Liquid metal in prohibiting polysulfides shuttling in metal sulfides anode for sodium-ion batteries

Metal sulfides are a class of promising anode materials for sodium-ion batteries(SIBs)owing to their high theoretical specific capacity.Nevertheless,the reactant products(polysulfides)could dissolve into electrolyte,shuttle across separator,and react with sodium anode,leading to severe capacity loss and safety concerns.Herein,for the first time,gallium(Ga)-based liquid metal(LM)alloy is incorporated with MoS_(2)nanosheets to work as an anode in SIBs.The electron-rich,ultrahigh electrical conductivity,and self-healing properties of LM endow the heterostructured MoS_(2)-LM with highly improved conductivity and electrode integrity.Moreover,LM is demonstrated to have excellent capability for the adsorption of polysulfides(e.g.,Na_(2)S,Na_(2)S_(6),and S_(8))and subsequent catalytic conversion of Na_(2)S.Consequently,the MoS_(2)-LM electrode exhibits superior ion diffusion kinetics and long cycling performance in SIBs and even in lithium/potassium-ion battery(LIB/PIB)systems,far better than those electrodes with conventional binders(polyvinylidene difluoride(PVDF)and sodium carboxymethyl cellulose(CMC)).This work provides a unique material design concept based on Ga-based liquid metal alloy for metal sulfide anodes in rechargeable battery systems and beyond.

Integrated host configuration of flexibly fibrous skeleton towards efficient polysulfide conversion and dendrite-free behavior in stable lithium-sulfur pouch cells

The commercialization of lithium-sulfur(Li-S) batteries is obstructed by the sluggish sulfur electrochemical reaction,severe polysulfide shuttling effect,and damaging dendritic lithium growth.Herein,a threedimensional(3D) conductive carbon nanofibers skeleton-based bifunctional electrode host material is fabricated,which consists of a two-dimensional(2D) ultra-thin NiSe_(2)-CoSe_(2)heterostructured nanosheet built on one-dimensional(1D) carbon nanofibers(NiSe_(2)-CoSe_(2)@CNF).When serving as cathodic host,the heterostructured NiSe_(2)-CoSe_(2)@CNF offers a synergistic function of polysulfide confinement and catalysis conversion.The S/NiSe_(2)-CoSe_(2)@CNF cathode shows outstanding cycling stability of 0.03% capacity decay rate per cycle over 500 cycles at 1 C.As anodic host,the NiSe_(2)-CoSe_(2)@CNF with high-flux Li+diffusion property and good lithiophilic capability realizes dendrite-free Li plating/stripping behavior.Benefiting from these synergistically merits,the Li-S full cell with S/NiSe_(2)-CoSe_(2)@CNFILi/NiSe_(2)-CoSe_(2)@CNF electrodes exhibits excellent electrochemical performance including a high specific capacity of1021 mA h g^(-1)over 100 cycles at 0.2 C and reversible areal capacity of 3.05 mA h cm^(-2)under a high sulfur loading of 4.33 mg cm^(-2)at 0.1 C.The pouch cell also delivers ultra-stable Li/S electrochemistry.This study demonstrates a rational and universal electrode construction strategy for developing practical and high-energy Li-S batteries.

Sulfhydryl-functionalized COF-based electrolyte strengthens chemical affinity toward polysulfides in quasi-solid-state Li-S batteries

For lithium-sulfur batteries(Li-S batteries),a high-content electrolyte typically can exacerbate the shuttle effect,while a lean electrolyte may lead to decreased Li-ion conductivity and reduced catalytic conversion efficiency,so achieving an appropriate electrolyte-to-sulfur ratio(E/S ratio)is essential for improving the battery cycling efficiency.A quasi-solid electrolyte(COF-SH@PVDF-HFP)with strong adsorption and high catalytic conversion was constructed for in situ covalent organic framework(COF)growth on highly polarized polyvinylidene fluoride-hexafluoropropylene(PVDF-HFP)fibers.COF-SH@PVDF-HFP enables efficient Li-ion conductivity with low-content liquid electrolyte and effectively suppresses the shuttle effect.The results based on in situ Fourier-transform infrared,in situ Raman,UV–Vis,X-ray photoelectron,and density functional theory calculations confirmed the high catalytic conversion of COF-SH layer containing sulfhydryl and imine groups for the lithium polysulfides.Lithium plating/stripping tests based on Li/COF-SH@PVDF-HFP/Li show excellent lithium compatibility(5 mAh cm^(-2) for 1400 h).The assembled Li-S battery exhibits excellent rate(2 C 688.7 mAh g^(-1))and cycle performance(at 2 C of 568.8 mAh g^(-1) with a capacity retention of 77.3%after 800 cycles).This is the first report to improve the cycling stability of quasi-solid-state Li-S batteries by reducing both the E/S ratio and the designing strategy of sulfhydryl-functionalized COF for quasi-solid electro-lytes.This process opens up the possibility of the high performance of solid-state Li-S batteries.

