Engineering Strategies for Suppressing the Shuttle Effect in Lithium–Sulfur Batteries

Lithium–sulfur(Li–S)batteries are supposed to be one of the most potential next-generation batteries owing to their high theoretical capacity and low cost.Nevertheless,the shuttle effect of firm multi-step two-electron reaction between sulfur and lithium in liquid electrolyte makes the capacity much smaller than the theoretical value.Many methods were proposed for inhibiting the shuttle effect of polysulfide,improving corresponding redox kinetics and enhancing the integral performance of Li–S batteries.Here,we will comprehensively and systematically summarize the strategies for inhibiting the shuttle effect from all components of Li–S batteries.First,the electrochemical principles/mechanism and origin of the shuttle effect are described in detail.Moreover,the efficient strategies,including boosting the sulfur conversion rate of sulfur,confining sulfur or lithium polysulfides(LPS)within cathode host,confining LPS in the shield layer,and preventing LPS from contacting the anode,will be discussed to suppress the shuttle effect.Then,recent advances in inhibition of shuttle effect in cathode,electrolyte,separator,and anode with the aforementioned strategies have been summarized to direct the further design of efficient materials for Li–S batteries.Finally,we present prospects for inhibition of the LPS shuttle and potential development directions in Li–S batteries.

Enhancing Li cycling coulombic efficiency while mitigating “shuttle effect” of Li-S battery through sustained release of LiNO_(3)

In practical lithium-sulfur batteries(LSBs),the shuttle effect and Li cycling coulombic efficiency(CE) are strongly affected by the physicochemical properties of solid electrolyte interphase(SEI).LiNO_(3) is widely used as an additive in electrolytes to build a high-quality SEI,but its self-sacrificial nature limits the ability to mitigate the shuttle effect and stabilize Li anode during long-term cycling.To counteract LiNO_(3) consumption during long-term cycling without using a high initial concentration,inspired by sustainedrelease drugs,we encapsulated LiNO_(3) in lithiated Nafion polymer and added an electrolyte co-solvent(1,1,2,2-tetrafluoroethylene 2,2,2-trifluoromethyl ether) with poor LiNO_(3) solubility to construct highquality and durable F-and N-rich SEI.Theoretical calculations,experiments,multiphysics simulations,and in-situ observations confirmed that the F-and N-rich SEI can modulate lithium deposition behavior and allow persistent repair of SEI during prolonged cycling.Hence,the F-and N-rich SEI improves the Li anode cycling CE to 99.63% and alleviates the shuttle effect during long-term cycling.The lithium anode with sustainable F-and N-rich SEI shows a stable Li plating/stripping over 2000 h at 1 mA cm^(-2).As expected,Li‖S full cells with this SEI achieved a long lifespan of 250 cycles,far exceeding cells with a routine SEI.The Li‖S pouch cell based on F-and N-rich SEI also can achieve a high energy density of about300 Wh kg^(-1) at initial cycles.This strategy provides a novel design for high-quality and durable SEls in LSBs and may also be extendable to other alkali metal batteries.

Cellulose nanofiber separator for suppressing shuttle effect and Li dendrite formation in lithium-sulfur batteries

Lithium-sulfur battery(LSB) has high energy density but is limited by the polysulfides shuttle and dendrite growth during cycling. Herein, a free-standing cellulose nanofiber(CNF) separator is designed and fabricated in isopropanol/water suspension through vacuum filtration progress. CNFs with abundant polar oxygen-containing functional groups can chemically immobilize the polysulfides, and suppress the formation of the dendrites by controlling the surface morphology of the SEI on lithium metal in LSB. The isopropanol content in a suspension can fine-tune the pore structure of the membrane to achieve optimal electrochemical performance. The prepared separator displays integrated advantages of an ultrathin thickness(19 μm), lightweight(0.87 mg cm^(-2)), extremely high porosity(98.05%), and decent electrolyte affinity. As a result, the discharge capacity of the LSB with CNF separator at the first and 100 th cycle is 1.4 and 1.3 times that of PP separator, respectively. Our research provides an environmentalfriendly and facile strategy for the preparation of multifunctional separators for LSBs.

