Highly Safe Electrolyte Enabled via Controllable Polysulfide Release and Efficient Conversion for Advanced Lithium–Sulfur Batteries

Conventional lithium–sulfur batteries often suffer from fatal problems such as high flammability, polysulfide shuttling, and lithium dendrites growth. Here, highly‐safe lithium–sulfur batteries based on flame‐retardant electrolyte (dimethoxyether/1,1,2,2‐tetrafluoroethyl 2,2,3,3‐tetrafluoropropyl ether) coupled with functional separator (nanoconductive carbon‐coated cellulose nonwoven) to resolve aforementioned bottle‐neck issues are demonstrated. It is found that this flame‐retardant electrolyte exhibits excellent flame retardancy and low solubility of polysulfide. In addition, Li/Li symmetrical cells using such flame‐retardant electrolyte deliver extraordinary long‐term cycling stability (less than 10 mV overpotential) for over 2500 h at 1.0 mA cm^?2 and 1.0 mAh cm^?2. Moreover, bare sulfur cathode–based lithium–sulfur batteries using this flame retardant electrolyte coupled with nanoconductive carbon‐coated cellulose separator can retain 83.6% discharge capacity after 200 cycles at 0.5 C. Under high charge/discharge rate (4 C), lithium–sulfur cells still show high charge/discharge capacity of ≈350 mAh g^?1. Even at an elevated temperature of 60 °C, discharge capacity of 870 mAh g^?1 can be retained. More importantly, high‐loading bare sulfur cathode (4 mg cm^?2)–based lithium–sulfur batteries can also deliver high charge/discharge capacity over 806 mAh g^?1 after 56 cycles. Undoubtedly, the strategy of flame retardant electrolyte coupled with carbon‐coated separator enlightens highly safe lithium–sulfur batteries at a wide range of temperature.     

Rational Design of Statically and Dynamically Stable Lithium–Sulfur Batteries with High Sulfur Loading and Low Electrolyte/Sulfur Ratio

The primary challenge with lithium–sulfur battery research is the design of sulfur cathodes that exhibit high electrochemical efficiency and stability while keeping the sulfur content and loading high and the electrolyte/sulfur ratio low. With a systematic investigation, a novel graphene/cotton‐carbon cathode is presented here that enables sulfur loading and content as high as 46 mg cm^?2 and 70 wt% with an electrolyte/sulfur ratio of as low as only 5. The graphene/cotton‐carbon cathodes deliver peak capacities of 926 and 765 mA h g^?1, respectively, at C/10 and C/5 rates, which translate into high areal, gravimetric, and volumetric capacities of, respectively, 43 and 35 mA h cm^?2, 648 and 536 mA h g^?1, and 1067 and 881 mA h cm^?3 with a stable cyclability. They also exhibit superior cell‐storage capability with 95% capacity‐retention, a low self‐discharge constant of just 0.0012 per day, and stable poststorage cyclability after storing over a long period of six months. This work demonstrates a viable approach to develop lithium–sulfur batteries with practical energy densities exceeding that of lithium‐ion batteries.     

Yolk–Shelled C@Fe3O4 Nanoboxes as Efficient Sulfur Hosts for High‐Performance Lithium–Sulfur Batteries

Owing to the high theoretical specific capacity (1675 mA h g^?1) and low cost, lithium–sulfur (Li–S) batteries offer advantages for next‐generation energy storage. However, the polysulfide dissolution and low electronic conductivity of sulfur cathodes limit the practical application of Li–S batteries. To address such issues, well‐designed yolk–shelled carbon@Fe₃O₄ (YSC@Fe₃O₄) nanoboxes as highly efficient sulfur hosts for Li–S batteries are reported here. With both physical entrapment by carbon shells and strong chemical interaction with Fe₃O₄ cores, this unique architecture immobilizes the active material and inhibits diffusion of the polysulfide intermediates. Moreover, due to their high conductivity, the carbon shells and the polar Fe₃O₄ cores facilitate fast electron/ion transport and promote continuous reactivation of the active material during the charge/discharge process, resulting in improved electrochemical utilization and reversibility. With these merits, the S/YSC@Fe₃O₄ cathodes support high sulfur content (80 wt%) and loading (5.5 mg cm^?2) and deliver high specific capacity, excellent rate capacity, and long cycling stability. This work provides a new perspective to design a carbon/metal‐oxide‐based yolk–shelled framework as a high sulfur‐loading host for advanced Li–S batteries with superior electrochemical properties.     

