Lithium-sulfur batteries(LSBs)are being recognized as potential successor to ubiquitous LIBs in daily life due to their higher theoretical energy density and lower cost effectiveness.However,the development of the LSB...Lithium-sulfur batteries(LSBs)are being recognized as potential successor to ubiquitous LIBs in daily life due to their higher theoretical energy density and lower cost effectiveness.However,the development of the LSB is beset with some tenacious issues,mainly including the insulation nature of the S or Li_(2)S(the discharged product),the unavoidable dissolution of the reaction intermediate products(mainly as lithium polysulfides(LiPSs)),and the subsequent LiPSs shuttling across the separator,resulting in the continuous loss of active material,anode passivation,and low coulombic efficiency.Containment methods by introducing the high-electrical conductivity host are commonly used in improving the electrochemical performances of LSBs.However,such prevalent technologies are in the price of reduced energy density since they require more addition of amount of host materials.Adding trace of catalysts that catalyze the redox reaction between S/Li_(2)S and Li_(2)Sn(3<n≤8),shows ingenious design,which not only accelerates the conversion reaction between the solid S species and dissolved S species,alleviating the shuttle effect,but also expedites the electron transport thus reducing the polarization of the electrode.In this review,the redox reaction process during Li-S chemistry are firstly highlighted.Recent developed catalysts,including transitionmetal oxides,chalcogenides,phosphides,nitrides,and carbides/borides are then outlined to better understand the role of catalyst additives during the polysulfide conversion.Finally,the critical issues,challenges,and perspectives are discussed to demonstrate the potential development of LSBs.展开更多
Lithium-sulfur (Li-S) batteries are considered appealing power sources due to their high theoretical energy density (2600 Wh kg-1), low cost, and environmental friendliness. However, their widespread applicability is ...Lithium-sulfur (Li-S) batteries are considered appealing power sources due to their high theoretical energy density (2600 Wh kg-1), low cost, and environmental friendliness. However, their widespread applicability is restricted by two scientific problems: sluggish sulfur reaction kinetics and severe polysulfide shuttle effects. Multifarious strategies have been developed to overcome these two obstacles and achieve high sulfur utilization and capacity retention. Among these strategies, the introduction of catalytic materials into the Li-S battery system can greatly accelerate sulfur conversion and effectively inhibit the polysulfide shuttle effects. Herein, we have comprehensively reviewed the recent progress of catalytic engineering for polysulfide conversion in high-performance lithium-sulfur batteries. First, various catalytic materials serve as sulfur hosts, functionalized separators, and electrolyte additives;the mechanisms by which these materials promote the conversion of polysulfides in Li-S batteries have been systematically summarized. The relationship of structure, preparation, property, advantages, and limitations of these catalytic materials are comprehensively presented. Subsequently, the advanced characterization techniques of these catalytic processes are discussed, shedding light on the fundamental understanding of catalytic effects for improved electrochemical performance. Furthermore, future design tactics for high-performance Li-S batteries are discussed.展开更多
Modulating the electronic structure has emerged as an effective strategy for optimizing the adsorption and catalytic capabilities of electrocatalysts in lithium-sulfur(Li-S)batteries.However,the regulation of electron...Modulating the electronic structure has emerged as an effective strategy for optimizing the adsorption and catalytic capabilities of electrocatalysts in lithium-sulfur(Li-S)batteries.However,the regulation of electronic structure involving spin-related charge transfer and orbital interactions has been largely underexplored in sulfur electrocatalysts.Herein,selenium-deficient bimetallic selenides embedded in a coaxial carbon layer(CoSe_(2-x)/ZnSe)were meticulously fabricated as electrocatalysts,aiming to modulate the electron spin state of Co catalytic sites to enhance the bidirectional lithium polysulfides(LiPSs)conversion kinetics and suppress the LiPSs shuttling effect.Density functional theory(DFT)calculations and experimental results indicate that the selenium vacancies at the CoSe_(2-x)/ZnSe heterointerfaces weaken the ligand fields and drive the Co 3d orbital electronic structure transition from low-spin to high-spin states.Such tailored spin state configuration generates more unpaired electrons and upshifts the dband center,thus accelerating the charge transfer and strengthening the orbital interactions between LiPSs and Co catalytic sites.As a consequence,the assembled Li-S batteries with CoSe_(2-x)/ZnSe electrocatalysts exhibit an ultralow average decay rate of 0.028%per cycle at 1 C over 1000 cycles.This work presents a novel strategy for manipulating ligand fields to realize electron spin state modulation in sulfur electrocatalysts.展开更多