Polymer electrolytes for Li-S batteries:Polymeric fundamentals and performance optimization

Lithium-sulfur(Li-S) batteries have been considered as one of the most promising candidates to traditional lithium ion batteries due to its low cost,high theoretical specific capacity(1675 mAh g^(-1)) and energy density(2600 Wh kg^(-1)) of sulfur.Compared with traditional liquid electrolytes,polymer electrolytes(PEs) are ever-increasingly preferred due to their higher safety,superior compatibility,long cycling stability and so on.Despite some progresses on PEs,however,there remain lots of hurdles to be addressed prior to commercial applications.This review begins with native advantages for PEs to replace LEs,and then proposes the ideal requirements for PEs.Furthermore,a brief development history of typical PEs for Li-S batteries is presented to systematically summarize the recent achievements in Li-S batteries with PEs.Noted that the structure-performance relationships of polymer matrixes for PEs are highlighted.Finally,the challenges and opportunities on the future development of PEs are presented.We hold the view that composite polymer electrolytes in virtue of the high ionic conductivity and the compatible interfacial property will be promising solution for high performance Li-S batteries.

Designing metal sulfide-based cathodes and separators for suppressing polysulfide shuttling in lithium-sulfur batteries

Lithium-sulfur(Li-S)batteries,known for their high energy density,are attracting extensive research interest as a promising next-generation energy storage technology.However,their widespread use has been hampered by certain issues,including the dissolution and migration of polysulfides,along with sluggish redox kinetics.Metal sulfides present a promising solution to these obstacles regarding their high electrical conductivity,strong chemical adsorption with polysulfides,and remarkable electrocatalytic capabilities for polysulfide conversion.In this review,the recent progress on the utilization of metal sulfide for suppressing polysulfide shuttling in Li-S batteries is systematically summarized,with a special focus on sulfur hosts and functional separators.The critical roles of metal sulfides in realizing high-performing Li-S batteries have been comprehensively discussed by correlating the materials’structure and electrochemical performances.Moreover,the remaining issues/challenges and future perspectives are highlighted.By offering a detailed understanding of the crucial roles of metal sulfides,this review dedicates to contributing valuable knowledge for the pursuit of high-efficiency Li-S batteries based on metal sulfides.

Higher-order polysulfides induced thermal runaway for 1.0 Ah lithium sulfur pouch cells

Comprehensive analyses on thermal runaway mechanisms are critically vital to achieve the safe lithium-sulfur(Li-S)batteries.The reactions between dissolved higher-order polysulfides and Li metal were found to be the origins for the thermal runaway of 1.0 Ah cycled Li-S pouch cells.16-cycle pouch cell indicates high safety,heating from 30 to 300 ℃ without thermal runaway,while 16-cycle pouch cell with additional electrolyte undergoes severe thermal runaway at 147.9 ℃,demonstrating the key roles of the electrolyte on the thermal safety of batteries.On the contrary,thermal runaway does not occur for 45-cycle pouch cell despite the addition of the electrolyte.It is found that the higher-order polysulfides(Li_(2)S_(x) ≥ 6)are discovered in 16-cycle electrolyte while the sulfur species in 45-cycle electrolyte are Li_(2)S_(x) ≤ 4.In addition,strong exothermic reactions are discovered between cycled Li and dissolved higher-order polysulfide(Li_(2)S_(6) and Li_(2)S_(8))at 153.0 ℃,driving the thermal runaway of cycled Li-S pouch cells.This work uncovers the potential safety risks of Li-S batteries and negative roles of the polysulfide shuttle for Li-S batteries from the safety view.