Robust,Ultra‐Tough Flexible Cathodes for High‐Energy Li–S Batteries

Sulfur cathodes have become appealing for rechargeable batteries because of their high theoretical capacity (1675 mA h g^?1). However, the conventional cathode configuration borrowed from lithium‐ion batteries may not allow the pure sulfur cathode to put its unique materials chemistry to good use. The solid_(sulfur)–liquid_{(polysulfides)}–solid_(sulfides) phase transitions generate polysulfide intermediates that are soluble in the commonly used organic solvents in Li–S cells. The resulting severe polysulfide diffusion and the irreversible active‐material loss have been hampering the development of Li–S batteries for years. The present study presents a robust, ultra‐tough, flexible cathode with the active‐material fillings encapsulated between two buckypapers (B), designated as buckypaper/sulfur/buckypaper (B/S/B) cathodes, that suppresses the irreversible polysulfide diffusion to the anode and offers excellent electrochemical reversibility with a low capacity fade rate of 0.06% per cycle after 400 cycles. Engineering enhancements demonstrate that the B/S/B cathodes represent a facile approach for the development of high‐performance sulfur electrodes with a high areal capacity of 5.1 mA h cm^?2, which increases further to approach 7 mA h cm^?2 on coupling with carbon‐coated separators.     

Pyrrolic‐Type Nitrogen‐Doped Hierarchical Macro/Mesoporous Carbon as a Bifunctional Host for High‐Performance Thick Cathodes for Lithium‐Sulfur Batteries

Lithium‐sulfur (Li‐S) batteries are highly considered as a next‐generation energy storage device due to their high theoretical energy density. For practical viability, reasonable active‐material loading of >4.0 mg cm^?2 must be employed, at a cost to the intrinsic instability of sulfur cathodes. The incursion of lithium polysulfides (LiPS) at higher sulfur loadings results in low active material utilization and poor cell cycling capability. The use of high‐surface‐area hierarchical macro/mesoporous inverse opal (IOP) carbons to investigate the effects of pore volume and surface area on the electrochemical stability of high‐loading, high‐thickness cathodes for Li‐S batteries is presented here. The IOP carbons are additionally doped with pyrrolic‐type nitrogen groups (N‐IOP) to act as a polar polysulfide mediator and enhance the active‐material reutilization. With a high sulfur loading of 6.0 mg cm^?2, the Li‐S cells assembled with IOP and N‐IOP carbons are able to attain a high specific capacity of, respectively, 1242 and 1162 mA h g^?1. The N‐IOP enables the Li‐S cells to demonstrate good electrochemical performance over 300 cycles.     

Polyethylenimine Expanded Graphite Oxide Enables High Sulfur Loading and Long‐Term Stability of Lithium–Sulfur Batteries