Unraveling Shuttle Effect and Suppression Strategy in Lithium/Sulfur Cells by In Situ/Operando X-ray Absorption Spectroscopic Characterization

The polysulfides shuttle effect represents a great challenge in achieving high capacity and long lifespan of lithium/sulfur(Li/S)cells.A comprehensive understanding of the shuttle-related sulfur speciation and diffusion process is vital for addressing this issue.Herein,we employed in situ/operando X-ray absorption spectroscopy(XAS)to trace the migration of polysulfides across the Li/S cells by precisely monitoring the sulfur chemical speciation at the cathodic electrolyte-separator and electrolyte-anode interfaces,respectively,in a real-time condition.After we adopted a shuttle-suppressing strategy by introducing an electrocatalytic layer of twinborn bismuth sulfide/bismuth oxide nanoclusters in a carbon matrix(BSOC),we found the Li/S cell showed greatly improved sulfur utilization and longer life span.The operando S Kedge XAS results revealed that the BSOC modification was bi-functional:trapping polysulfides and catalyzing conversion of sulfur species simultaneously.We elucidated that the polysulfide trapping-and-catalyzing effect of the BSOC electrocatalytic layer resulted in an effective lithium anode protection.Our results could offer potential stratagem for designing more advanced Li/S cells.

Strategies to suppress the shuttle effect of redox mediators in lithium-oxygen batteries

Rechargeable lithium-oxygen(Li-O_(2))batteries are the next generation energy storage devices due to their ultrahigh theoretical capacity.Redox mediators(RMs)are widely used as a homogenous electrocatalyst in non-aqueous Li-O_(2)batteries to enhance their discharge capacity and reduce charge overpotential.However,the shuttle effect of RMs in the electrolyte solution usually leads to corrosion of the Li metal anode and uneven Li deposition on the anode surface,resulting in unwanted consumption of electrocatalysts and deterioration of the cells.It is therefore necessary to take some measures to prevent the shuttle effect of RMs and fully utilize the soluble electrocatalysts.Herein,we summarize the strategies to suppress the RM shuttle effect reported in recent years,including electrolyte additives,protective separators and electrode modification.The mechanisms of these strategies are analyzed and their corresponding requirements are discussed.The electrochemical properties of Li-O_(2)batteries with different strategies are summarized and compared.The challenges and perspectives on preventing the shuttle effect of RMs are described for future study.This review provides guidance for achieving shuttle-free redox mediation and for designing Li-O_(2)cells with a long cycle life,high energy efficiency and highly reversible electrochemical reactions.

Labyrinth maze-like long travel-reduction of sulfur and polysulfides in micropores of a spherical honeycomb carbon to greatly confine shuttle effects in lithium-sulfur batteries

Polysulfide absorption in a micropore-rich structure has been reported to be capable of efficiently confining the shuttle effect for high-performance lithium-sulfur(Li–S)batteries.Here,a labyrinth maze-like spherical honeycomb-like carbon with micropore-rich structure was synthesized,which is employed as a template host material of sulfur to study the shuttle effects.The results strongly confirm that a diffusion controlled process rather than an absorption resulted surface-controlled process occurs in an even micropore-rich cathode but still greatly inhibits the shuttle effect.Thus,the battery achieves a high initial discharge specific capacity of 1120 mAh g1 at 0.25 C and super cycling stability for 1635 cycles with only 0.035%capacity decay per cycle with 100%Coulombic efficiency.We would like to propose a new mechanism for shuttle effect inhibition in micropores.In terms of the diffusion control process in microporous paths of a labyrinth maze structure,polysulfides experience a long travel to realize continuous reductions of sulfur and polysulfides until formation of the final solid product.This efficiently prevents the polysulfides escaping to electrolyte.The labyrinth maze-like honeycomb structure also offers fast electron transfer and enhanced mass transport as well as robust mechanical strength retaining intact structure for long cycle life.This work sheds lights on new fundamental insights behind the shuttle effects with universal significance while demonstrating prominent merits of a robust labyrinth maze-like structure in high performance cathode for high-performance Li–S batteries.