The growing demand for efficient and sustainable energy storage technologies has spurred significant research into alternatives to traditional lithium-ion batteries.Benefiting from the high energy density and abundant...The growing demand for efficient and sustainable energy storage technologies has spurred significant research into alternatives to traditional lithium-ion batteries.Benefiting from the high energy density and abundant,environmentally friendly properties of sulfur,metal−sulfur(M-S)batteries represent some of the most promising candidates for nextgeneration energy storage.1,2 Among them,lithium−sulfur(Li−S)and sodium−sulfur(Na−S)batteries have garnered attention due to their potential to surpass the performance of current energy storage technologies in terms of both energy capacity and cost-effectiveness,making them particularly attractive for applications in electric vehicles(EVs),gridscale energy storage,and portable electronics,where high energy density is a crucial factor.展开更多
Lithium-sulfur(Li-S)batteries promise high energy density but suffer from low conductivity,polysulfide shuttling,and sluggish conversion kinetics.The construction of heterointerfaces is an effective strategy for enhan...Lithium-sulfur(Li-S)batteries promise high energy density but suffer from low conductivity,polysulfide shuttling,and sluggish conversion kinetics.The construction of heterointerfaces is an effective strategy for enhancing both polysulfide adsorption and conversion;however,the poor lattice compatibility in the heterointerface formed by different materials hinders interfacial charge transfer.In response to these challenges,herein,a biphasic homojunction of TiO_(2)enriched with oxygen vacancies and decorated with nitrogen-doped carbon nanotubes(B-TiO_(2-x)@NCNT)was designed to simultaneously enhance adsorption ability and catalytic activity.This homojunction interface composed of rutile(110)and anatase(101)plane exhibits excellent compatibility,and density functional theory(DFT)calculations reveal that this biphasic interface possesses a much higher binding energy to polysulfides compared to single-phase TiO_(2).Additionally,NCNTs are in situ grown on both interior and exterior surfaces of the hollow TiO_(2)nanospheres,facilitating rapid electron transfer for the encapsulated sulfur.The homojunction interface synergistically leverages the oxygen vacancies and highly conductive NCNTs to enhance the bidirectional catalytic activity for polysulfide conversion.Therefore,in this multifunctional sulfur-host,polysulfides are first strongly adsorbed at the homojunction interfaces and subsequently undergo smooth conversion,nucleation,and decomposition,completing a rapid sulfur redox cycle.The assembled Li-S battery delivered a high specific capacity of 1234.3 mAh g^(-1)at 0.2 C,long cycling stability for over 1000 cycles at 5 C with a low decay rate of 0.035%,and exciting areal capacity at a high sulfur loading of 5.6 mg cm^(-2)for 200cycles.展开更多
To tackle undesirable shuttle reaction and sluggish reaction kinetics in lithium–sulfur(Li–S)batteries,we develop a porous and high-density oxygen-doped tantalum nitride nanostructure(nano-TaNO)as an efficient catal...To tackle undesirable shuttle reaction and sluggish reaction kinetics in lithium–sulfur(Li–S)batteries,we develop a porous and high-density oxygen-doped tantalum nitride nanostructure(nano-TaNO)as an efficient catalyst through delicate tailoring.Benefiting from well-defined interior and surface nanopore channels,the nano-TaNO favors abundant sulfur storage,easy electrolyte infiltration and good electrons/Li+transport.More importantly,high-density O dopant in nano-TaNO not only provides high conductivity,but also promotes polysulfide adsorption/conversion via Li–O chemical interactions and the generation of S3∗−radicals to activate additional evolution path from S8 to Li_(2)S.Consequently,the nano-TaNObased cathode exhibits excellent specific capacity and cyclability even under high sulfur loading condition.These interesting findings suggest the great potential of tantalum nitride and a high amount of anion doping engineering in manipulating intermediates and building high-performance Li−S rechargeable batteries.展开更多