To realize practical lithium–sulfur batteries (LSBs) with long cycling life, designing cathode hosts with a high specific surface area (SSA) is recognized as an efficient way to trap the soluble polysulfides. However, it is also blamed for diminishing the volumetric energy density and being susceptible to side reactions. Herein, polyethylenimine intercalated graphite oxide (PEI‐GO) with a low SSA of 4.6 m² g^?1 and enlarged interlayer spacing of 13 Å is proposed as a superior sulfur host, which enables homogeneous distribution of high sulfur content (73%) and facilitates Li⁺ transfer in thick sulfur electrode. LSBs with a moderate sulfur loading (3.4 mg S cm^?2) achieve an initial capacity of 1157 and 668 mAh g^?1 after 500 cycles at 0.5 C. Even when the sulfur loading is increased to 7.3 mg cm^?2, the electrode still delivers a high areal capacity of 4.7 mAh cm^?2 (641 mAh g^?1) after 200 cycles at 0.2 C. The excellent electrochemical properties of PEI‐GO are mainly attributed to the homogeneous distribution of sulfur in PEI‐GO and the strong chemical interactions between polysulfides and amine groups, which can mitigate the loss of active phases and contribute to the better cycling stability.     

Compactly Coupled Nitrogen‐Doped Carbon Nanosheets/Molybdenum Phosphide Nanocrystal Hollow Nanospheres as Polysulfide Reservoirs for High‐Performance Lithium–Sulfur Chemistry

Lithium–sulfur (Li–S) batteries have been disclosed as one of the most promising energy storage systems. However, the low utilization of sulfur, the detrimental shuttling behavior of polysulfides, and the sluggish kinetics in electrochemical processes, severely impede their application. Herein, 3D hierarchical nitrogen‐doped carbon nanosheets/molybdenum phosphide nanocrystal hollow nanospheres (MoP@C/N HCSs) are introduced to Li–S batteries via decorating commercial separators to inhibit polysulfides diffusion. It acts not only as a polysulfides immobilizer to provide strong physical trapping and chemical anchoring toward polysulfides, but also as an electrocatalyst to accelerate the kinetics of the polysulfides redox reaction, and to lower the Li₂S nucleation/dissolution interfacial energy barrier and self‐discharge capacity loss in working Li–S batteries, simultaneously. As a result, the Li–S batteries with MoP@C/N HCS‐modified separators show superior rate capability (920 mAh g^?1 at 2 C) and stable cycling life with only 0.04% capacity decay per cycle over 500 cycles at 1 C with nearly 100% Coulombic efficiency. Furthermore, the Li–S battery can achieve a high area capacity of 5.1 mAh cm^?2 with satisfied capacity retention when the cathode loading reaches 5.5 mg cm^?2. This work offers a brand new guidance for rational separator design into the energy chemistry of high‐stable Li–S batteries.     

Inkjet‐Printed Lithium–Sulfur Microcathodes for All‐Printed,Integrated Nanomanufacturing

Improved thin‐film microbatteries are needed to provide appropriate energy‐storage options to power the multitude of devices that will bring the proposed “Internet of Things” network to fruition (e.g., active radio‐frequency identification tags and microcontrollers for wearable and implantable devices). Although impressive efforts have been made to improve the energy density of 3D microbatteries, they have all used low energy‐density lithium‐ion chemistries, which present a fundamental barrier to miniaturization. In addition, they require complicated microfabrication processes that hinder cost‐competitiveness. Here, inkjet‐printed lithium–sulfur (Li–S) cathodes for integrated nanomanufacturing are reported. Single‐wall carbon nanotubes infused with electronically conductive straight‐chain sulfur (S@SWNT) are adopted as an integrated current‐collector/active‐material composite, and inkjet printing as a top‐down approach to achieve thin‐film shape control over printed electrode dimensions is used. The novel Li–S cathodes may be directly printed on traditional microelectronic semicoductor substrates (e.g., SiO₂) or on flexible aluminum foil. Profilometry indicates that these microelectrodes are less than 10 µm thick, while cyclic voltammetry analyses show that the S@SWNT possesses pseudocapacitive characteristics and corroborates a previous study suggesting the S@SWNT discharge via a purely solid‐state mechanism. The printed electrodes produce ≈800 mAh g^?1 S initially and ≈700 mAh g^?1 after 100 charge/discharge cycles at C/2 rate.     

