organic framework is developed as the host for a sulfur cathode. This host structure combines the reported positive effects, including high conductivity, high sulfur loading, effective stress release, fast lithium‐ion kinetics, fast interface charge transport, fast redox of Li₂S_n, and strong physical/chemical absorption, achieving a long cycle life (86% of capacity retention at 1C within 500 cycles) and high rate performance (600 mAh g^?1 at 5C) for a Li–S battery. By combining experiments and density functional theoretical calculations, it is demonstrated that the well‐dispersed cobalt clusters play an important role in greatly improving the diffusion dynamics of lithium, and enhance the absorption and conversion capability of polysulfides in the host structure.     

Plasma‐Enhanced Atomic Layer Deposition of Ultrathin Oxide Coatings for Stabilized Lithium–Sulfur Batteries

One of the most challenging problems in the development of lithium–sulfur batteries is polysulfide dissolution, which leads to cell overcharge and low columbic efficiency. Here, we propose the formation of a thin conformal Li‐ion permeable oxide layer on the sulfur‐carbon composite electrode surface by rapid plasma enhanced atomic layer deposition (PEALD) in order to prevent this dissolution, while preserving electrical connectivity within the individual electrode particles. PEALD synthesis offers a fast deposition rate combined with a low operating temperature, which allows sulfur evaporation during deposition to be avoided. After PEALD of a thin layer of aluminium oxide on the surface of electrode composed of large (ca. 10 μm in diameter) S‐infiltrated activated carbon fibers (S‐ACF), significantly enhanced cycle life is observed, with a capacity in excess of 600 mA·h·g^?1 after 300 charge–discharge cycles. Scanning electron microscopy (SEM) shows a significant amount of redeposited lithium sulfides on the external surface of regular S‐ACF electrodes. However, the PEALD alumina‐coated electrodes show no lithium sulfide deposits on the fiber surface. Energy dispersive spectroscopy (EDS) studies of the electrodes’ chemical composition further confirms that PEALD alumina coatings dramatically reduce S dissolution from the cathodes by confining the polysulfides inside the alumina barrier.     

Sulfur‐Embedded Activated Multichannel Carbon Nanofiber Composites for Long‐Life,High‐Rate Lithium–Sulfur Batteries

Despite the 3–5 fold higher energy density than the conventional Li‐ion cells at a lower cost, commercialization of Li–S batteries is hindered by the insulating nature of sulfur and the dissolution of intermediate polysulfides (Li₂S _X , 4 < X ≤ 8) into the electrolyte. The authors demonstrate here multichannel carbon nanofibers that are composed of parallel mesoporous channels connected with micropores as sulfur containment. In addition, hydroxyl functional groups are formed on the carbon surface through a chemical activation to enhance the interaction between sulfur and carbon. In the sulfur embedded composite, the mesoporous multichannel enhances the active material utilization and sulfur loading, while the micropores act as a reaction chamber for sulfur component and trap site for polysulfide with the assistance of the functional groups. This sulfur–carbon composite electrode with 2.2 mg cm^?2 sulfur displays excellent performance with high rate capability (initial capacity of 1351 mA h g^?1 at C/5 rate and 847 mA h g^?1 at 5C rate), maintaining 920 mA h g^?1 even after 300 cycles (a decay of 0.07% per cycle). Furthermore, a stable reversible capacity of as high as ≈1100 mA h g^?1 is realized with a higher sulfur loading of 4.6 mg cm^?2.     

Capture and Catalytic Conversion of Polysulfides by In Situ Built TiO2‐MXene Heterostructures for Lithium–Sulfur Batteries

The detrimental shuttle effect in lithium–sulfur batteries mainly results from the mobility of soluble polysulfide intermediates and their sluggish conversion kinetics. Herein, presented is a multifunctional catalyst with the merits of strong polysulfides adsorption ability, superior polysulfides conversion activity, high specific surface area, and electron conductivity by in situ crafting of the TiO₂‐MXene (Ti₃C₂T_x) heterostructures. The uniformly distributed TiO₂ on MXene sheets act as capturing centers to immobilize polysulfides, the hetero‐interface ensures rapid diffusion of anchored polysulfides from TiO₂ to MXene, and the oxygen‐terminated MXene surface is endowed with high catalytic activity toward polysulfide conversion. The improved lithium–sulfur batteries deliver 800 mAh g^?1 at 2 C and an ultralow capacity decay of 0.028% per cycle over 1000 cycles at 2 C. Even with a high sulfur loading of 5.1 mg cm^?2, the capacity retention of 93% after 200 cycles is still maintained. This work sheds new insights into the design of high‐performance catalysts with manipulated chemical components and tailored surface chemistry to regulate polysulfides in Li–S batteries.     

MoN Supported on Graphene as a Bifunctional Interlayer for Advanced Li‐S Batteries

Rational design of effective polysulfide barriers is highly important for high‐performance lithium‐sulfur (Li‐S) batteries. A variety of adsorbents have been applied as interlayers to alleviate the shuttle effect. Nevertheless, the unsuccessful oxidation of Li₂S on interlayers leads to loss of active materials and blocks Li ion transport. In this work, a MoN‐based interlayer sandwiched between the C‐S cathode and the separator is developed. Such an interlayer not only strongly binds lithium polysulfides via Mo‐S bonding but also efficiently accelerates the decomposition of Li₂S. The acceleration mechanism toward Li₂S decomposition is determined to be a combination of contributions of catalytic cleavage of Li‐S bond in Li₂S based on the proposed covalence‐activation mechanism and rapid migration of the produced Li ions. As a result, the C–S cathodes with the as‐developed interlayer manifest a negligible charging potential barrier and outstanding cycling stability with a very low capacity fading rate of 0.023% per cycle during 1500 cycles at 1 C. High areal capacity of 6.02 mAh cm^?2 is achieved for high sulfur loading of 7.0 mg cm^?2 after cycling at 0.1 C. The material and strategy demonstrated in this work can open the door toward developing shuttle suppression interlayers without impairing cathode performance.     

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.