Atomically Dispersed Iron Active Sites Promoting Reversible Redox Kinetics and Suppressing Shuttle Effect in Aluminum-Sulfur Batteries

Rechargeable aluminum-sulfur(Al-S)batteries have been considered as a highly potential energy storage system owing to the high theoretical capacity,good safety,abundant natural reserves,and low cost of Al and S.However,the research progress of Al-S batteries is limited by the slow kinetics and shuttle effect of soluble polysulfides intermediates.Herein,an interconnected free-standing interlayer of iron sin-gle atoms supported on porous nitrogen-doped carbon nanofibers(FeSAs-NCF)on the separator is developed and used as both catalyst and chemical barrier for Al-S batteries.The atomically dispersed iron active sites(Fe-N_(4))are clearly identified by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption near-edge structure.The Al-S battery with the FeSAs-NCF shows an improved specific capacity of 780 mAh g^(−1)and enhanced cycle stability.As evidenced by experimental and theoretical results,the atomically dispersed iron active centers on the separator can chemically adsorb the polysulfides and accelerate reaction kinetics to inhibit the shuttle effect and promote the reversible conversion between aluminum polysulfides,thus improving the electrochemical performance of the Al-S battery.This work provides a new way that can not only promote the conversion of aluminum sulfides but also suppress the shuttle effect in Al-S batteries.

Laser irradiation constructing all-in-one defective graphenepolyimide separator for effective restraint of lithium dendrites and shuttle effect

The commercialization of lithium-sulfur(Li-S)batteries faces several bottlenecks,and the major two of which are the shuttle effect of polysulfides and the wild growth of Li dendrites,responsible for fast capacity decay and severe safety issues.As an essential component of Li-S batteries,the structure and properties of the separators are closely related to the above problems,and the exploration of multifunctional separators is highly sought-after.Herein,an integrated separator composited of defective graphene and polyimide(DG-PI)was innovatively fabricated by electrospinning combined with the laser-induced carbonization strategy.The all-in-one compact architecture with well-interconnected channels shows superior mechanical and thermal stability and wettability.More importantly,the PI nanofibers containing N–/O–functional groups can induce the uniform deposition of lithium on the anode surface,while the DG framework with abundant pentagonal/heptagonal rings and vacancies can strongly trap polysulfides and accelerate polysulfide transformation on the cathode side.The strong chemical interaction between the insulative PI layer and the conductive DG layer modulates the surface charge distribution of each other,leading to more prominent contributions to restraining lithium dendrites and shuttle effect.Therefore,the Li-S batteries based on the integrated DG-PI separators afford an excellent performance in protecting lithium anode(stable cycles of 200 h at 5 mA·cm^(−2))and good cycling stability with a low capacity decay of 0.05%per cycle after 700 cycles at 1 C.This work offers a new design concept of multifunctional Li-S battery separators and broadens the application scope of laser micro-nano fabrication technology.

A molecular sieve-containing protective separator to suppress the shuttle effect of redox mediators in lithium-oxygen batteries

Lithium-oxygen(Li-O_(2))batteries have a great potential in energy storage and conversion due to their ultra-high theoretical specific energy,but their applications are hindered by sluggish redox reaction kinetics in the charge/discharge processes.Redox mediators(RMs),as soluble catalysts,are widely used to facilitate the electrochemical processes in the Li-O_(2)batteries.A drawback of RMs is the shuttle effect due to their solubility and mobility,which leads to the corrosion of a Li metal anode and the degradation of the electrochemical performance of the batteries.Herein,we synthesize a polymer-based composite protective separator containing molecular sieves.The nanopores with a diameter of 4Åin the zeolite powder(4A zeolite)are able to physically block the migration of 2,2,6,6-tetramethylpiperidinyloxy(TEMPO)molecules with a larger size;therefore,the shuttle effect of TEMPO is restrained.With the assistance of the zeolite molecular sieves,the cycle life of the Li-O_(2)batteries is significantly extended from~20 to 170 cycles at a current density of 250 mA·g^(-1)and a limited capacity of 500 mAh·g^(-1).Our work provides a highly effective approach to suppress the shuttle effects of RMs and boost the electrochemical performance of Li-O_(2)batteries.