Strong Surface‐Bound Sulfur in Carbon Nanotube Bridged Hierarchical Mo2C‐Based MXene Nanosheets for Lithium–Sulfur Batteries

In this work, hydroxyl‐functionalized Mo₂C‐based MXene nanosheets are synthesized by facilely removing the Sn layer of Mo₂SnC. The hydroxyl‐functionalized surface of Mo₂C suppresses the shuttle effect of lithium polysulfides (LiPSs) through strong interaction between Mo atoms on the MXenes surface and LiPSs. Carbon nanotubes (CNTs) are further introduced into Mo₂C phase to enlarge the specific surface area of the composite, improve its electronic conductivity, and alleviate the volume change during discharging/charging. The strong surface‐bound sulfur in the hierarchical Mo₂C‐CNTs host can lead to a superior electrochemical performance in lithium–sulfur batteries. A large reversible capacity of ≈925 mAh g ^{? 1} is observed after 250 cycles at a current density of 0.1 C (1 C = 1675 mAh g^?1) with good rate capability. Notably, the electrodes with high loading amounts of sulfur can also deliver good electrochemical performances, i.e., initial reversible capacities of ≈1314 mAh g^?1 (2.4 mAh cm^?2), ≈1068 mAh g^?1 (3.7 mAh cm^?2), and ≈959 mAh g^?1 (5.3 mAh cm^?2) at various areal loading amounts of sulfur (1.8, 3.5, and 5.6 mg cm^?2) are also observed, respectively.     

Greatly Improved Conductivity of Double‐Chain Polymer Network Binder for High Sulfur Loading Lithium–Sulfur Batteries with a Low Electrolyte/Sulfur Ratio

Binders have been considered to play a key role in realizing high‐energy‐density lithium–sulfur batteries. However, the accompanying problems of limited conductivity and inferior affinity of soluble polysulfide intermediates bring down their comprehensive performance for practical applications. Herein, the synthesis of a novel double‐chain polymer network (DCP) binder by polymerizing 4,4′‐biphenyldisulfonic acid connected pyrrole monomer onto viscous sodium carboxymethyl cellulose matrix, yielding a primary crystal structure is reported. Consequently, the resulted binder enables superior rate performance from 0.2 C (1326.9 mAh g^?1) to 4 C (701.4 mAh g^?1). Moreover, a high sulfur loading of 9.8 mg cm^?2 and a low electrolyte/sulfur ratio (5:1, µL mg^?1) are achieved, exhibiting a high area capacity of 9.2 mAh cm^?2. In situ X‐ray diffraction analysis is conducted to monitor the structural modifications of the cathode, confirming the occurrence of sulfur reduction/recrystallization during charge–discharge process. In addition, in situ UV–vis measurements demonstrate that DCP binder impedes the polysulfide migration, thereby giving rise to high capacity retention for 400 cycles.     

Long‐Life Lithium–Sulfur Batteries with a Bifunctional Cathode Substrate Configured with Boron Carbide Nanowires

Developing high‐energy‐density lithium–sulfur (Li–S) batteries relies on the design of electrode substrates that can host a high sulfur loading and still attain high electrochemical utilization. Herein, a new bifunctional cathode substrate configured with boron‐carbide nanowires in situ grown on carbon nanofibers (B₄C@CNF) is established through a facile catalyst‐assisted process. The B₄C nanowires acting as chemical‐anchoring centers provide strong polysulfide adsorptivity, as validated by experimental data and first‐principle calculations. Meanwhile, the catalytic effect of B₄C also accelerates the redox kinetics of polysulfide conversion, contributing to enhanced rate capability. As a result, a remarkable capacity retention of 80% after 500 cycles as well as stable cyclability at 4C rate is accomplished with the cells employing B₄C@CNF as a cathode substrate for sulfur. Moreover, the B₄C@CNF substrate enables the cathode to achieve both high sulfur content (70 wt%) and sulfur loading (10.3 mg cm^?2), delivering a superb areal capacity of 9 mAh cm^?2. Additionally, Li–S pouch cells fabricated with the B₄C@CNF substrate are able to host a high sulfur mass of 200 mg per cathode and deliver a high discharge capacity of 125 mAh after 50 cycles.     