Extensive research has been devoted to lithium-sulfur(Li-S)batteries due to their overwhelming promises and advantages such as high theoretical capacity(1675 m Ah g^(-1)),extremely cost effectiveness and abundance and...Extensive research has been devoted to lithium-sulfur(Li-S)batteries due to their overwhelming promises and advantages such as high theoretical capacity(1675 m Ah g^(-1)),extremely cost effectiveness and abundance and availability of sulfur.Nevertheless,a sluggish electrochemical kinetics of the battery limited by a slow conversion of lithium polysulfide(LiPSs)intermediates and Li PSs shuttle effect severely hinder its development towards industrial application.Herein,we designed the oxidized Nb2_(C)MXene with amorphous carbon(Nb_(2)O_(5)/C)composites as sulfur host using CO_(2)treatment to address the above issues.The Nb_(2)O_(5)/C composites with high conductivity are directly employed as sulfur hosts for Li-S battery capable to remarkably mitigate the shuttle phenomenon due to a combined effect of their Li PSs trapping ability and catalytic activity towards their accelerated conversion.Meanwhile,the unique layered structure of the composite facilitates ion transfer and accommodates the volume changes of the cathode during cycling.With this rational design,the resultant Li-S batteries exhibit superior electrochemical performance with a high initial specific capacity of 745 m Ah g^(-1)at 1.0 C and a reversible capacity of 620 m Ah g^(-1)at a high rate cycling at 3.0 C.展开更多
Thanks to the significantly higher energy density compared with universal commercialized Li-ion batteries,lithium–sulfur(Li–S)batteries are being investigated for use in prospective energy storage devices.However,th...Thanks to the significantly higher energy density compared with universal commercialized Li-ion batteries,lithium–sulfur(Li–S)batteries are being investigated for use in prospective energy storage devices.However,the inadequate electrochemical kinetics of reactants and intermediates hinder commercial utilization.This limitation results in substantial capacity degradation and short battery lifespans,thereby impeding the battery's power export.Meanwhile,the capacity attenuation induced by the undesirable shuttle effect further hinders their industrialization.Considerable effort has been invested in developing electrocatalysts to fix lithium polysulfides and boost their conversion effectively.In the conventional process,the planar electrodes are prepared by slurry-casting,which limits the electron and ion transfer paths,especially when the thickness of the electrodes is relatively large.Compared with traditional manufacturing methods,direct ink writing(DIW)technology offers unique advantages in both geometry shaping and rapid prototyping,and even complex three-dimensional structures with high sulfur loading.Hence,this review presents a detailed description of the current developments in terms of Li–S batteries in DIW of metal-based electrocatalysts.A thorough exploration of the behavior chemistry of electrocatalysis is provided,and the adhibition of metal-based catalysts used for Li–S batteries is summarized from the aspect of material usage and performance enhancement.Then,the working principle of DIW technology and the requirements of used inks are presented,with a detailed focus on the latest advancements in DIW of metal-based catalysts in Li–S battery systems.Their challenges and prospects are discussed to guide their future development.展开更多
Lithium-sulfur batteries(LSBs)are considered as the most promising energy storage technologies owing to their large theoretical energy density(2500Wh/kg)and specific capacity(1675 mAh/g).However,the heavy shuttle effe...Lithium-sulfur batteries(LSBs)are considered as the most promising energy storage technologies owing to their large theoretical energy density(2500Wh/kg)and specific capacity(1675 mAh/g).However,the heavy shuttle effect of polysulfides and the growth of lithium dendrites greatly hinder their further development and commercial application.In this paper,cobalt-molybdenum bimetallic carbides heterostructure(Co_(6)Mo_(6)C_(2)@Co@NC)was successfully prepared through chemical etching procedure of ZIF-67 precursor with sodium molybdate and the subsequent high temperature annealing process.The obtained dodecahedral Co_(6)Mo_(6)C_(2)@Co@NC with hollow and porous structure provides large specific surface area and plentiful active sites,which speeds up the chemisorption and catalytic conversion of polysulfides,thus mitigating the shuttle effect of polysulfides and the generation of lithium dendrites.When applied as the LSBs separator modifier layer,the cell with modified separator present excellent rate capability and durable cycling stability.In particular,the cell with Co_(6)Mo_(6)C_(2)@Co@NC/PP separator can maintain the high capacity of 738 mAh/g at the current density of 2 C and the specific capacity of 782.6 mAh/g after 300 cycles at 0.5 C,with the coulombic efficiency(CE)near to 100%.Moreover,the Co_(6)Mo_(6)C_(2)@Co@NC/PP battery exhibits the impressive capacity of 431 mAh/g in high sulfur loading(4.096 mg/cm^(2))at 0.5 C after 200 cycles.This work paves the way for the development of bimetallic carbides heterostructure multifunctional catalysts for durable Li-S battery applications and reveals the synergistic regulation of polysulfides and lithium dendrites through the optimization of the structure and composition.展开更多