VSe_(2)/V_(2)C heterocatalyst with built-in electric field for efficient lithium-sulfur batteries:Remedies polysulfide shuttle and conversion kinetics

Lithium sulfur(Li-S)battery is a kind of burgeoning energy storage system with high energy density.However,the electrolyte-soluble intermediate lithium polysulfides(Li PSs)undergo notorious shuttle effect,which seriously hinders the commercialization of Li-S batteries.Herein,a unique VSe_(2)/V_(2)C heterostructure with local built-in electric field was rationally engineered from V_(2)C parent via a facile thermal selenization process.It exquisitely synergizes the strong affinity of V_(2)C with the effective electrocatalytic activity of VSe_(2).More importantly,the local built-in electric field at the heterointerface can sufficiently promote the electron/ion transport ability and eventually boost the conversion kinetics of sulfur species.The Li-S battery equipped with VSe_(2)/V_(2)C-CNTs-PP separator achieved an outstanding initial specific capacity of 1439.1 m A h g^(-1)with a high capacity retention of 73%after 100 cycles at0.1 C.More impressively,a wonderful capacity of 571.6 mA h g^(-1)was effectively maintained after 600cycles at 2 C with a capacity decay rate of 0.07%.Even under a sulfur loading of 4.8 mg cm^(-2),areal capacity still can be up to 5.6 m A h cm^(-2).In-situ Raman tests explicitly illustrate the effectiveness of VSe_(2)/V_(2)C-CNTs modifier in restricting Li PSs shuttle.Combined with density functional theory calculations,the underlying mechanism of VSe_(2)/V_(2)C heterostructure for remedying Li PSs shuttling and conversion kinetics was deciphered.The strategy of constructing VSe_(2)/V_(2)C heterocatalyst in this work proposes a universal protocol to design metal selenide-based separator modifier for Li-S battery.Besides,it opens an efficient avenue for the separator engineering of Li-S batteries.

Effects of Catalysis and Separator Functionalization on High-Energy Lithium–Sulfur Batteries:A Complete Review

Lithium–sulfur(Li-S)batteries have the advantages of high theoretical specific capacity(1675 mAh g^(−1)),rich sulfur resources,low production cost,and friendly environment,which makes it one of the most promising next-generation rechargeable energy storage devices.However,the“shuttle effect”of polysulfide results in the passivation of metal lithium anode,the decrease of battery capacity and coulombic efficiency,and the deterioration of cycle stability.To realize the commercialization of Li-S batteries,its serious“shuttle effect”needs to be suppress.The commercial separators are ineffective to suppress this effect because of its large pore size.Therefore,it is an effective strategy to modify the separator surface and introduce functional modified layer.In addition to the blocking strategy,the catalysis of polysulfide conversion reaction is also an important factor hindering the migration of polysulfides.In this review,the principles of separator modification,functionalization,and catalysis in Li-S batteries are reviewed.Furthermore,the research trend of separator functionalization and polysulfide catalysis in the future is prospected.

Inhibited shuttle effect by functional separator for room-temperature sodium-sulfur batteries

According to a statistic,approximately 6 trillion cigarettes are smoked each year all over the world,which produces approximately 1.2 million tons of discarded cigarette butts.The discarded cigarette filters are non-biodegradable,thus they produce a mass of waste disposal and cause environmental pollution is-sue.For the purpose of transforming waste into wealth and reducing environmental pollution,nitrogen and sulfur co-doped carbon nanofiber/carbon black(N,S-CNF/CB)composite derived from the discarded cigarette filters is employed to modify glass fiber(GF)separator for the first time in this study.N,S-CNF improves binding ability towards sodium polysulfides(SPSs)by chemisorption.Non-polar CB limits the dissolution of SPSs in the liquid electrolyte by physisorption.The experiment and density functional theory calculation results indicate that a RT-Na/S battery with a N,S-CNF/CB+GF separator exhibits good cycling stability and rate performance.After 100 cycles at a low current rate of 0.1 C,a RT-Na/S battery with a sulfur mass fraction of 71%delivers a discharge capacity of 703 mAh g^(−1).In addition,at a high current rate of 0.5 C,a discharge capacity of 527 mAh g^(−1) is still maintained after 900 cycles with a very low capacity fading rate of 0.035%per cycle.