The Structural and Electronic Engineering of Molybdenum Disulfide Nanosheets as Carbon-Free Sulfur Hosts for Boosting Energy Density and Cycling Life of Lithium–Sulfur Batteries

The compact sulfur cathodes with high sulfur content and high sulfur loading are crucial to promise high energy density of lithium–sulfur (Li–S) batteries. However, some daunting problems, such as low sulfur utilization efficiency, serious polysulfides shuttling, and poor rate performance, are usually accompanied during practical deployment. The sulfur hosts play key roles. Herein, the carbon-free sulfur host composed of vanadium-doped molybdenum disulfide (VMS) nanosheets is reported. Benefiting from the basal plane activation of molybdenum disulfide and structural advantage of VMS, high stacking density of sulfur cathode is allowed for high areal and volumetric capacities of the electrodes together with the effective suppression of polysulfides shuttling and the expedited redox kinetics of sulfur species during cycling. The resultant electrode with high sulfur content of 89 wt.% and high sulfur loading of 7.2 mg cm⁻² achieves high gravimetric capacity of 900.9 mAh g⁻¹, the areal capacity of 6.48 mAh cm⁻², and volumetric capacity of 940 mAh cm⁻³ at 0.5 C. The electrochemical performance can rival with the state-of-the-art those in the reported Li–S batteries. This work provides methodology guidance for the development of the cathode materials to achieve high-energy-density and long-life Li–S batteries.     

Cationic Covalent‐Organic Framework as Efficient Redox Motor for High‐Performance Lithium–Sulfur Batteries

The shuttle effect of soluble lithium polysulfides (LiPSs) leads to the rapid decay of sulfur cathode, severely hindering the practical applications of lithium‐sulfur (Li‐S) batteries. To this point, a covalent‐organic framework (COF) with proper cationic sites, which can be utilized as the cathode host of high‐performance Li–S batteries, is reported. The chemical sulfur anchoring within micropores effectively suppresses the dissolution of LiPSs into the electrolyte. During the discharge step, the cationic sites can accept electrons from anode and deliver them to polysulfides to facilitate the polysulfides' disintegration. Meanwhile, the cationic sites can receive electrons from polysulfides and then send them to the anode during the charge process, which promotes the polysulfides oxidation. Thus, both experiments and computational modeling show that the cationic COF can effectively inhibit the shuttle effect of LiPSs and improve the batteries' performances. Compared with electrically neutral COFs, the cationic COF‐based batteries show much better cycling stability even at high current density, for instance, a high specific capacity of 468 mA h g^?1 is retained after 300 cycles at a current density of 4.0 C.     

Rational Integration of Polypropylene/Graphene Oxide/Nafion as Ternary‐Layered Separator to Retard the Shuttle of Polysulfides for Lithium–Sulfur Batteries

The reversible electrochemical transformation from lithium (Li) and sulfur (S) into Li₂S through multielectron reactions can be utilized in secondary Li–S batteries with very high energy density. However, both the low Coulombic efficiency and severe capacity degradation limits the full utilization of active sulfur, which hinders the practical applications of Li–S battery system. The present study reports a ternary‐layered separator with a macroporous polypropylene (PP) matrix layer, graphene oxide (GO) barrier layer, and Nafion retarding layer as the separator for Li–S batteries with high Coulombic efficiency and superior cyclic stability. In the ternary‐layered separator, ultrathin layer of GO (0.0032 mg cm^?2, estimated to be around 40 layers) blocks the macropores of PP matrix, and a dense ion selective Nafion layer with a very low loading amount of 0.05 mg cm^?2 is attached as a retarding layer to suppress the crossover of sulfur‐containing species. The ternary‐layered separators are effective in improving the initial capacity and the Coulombic efficiency of Li–S cells from 969 to 1057 mAh g^?1, and from 80% to over 95% with an LiNO₃‐free electrolyte, respectively. The capacity degradation is reduced from 0.34% to 0.18% per cycle within 200 cycles when the PP separator is replaced by the ternary‐layered separators. This work provides the rational design strategy for multifunctional separators at cell scale to effective utilizing of active sulfur and retarding of polysulfides, which offers the possibility of high energy density Li–S cells with long cycling life.     