The shuttle effect derived from diffusion of lithium polysulfides(LiPSs) and sluggish redox kinetic bring about poor cycling stability and low utilization of sulfur,which have always been the key challenging issues fo...The shuttle effect derived from diffusion of lithium polysulfides(LiPSs) and sluggish redox kinetic bring about poor cycling stability and low utilization of sulfur,which have always been the key challenging issues for the commercial application of lithium-sulfur(Li-S) batteries.Rational design of cathode materials to catalyze Li_(2)S dissociation/nucleation processes is an appealing and valid strategy to develop high-energy practical Li-S batteries.Herein,considering the synergistic effect of bidirectional catalysis on LiPSs conversion and enhanced chemical immobilization for LiPSs by heteroatom doping,Pt nanoparticles loaded on nitrogen-doped carbon spheres(Pt/NCS composites) were constructed as cathode materials.According to the dynamic evolution of Pt catalysts and sulfur species,Pt~0 and Pt^(2+) species were identified as active species for the accelerated dissociation and nucleation of Li_(2)S,respectively.Meanwhile,in-situ Raman results demonstrated the expedited conversion of sulfur species resulted from bidirectional catalysis of active Pt species,corresponding to boosted redox kinetics.Consequently,Pt/NCS cathode exhibited improved long-term cyclability with high initial capacity,along with enhanced rate capability.This work provides a facile approach to construct cathode materials with bidirectional catalysis on Li_(2)S dissociation/nucleation,and sheds light on a more global understanding of the catalytic mechanism of metal catalysts during LiPSs conversion.展开更多
The exploration of new catalytic hosts is highly important to tackle the sluggish electrochemical kinetics of sulfur redox for achieving high energy density of lithium–sulfur batteries.Herein,for the first time,we pr...The exploration of new catalytic hosts is highly important to tackle the sluggish electrochemical kinetics of sulfur redox for achieving high energy density of lithium–sulfur batteries.Herein,for the first time,we present high-entropy oxide(HEO,(Mg_(0.2)Mn_(0.2)Ni_(0.2)Co_(0.2)Zn_(0.2))Fe_(2)O_(4))nanofibers as catalytic host of sulfur.The HEO nanofibers show a synergistic effect among multiple metal cations in spinel structure that enables strong chemical confinement of soluble polysulfides and fast kinetics for polysulfide conversion.Consequently,the S/HEO composite displays the high gravimetric capacity of 1368.7 mAh g^(−1) at 0.1 C rate,excellent rate capability with the discharge capacity of 632.1 mAh g^(−1) at 5 C rate,and desirable cycle stability.Furthermore,the S/HEO composite shows desirable sulfur utilization and good cycle stability under a harsh operating condition of high sulfur loading(4.6 mg cm^(−2))or low electrolyte/sulfur ratio(5μL mg^(−1)).More impressively,the high volumetric capacity of 2627.9 mAh cm^(−3) is achieved simultaneously for the S/HEO composite due to the high tap density of 1.92 g cm^(−3),nearly 2.5 times of the conventional sulfur/carbon composite.Therefore,based on high-entropy oxide materials,this work affords a fresh concept of elevating the gravimetric/volumetric capacities of sulfur cathodes for lithium–sulfur batteries.展开更多
Lithium-sulfur(Li-S)batteries are promising candidates for next-generation energy storage systems owing to their high energy density and low cost.However,critical challenges including severe shuttling of lithium polys...Lithium-sulfur(Li-S)batteries are promising candidates for next-generation energy storage systems owing to their high energy density and low cost.However,critical challenges including severe shuttling of lithium polysulfides(LiPSs)and sluggish redox kinetics limit the practical application of Li-S batteries.Carbon nitrides(C_(x)N_(y)),represented by graphitic carbon nitride(g-C_(3)N_(4)),provide new opportunities for overcoming these challenges.With a graphene-like structure and high pyridinic-N content,g-C_(3)N_(4) can effectively immobilize LiPSs and enhance the redox kinetics of S species.In addition,its structure and properties including electronic conductivity and catalytic activity can be regulated by simple methods that facilitate its application in Li-S batteries.Here,the recent progress of applying C_(x)N_(y)-based materials including the optimized g-C_(3)N_(4),g-C_(3)N_(4)-based composites,and other novel C_(x)N_(y) materials is systematically reviewed in Li-S batteries,with a focus on the structure-activity relationship.The limitations of existing C_(x)N_(y)-based materials are identified,and the perspectives on the rational design of advanced C_(x)N_(y)-based materials are provided for high-performance Li-S batteries.展开更多