Spinel-type bimetal sulfides derived from Prussian blue analogues as efficient polysulfides mediators for lithium-sulfur batteries

More and more attentions have been attracted by lithium-sulfur batteries(Li-S), owing to the high energy density for the increasingly advanced energy storage system. While the poor cycling stability, due to the inherent polysulfide shuttle, seriously hampered their practical application. Recently, some polar hosts,like single metal oxides and sulfides, have been employed as hosts to interact with polysulfide intermediates. However, due to the inherent poor electrical conductivity of these polar hosts, a relatively low specific capacity is obtained. Herein, a spinel-type bimetal sulfide NiCo_(2)S_(4)through a Prussian blue analogue derived methodology is reported as the novel host of polysulfide, which enables highperformance sulfur cathode with high Coulombic efficiency and low capacity decay. Notably, the Li-S battery with NiCo_(2)S_(4)-S composites cathode still maintains a capacity of 667 m Ah/g at 0.5 Cafter 300 cycles, and 399 m Ah/g at 1 C after 300 cycles. Even after 300 cycles at the current density of 0.5C, the capacity decays by 0.138% per cycle at high sulfur loading about 3 mg/cm;. And the capacity decays by0.026% per cycle after 1000 cycles, when the rate is 1C. More importantly, the cathode of Ni Co_(2)S_(4)-S composite shows the outstanding discharge capacity, owing to its good conduction, high catalytic ability and the strong confinement of polysulfides.

Promoting polysulfide conversions via cobalt single-atom catalyst for fast and durable lithium-sulfur batteries

Although promising strategies have been developed to resolve the critical drawbacks of lithium-sulfur(Li-S)batteries,the intractable issues including undesirable shuttling of polysulfides and sluggish redox reaction kinetics have still been unresolved thoroughly.Herein,a cobalt single-atom(CoSA)catalyst comprising of atomic Co distributed homogeneously within nitrogen(N)-doped porous carbon(Co-NPC)nanosphere is constructed and utilized as a separator coating in Li-S batteries.The Co-NPC exposes abundant active sites participating in sulfur redox reactions,and remarkable catalytic activity boosting the rapid polysulfide conversions.As a result,Li-S batteries with Co-NPC coating layer realize significantly enhanced specific capacity(1295 mAh·g^(-1)at 0.2 C),rate capability(753 mAh·g^(-1)at 3.0 C),and long-life cyclic stability(601 mAh·g^(-1)after 500 cycles at 1.0 C).Increasing the areal sulfur loading to 6.2 mg·cm^(-2),an extremely high areal capacity of 7.92 mAh·cm^(-2)is achieved.Further in situ X-ray diffraction,density functional theory calculations,and secondary ion mass spectrometry confirm the high catalytic capability of CoSA towards reversible polysulfide conversion.This study supplies new insights for adopting single-atom catalyst to upgrade the electrochemical performance of Li-S batteries.

Cage-confinement synthesis of MoC nanoclusers as efficient sulfiphilic and lithiophilic regulator for superior Li–S batteries

High-energy-density Li-S batteries are subjected to serious sulfur deactivation and short cycle lifetime caused by undesirable polysulfide shuttle effect and frantic lithium dendrite formation.In this work,a controllable cage-confinement strategy to fabricate molybdenum carbide(MoC)nanoclusters as a high-efficient sulfiphilic and lithiophilic regulator to mitigate the formidable issues of Li-S batteries is demonstrated.The sub-2 nm MoC nanoclusters not only guarantee robust chemisorption and fast electrocatalytic conversion of polysulfides to enhance the sulfur electrochemistry,but also homogenize Li^(+) flux to suppress the lithium dendrite growth.As a consequence,the MoC-modified separator endows the batteries with boosted reaction kinetics,promoted sulfur utilization,and improved cycling stability.A reversible capacity of 701 mAh·g^(−1) at a high rate of 5.0C and a small decay rate of 0.076%per cycle at 1.0C over 600 cycles are achieved.This study offers a rational route for design and synthesis of bifunctional nanoclusers with both sulfiphilicity and lithiophilicity for high-performance Li-S batteries.