MoS2/Celgard Separator as Efficient Polysulfide Barrier for Long‐Life Lithium–Sulfur Batteries

A high lithium conductive MoS₂/Celgard composite separator is reported as efficient polysulfides barrier in Li–S batteries. Significantly, thanks to the high density of lithium ions on MoS₂ surface, this composite separator shows high lithium conductivity, fast lithium diffusion, and facile lithium transference. When used in Li–S batteries, the separator is proven to be highly efficient for depressing polysulfides shuttle, leading to high and long cycle stability. With 65% of sulfur loading, the device with MoS₂/Celgard separator delivers an initial capacity of 808 mAh g^?1 and a substantial capacity of 401 mAh g^?1 after 600 cycles, corresponding to only 0.083% of capacity decay per cycle that is comparable to the best reported result so far. In addition, the Coulombic efficiency remains more than 99.5% during all 600 cycles, disclosing an efficient ionic sieve preventing polysulfides migration to the anode while having negligible influence on Li⁺ ions transfer across the separator. The strategy demonstrated in this work will open the door toward developing efficient separators with flexible 2D materials beyond graphene for energy‐storage devices.     

A Host‐Configured Lithium–Sulfur Cell Built on 3D Nickel Photonic Crystal with Superior Electrochemical Performances

The insulator of the sulfur cathode and the easy dendrites growth of the lithium anode are the main barriers for lithium–sulfur cells in commercial application. Here, a 3D NPC@S/3D NPC@Li full cell is reported based on 3D hierarchical and continuously porous nickel photonic crystal (NPC) to solve the problems of sulfur cathode and lithium anode at the same time. In this case, the 3D NPC@S cathode can not only offer a fast transfer of electron and lithium ion, but also effectively prevent the dissolution of polysulfides and the tremendous volume change during cycling, and the 3D NPC@Li anode can efficiently inhibit the growth of lithium dendrites and volume expansion, too. As a result, the cell exhibits a high reversible capacity of 1383 mAh g^?1 at 0.5 C (the current density of 837 mA g^?1), superior rate ability (the reversible capacity of 735 mAh g^?1 at the extremely high current density of 16 750 mA g^?1) with excellent coulombic efficiency of about 100% and an excellent cycle life over 500 cycles with only about 0.026% capacity loss per cycle.     

Self‐Supported and Flexible Sulfur Cathode Enabled via Synergistic Confinement for High‐Energy‐Density Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries have attracted much attention in the field of electrochemical energy storage due to their high energy density and low cost. However, the “shuttle effect” of the sulfur cathode, resulting in poor cyclic performance, is a big barrier for the development of Li–S batteries. Herein, a novel sulfur cathode integrating sulfur, flexible carbon cloth, and metal–organic framework (MOF)‐derived N‐doped carbon nanoarrays with embedded CoP (CC@CoP/C) is designed. These unique flexible nanoarrays with embedded polar CoP nanoparticles not only offer enough voids for volume expansion to maintain the structural stability during the electrochemical process, but also promote the physical encapsulation and chemical entrapment of all sulfur species. Such designed CC@CoP/C cathodes with synergistic confinement (physical adsorption and chemical interactions) for soluble intermediate lithium polysulfides possess high sulfur loadings (as high as 4.17 mg cm^–2) and exhibit large specific capacities at different C‐rates. Specially, an outstanding long‐term cycling performance can be reached. For example, an ultralow decay of 0.016% per cycle during the whole 600 cycles at a high current density of 2C is displayed. The current work provides a promising design strategy for high‐energy‐density Li–S batteries.     