Optimally arranged TiO_(2)@MoS_(2) heterostructures with effectively induced built-in electric field for high-performance lithium-sulfur batteries

To overcome the serious technological issues affecting lithium-sulfur(Li-S) batteries,such as sluggish sulfur redox kinetics and the detrimental shuttle effect,heterostructure engineering has been investigated as a strategy to effectively capture soluble lithium polysulfide intermediates and promote their conversion reaction by integrating highly polar metal oxides with catalytically active metals sulfides.However,to fully exploit the outstanding properties of heterostructure-based composites,their detailed structure and interfacial contacts should be designed rationally.Herein,optimally arranged TiO_(2)and MoS_(2)-based heterostructures(TiO_(2)@MoS_(2)) are fabricated on carbon cloth as a multifunctional interlayer to efficiently trap polysulfide intermediates and accelerate their redox kinetics.Owing to the synergistic effects between TiO_(2)and MoS_(2)and the uniform heterointerface distribution that induces the ideally oriented built-in electric field,Li-S batteries with TiO_(2)@MoS_(2)interlayers exhibit high rate capability(601 mA h g^(-1)at 5 C),good cycling stability(capacity-fade rate of 0.067% per cycle over 500 cycles at2 C),and satisfactory areal capacity(5.2 mA h cm^(-2)) under an increased sulfur loading of 5.2 mg cm^(-2).Moreover,by comparing with a MoS_(2)@TiO_(2)interlayer composed of reversely arranged heterostructures,the effect of the built-in electric field’s direction on the electrocatalytic reactions of polysulfide intermediates is thoroughly investigated for the first time.The superior electrocatalytic activities of the rationally arranged TiO_(2)@MoS_(2)interlayer demonstrate the importance of optimizing the built-in electric field of heterostructures for producing high-performance Li-S batteries.

NbN quantum dots anchored hollow carbon nanorods as efficient polysulfide immobilizer and lithium stabilizer for Li-S full batteries

The shuttle effect of lithium polysulfides(LiPSs)and uncontrollable lithium dendrite growth seriously hinder the practical application of lithium-sulfur(Li-S)batteries.To simultaneously address such issues,monodispersed Nb N quantum dots anchored on nitrogen-doped hollow carbon nanorods(NbN@NHCR)are elaborately developed as efficient Li PSs immobilizer and Li stabilizer for high-performance Li-S full batteries.Density functional theory(DFT)calculations and experimental characterizations demonstrate that the sulfiphilic and lithiophilic NbN@NHCR hybrid can not only efficiently immobilize the soluble Li PSs and facilitate diffusion-conversion kinetics for alleviating the shuttling effect,but also homogenize the distribution of Li+ions and regulate uniform Li deposition for suppressing Li-dendrite growth.As a result,the assembled Li-S full batteries(NbN@NHCR-S||Nb N@NHCR-Li)deliver excellent long-term cycling stability with a low decay rate of 0.031%per cycle over 1000 cycles at high rate of 2 C.Even at a high S loading of 5.8 mg cm^(-2)and a low electrolyte/sulfur ratio of 5.2μL mg^(-1),a large areal capacity of 6.2 mA h cm^(-2)can be achieved in Li-S pouch cell at 0.1 C.This study provides a new perspective via designing a dual-functional sulfiphilic and lithiophilic hybrid to address serious issues of the shuttle effect of S cathode and dendrite growth of Li anode.