Challenges and prospects for room temperature solid-state sodiumsulfur batteries

Room temperature sodium-sulfur(Na-S)batteries,known for their high energy density and low cost,are one of the most promising next-generation energy storage systems.However,the polysulfide shuttling and uncontrollable Na dendrite growth as well as safety issues caused by the use of organic liquid electrolytes in Na-S cells,have severely hindered their commercialization.Solid-state electrolytes instead of liquid electrolytes are considered to be the most direct and effective solution to solve the above problems.However,its practical application is still greatly challenged due to the poor interfacial compatibility between the all-solid-state electrolytes and the anode/cathode,ionic conductivity,and the shuttle effect caused by the presence of liquid phase in the quasi-solid-state electrolytes.This paper presents a comprehensive review of solid-state Na-S batteries from the perspective of regulating interfacial compatibility and improving ionic conductivity as well as suppressing polysulfide shuttle.According to different components,solid-state electrolytes were divided into five categories:solid inorganic electrolytes,solid polymer electrolytes,polymer/inorganic solid hybrid electrolytes,gel polymer electrolytes,and liquid–solid inorganic hybrid electrolytes.Finally,the prospect of developing high performance solid-state electrolytes to improve the cycling stability of room temperature Na-S cells is envisaged.

Review Article Electrocatalysts in lithium-sulfur batteries

Lithium-sulfur(Li-S)batteries with the merits of high theoretical capacity and high energy density have gained significant attention as the next-generation energy storage devices.Unfortunately,the main pressing issues of sluggish reaction kinetics and severe shuttling of polysulfides hampered their practical application.To overcome these obstacles,various strategies adopting high-efficient electrocatalysts have been explored to enable the rapid polysulfide conversions and thereby suppressing the polysulfide shuttling.This review first summarizes the recent progress on electrocatalysts involved in hosts,interlayers,and protective layers.Then,these electrocatalysts in Li-S batteries are analyzed by listing representative works,from the viewpoints of design concepts,engineering strategies,working principles,and electrochemical performance.Finally,the remaining issues/challenges and future perspectives facing electrocatalysts are given and discussed.This review may provide new guidance for the future construction of electrocatalysts and their further utilizations in high-performance Li-S batteries.

Demystifying the catalysis in lithium–sulfur batteries:Characterizationmethods and techniques

Lithium–sulfur(Li-S)batteries are promising next-generation energy storage systems with ultrahigh energy density.However,the intrinsic sluggish“solid–liquid–solid”reaction between S8 and Li2S causes unavoidable shuttling of polysulfides,severely limiting the practical energy density and cycling performance.Recently,the catalysis process has been introduced for the sulfur redox reaction to accelerate the conversion of polysulfides,providing a positive remedy for the polysulfides shuttling.Nevertheless,in-depth understanding of the catalyst evaluation criteria and catalytic mechanism still lies in the“black box”,and precise characterization technique is the key to unlock this puzzle.In this review,we provide a comprehensive overview of characterization techniques on the catalyst in Li-S batteries from two aspects of catalytic performance and catalytic mechanism,highlighting their significance and calling for more efforts to develop precise and fast techniques for Li-S catalysis.Moreover,we envision the future development of characterization for better understanding the catalysis toward practical Li-S battery.

Solution-based Preparation of High Sulfur Content Sulfur/Graphene Cathode Material for Li-S Battery

Practical Li-sulfur batteries require the high sulfur loading cathode to meet the large-capacity power demand of electrical equipment.However,the sulfur content in cathode materials is usually unsatisfactory due to the excessive use of carbon for improving the conductivity.Traditional cathode fabrication strategies can hardly realize both high sulfur content and homogeneous sulfur distribution without aggregation.Herein,we designed a cathode material with ultrahigh sulfur content of 88%(mass fraction)by uniformly distributing the water dispersible sulfur nanoparticles on three-dimensionally conductive graphene framework.The water processable fabrication can maximize the homogeneous contact between sulfur nanoparticles and graphene,improving the utilization of the interconnected conductive surface.The obtained cathode material showed a capacity of 500 mA·h/g after 500 cycles at 2.0 A/g with an areal loading of 2 mg/cm2.This strategy provides possibility for the mass production of high-performance electrode materials for high-capacity Li-S battery.