A Highly Conductive MOF of Graphene Analogue Ni3(HITP)2 as a Sulfur Host for High‐Performance Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries have been considered as one of the most promising energy storage systems owing to their high theoretical capacity and energy density. However, their commercial applications are obstructed by sluggish reaction kinetics and rapid capacity degradation mainly caused by polysulfide shuttling. Herein, the first attempt to utilize a highly conductive metal–organic framework (MOF) of Ni₃(HITP)₂ graphene analogue as the sulfur host material to trap and transform polysulfides for high‐performance Li–S batteries is made. Besides, the traditional conductive additive acetylene black is replaced by carbon nanotubes to construct matrix conduction networks for triggering the rate and cycling performance of the active cathode. As a result, the S@Ni₃(HITP)₂ with sulfur content of 65.5 wt% shows excellent sulfur utilization, rate performance, and cyclic durability. It delivers a high initial capacity of 1302.9 mAh g^?1 and good capacity retention of 848.9 mAh g^?1 after 100 cycles at 0.2 C. Highly reversible discharge capacities of 807.4 and 629.6 mAh g^?1 are obtained at 0.5 and 1 C for 150 and 300 cycles, respectively. Such kinds of pristine MOFs with high conductivity and abundant polar sites reveal broad promising prospect for application in the field of high‐performance Li–S batteries.     

A Quinonoid‐Imine‐Enriched Nanostructured Polymer Mediator for Lithium–Sulfur Batteries

The reversible formation of chemical bonds has potential for tuning multi‐electron redox reactions in emerging energy‐storage applications, such as lithium?sulfur batteries. The dissolution of polysulfide intermediates, however, results in severe shuttle effect and sluggish electrochemical kinetics. In this study, quinonoid imine is proposed to anchor polysulfides and to facilitate the formation of Li₂S₂/Li₂S through the reversible chemical transition between protonated state (? NH⁺ ?) and deprotonated state (? N?). When serving as the sulfur host, the quinonoid imine‐doped graphene affords a very tiny shuttle current of 2.60 × 10^?4 mA cm^?2, a rapid redox reaction of polysulfide, and therefore improved sulfur utilization and enhanced rate performance. A high areal specific capacity of 3.72 mAh cm^?2 is achieved at 5.50 mA cm^?2 on the quinonoid imine‐doped graphene based electrode with a high sulfur loading of 3.3 mg cm^?2. This strategy sheds a new light on the organic redox mediators for reversible modulation of electrochemical reactions.     

Dual‐Function,Tunable, Nitrogen‐Doped Carbon for High‐Performance Li Metal–Sulfur Full Cell

Lithium metal–sulfur (Li–S) batteries are attracting broad interest because of their high capacity. However, the batteries experience the polysulfide shuttle effect in cathode and dendrite growth in the Li metal anode. Herein, a bifunctional and tunable mesoporous carbon sphere (MCS) that simultaneously boosts the performance of the sulfur cathode and the Li anode is designed. The MCS homogenizes the flux of Li ions and inhibits the growth of Li dendrites due to its honeycomb structure with high surface area and abundance of nitrogen sites. The Li@MCS cell exhibits a small overpotential of 29 mV and long cycling performance of 350 h under the current density of 1 mA cm^‐2. Upon covering one layer of amorphous carbon on the MCS (CMCS), an individual carbon cage is able to encapsulate sulfur inside and reduce the polysulfide shuttle, which improves the cycling stability of the Li–S battery. As a result, the S@CMCS has a maximum capacity of 411 mAh g^‐1 for 200 cycles at a current density of 3350 mA g^‐1. Based on the excellent performance, the full Li–S cell assembled with Li@MCS anode and S@CMCS cathode shows much higher capacity than a cell assembled with Li@Cu anode and S@CMCS cathode.