Advanced preparation and application of bimetallic materials in lithium-sulfur batteries:A review

Lithium-sulfur(Li-S)batteries are considered highly promising as next-generation energy storage systems due to high theoretical capacity(2600 Wh kg^(-1))and energy density(1675 mA h g^(-1))as well as the abundant natural reserves,low cost of elemental sulfur,and environmentally friendly properties.However,several challenges impede its commercialization including low conductivity of sulfur itself,the severe“shuttle effect”caused by lithium polysulfides(LiPSs)during charge–discharge processes,volume expansion effects and sluggish reaction kinetics.As a solution,polar metal particles and their compounds have been introduced as the main hosts for sulfur cathode due to their robust catalytic activity and adsorption capability,effectively suppressing the“shuttle effect”of Li PSs.Bimetallic alloys and their compounds with multi-functional properties exhibit remarkable electrochemical performance more readily when compared to single-metal materials.Well-designed bimetallic materials demonstrate larger specific surface areas and richer active sites,enabling simultaneous high adsorption capability and strong catalytic properties.The synergistic effect of the“adsorption-catalysis”sites accelerates the adsorptiondiffusion-conversion process of Li PSs,ultimately achieving a long-lasting Li-S battery.Herein,the latest progress and performance of bimetallic materials in cathodes,separators,and interlayers of Li-S batteries are systematically reviewed.Firstly,the principles and challenges of Li-S batteries are briefly analyzed.Then,various mechanisms for suppressing“shuttle effects”of Li PSs are emphasized at the microscale.Subsequently,the performance parameters of various bimetallic materials are comprehensively summarized,and some improvement strategies are proposed based on these findings.Finally,the future prospects of bimetallic materials are discussed,with the hope of providing profound insights for the rational design and manufacturing of high-performance bimetallic materials for LSBs.

A gelatin-based artificial SEI for lithium deposition regulation and polysulfide shuttle suppression in lithium-sulfur batteries

Lithium-sulfur(Li-S) battery is one of the best candidates for the next-generation energy storage system due to its high theoretical capacity(1675 mA h-1),low cost and environment friendliness.However,lithium(Li) dendrites formation and polysulfide shuttle effect are two major challenges that limit the commercialization of Li-S batteries.Here we design a facile bifunctional interlayer of gelatin-based fibers(GFs),aiming to protect the Li anode surface from the dendrites growth and also hinder the polysulfide shuttle effect.We reveal that the 3D structural network of GFs layer with abundant polar sites helps to homogenize Li-ion flux,leading to uniform Li-ion deposition.Meanwhile,the polar moieties also immobilize the lithium polysulfides and protect the Li metal from the side-reaction.As a result,the anodeprotected batteries have shown significantly enhanced performance.A high coulombic efficiency of 96% after 160 cycles has been achieved in the Li-Cu half cells.The Li-Li symmetric cells exhibit a prolonged lifespan for 800 h with voltage hysteresis(10 mV).With the as-prepared GFs layer,the Li-S battery shows approximately 14% higher capacity retention than the pristine battery at 0.5 C after 100 cycles.Our work presents that this gelatin-based bi-functional interlayer provides a viable strategy for the manufacturing of advanced Li-S batteries.

Multivalent metal-sulfur batteries for green and cost-effective energy storage:Current status and challenges

Multivalent metal-sulfur(M-S,where M=Mg,Al,Ca,Zn,Fe,etc.)batteries offer unique opportunities to achieve high specific capacity,elemental abundancy and cost-effectiveness beyond lithium-ion batteries(LIBs).However,the slow diffusion of multivalent-metal ions and the shuttle of soluble polysulfide result in impoverished reversible capacity and limited cycle performance of M-S(Mg-S,Al-S,Ca-S,Zn-S,Fe-S,etc.)batteries.It is a necessity to optimize the electrochemical performance,while deepening the understanding of the unique electrochemical reaction mechanism,such as the intrinsic multi-electron reaction process,polysulfides dissoluti on and the in stability of metal an odes.To solve these problems,we have summarized the state-of-the-art progress of current M-S batteries,and sorted out the existing challen ges for different multivalent M-S batteries according to sulfur cathode,electrolytes,metallic an ode and current collectors/separators,respectively.In this literature,we have surveyed and exemplified the strategies developed for better M-S batteries to strengthen the application of green,cost-effective and high energy density M-S batteries.

Atomic/nano-scale in-situ probing the shuttling effect of redox mediator in Na-O_(2) batteries

Sodium-oxygen batteries(Na-O_(2))have attracted extensive attention as promising energy storage systems due to their high energy density and low cost.Redox mediators are often employed to improve Na-O_(2) battery performance,however,their effect on the formation mechanism of the oxygen reduction product(NaO_(2))is still unclear.Here,we have investigated the formation mechanism of NaO_(2) during the discharge process in the presence of a redox mediator with the help of atomic/nano-scale in-situ characterization tools used in concert(e.g.atomic force microscope,electrochemical quartz crystal microbalance(EQCM)and laser nano-particle analyzer).As a result,real-time observations on different time scales show that by shuttling electrons to the electrolyte,the redox mediator enables formation of NaO_(2) in the solution-phase instead of within a finite region near the electrode surface.These findings provide new fundamental insights on the understanding of Na-O_(2) batteries and new consequently perspectives on designing high performance metal-O_(2) batteries and other related functions.

Nickel single atom overcoordinated active sites to accelerate the electrochemical reaction kinetics for Li-S cathode

Lithium-sulfur(Li-S)batteries with high theoretical energy density are promising advanced energy storage devices.However,shuttling of dissolute lithium polysulfide(LiPSs)and sluggish conversion kinetics impede their applications.Herein,single nickel(Ni)atoms on two-dimensional(2D)nitrogen(N)-doped carbon with Ni-N_(4)-O overcoordinated structure(SANi-N_(4)-O/NC)are prepared and firstly used as a sulfur host of Li-S batteries.Due to the efficient polysulfides traps and highly LiPSs conversion effect of SANi-N_(4)-O/NC,the electrochemical performance of Li-S batteries obviously improved.The batteries can well operate even under high sulfur loading(5.8 mg cm^(-2))and lean electrolyte(6.1μL mg^(-1))condition.Meanwhile,density functional theory(DFT)calculations demonstrate that Ni single atom’s active sites decrease the energy barriers of conversion reactions from Li_(2)S_(8)to Li2S due to the strong interaction between SANi-N_(4)-O/NC and LiPSs.Thus,the kinetic conversion of LiPSs was accelerated and the shuttle effect is suppressed on SANi-N_(4)-O/NC host.This study provides a new design strategy for a 2D structure with single-atom overcoordinated active sites to facilitate the fast kinetic conversion of LiPSs for Li-S cathode.

Dual-Functional Lithiophilic/Sulfiphilic Binary-Metal Selenide Quantum Dots Toward High-Performance Li-S Full Batteries

The commercial viability of lithium-sulfur batteries is still challenged by the notorious lithium polysulfides(Li PSs)shuttle effect on the sulfur cathode and uncontrollable Li dendrites growth on the Li anode.Herein,a bi-service host with Co-Fe binary-metal selenide quantum dots embedded in three-dimensional inverse opal structured nitrogen-doped carbon skeleton(3DIO FCSe-QDs@NC)is elaborately designed for both sulfur cathode and Li metal anode.The highly dispersed FCSe-QDs with superb adsorptive-catalytic properties can effectively immobilize the soluble Li PSs and improve diffusion-conversion kinetics to mitigate the polysulfide-shutting behaviors.Simultaneously,the 3D-ordered porous networks integrated with abundant lithophilic sites can accomplish uniform Li deposition and homogeneous Li-ion flux for suppressing the growth of dendrites.Taking advantage of these merits,the assembled Li-S full batteries with 3DIO FCSe-QDs@NC host exhibit excellent rate performance and stable cycling ability(a low decay rate of 0.014%over 2,000 cycles at 2C).Remarkably,a promising areal capacity of 8.41 mAh cm^(-2)can be achieved at the sulfur loading up to 8.50 mg cm^(-2)with an ultra-low electrolyte/sulfur ratio of 4.1μL mg^(-1).This work paves the bi-serve host design from systematic experimental and theoretical analysis,which provides a viable avenue to solve the challenges of both sulfur and Li electrodes for practical Li-S full batteries.