Lithium–sulfur(Li-S)batteries are regarded as one of the most promising energy storage devices because of their low cost,high energy density,and environmental friendliness.However,Li-S batteries suffer from sluggish ...Lithium–sulfur(Li-S)batteries are regarded as one of the most promising energy storage devices because of their low cost,high energy density,and environmental friendliness.However,Li-S batteries suffer from sluggish reaction kinetics and serious“shuttle effect”of lithium polysulfides(LiPSs),which causes rapid decay of battery capacity and prevent their practical application.To address these problems,introducing single-atom catalysts(SACs)is an effective method to improve the electrochemical performance of Li-S batteries,due to their high catalytic efficiency and definite active sites for LiPSs.In this paper,we summarized the latest developments in enhancing the electrochemical performance of cathode for Li-S batteries through introducing different SACs.Furthermore,we briefly introduced the catalytic mechanism of SACs and discussed the strategies of synthesizing SACs,including the spatial confinement strategy and the coordination design strategy.Finally,the challenges and prospects in this field are proposed.We believe that this review would help to design and fabricate high-performance Li-S batteries via introducing SACs and boost their practical application.展开更多
Lithium-sulfur(Li-S) batteries are promising for high energy-storage applications but suffer from sluggish conversion reaction kinetics and substantial lithium sulfide(Li_(2)S) oxidation barrier,especially under high ...Lithium-sulfur(Li-S) batteries are promising for high energy-storage applications but suffer from sluggish conversion reaction kinetics and substantial lithium sulfide(Li_(2)S) oxidation barrier,especially under high sulfur loadings.Here,we report a Li cation-doped tungsten oxide(Li_(x)WO_(x)) electrocatalyst that efficiently accelerates the S■HLi_(2)S interconversion kinetics.The incorporation of Li dopants into WO_(x) cationic vacancies enables bidirectional electrocatalytic activity for both polysulfide reduction and Li_(2)S oxidation,along with enhanced Li^(+) diffusion.In conjunction with theoretical calculations,it is discovered that the improved electrocatalytic activity originates from the Li dopant-induced geometric and electronic structural optimization of the Li_(x)WO_(x),which promotes the anchoring of sulfur species at favourable adsorption sites while facilitating the charge transfer kinetics.Consequently,Li-S cells with the Li_(x)WO_(x) bidirectional electrocatalyst show stable cycling performance and high sulfur utilization under high sulfur loadings.Our approach provides insights into cation engineering as an effective electrocatalyst design strategy for advancing high-performance Li-S batteries.展开更多
Designing electrochemical catalysts has become a research hotspot due to their accelerating the polysulfide conversion of the sulfur cathode to inhibit the“shuttle effect”in lithium-sulfur batteries.However,it is st...Designing electrochemical catalysts has become a research hotspot due to their accelerating the polysulfide conversion of the sulfur cathode to inhibit the“shuttle effect”in lithium-sulfur batteries.However,it is still a great challenge to design the heterogeneous selective electrochemical catalyst for inhibiting the“shuttle effect”.Herein,nickel cobalt phosphide and cobalt phosphide as the heterogeneous catalyst active sites embedded in the nitrogen-doped hollow carbon nanocages(NiCoP@CoP/NC)are reported,used for multi-step and multi-phase sulfur electrode reaction,and it is found that metal-sulfur d-p hybridization can effectively indicate the intrinsic catalytic activity of metal site.Division of labor and cooperation of the bi-active NiCoP@CoP as heterogeneous catalysts propel the stepwise polysulfide conversion.NiCoP and CoP sites preferentially accelerate the long-chain polysulfide conversion reaction(S_(8)■LiPSs)and the short-chain polysulfide conversion reactions(LiPSs■Li_(2)S),respectively.Moreover,the hollow and porous N-doped carbon structure can successfully suppress the volume effect and improve the conductivity of the sulfur cathode.The unique design can obtain an effective inhibition of the shuttle effect and rapid electrode reaction.As a result,Li-S batteries demonstrate a high initial capacity of 1063 mAh g^(-1) and a low-capacity decay of 0.04% per cycle within 1000 cycles.Our work provides a feasible idea for the design of host materials in Li-S batteries.展开更多
Heterostructure engineering for sulfur hosts is an effective way to achieve interfacial synergistic effects on suppressing the“shuttle effect”of polysulfides and thus improve electrochemical performance of lithium–...Heterostructure engineering for sulfur hosts is an effective way to achieve interfacial synergistic effects on suppressing the“shuttle effect”of polysulfides and thus improve electrochemical performance of lithium–sulfur(Li–S)batteries.Rational selection and design of different components into heterostructures is vital to enhance the synergistic effect.Herein,MoS_(2)/MoP Mott–Schottky heterostructure nanoparticles decorated on reduced graphene oxide(MoS_(2)/MoP@rGO)are fabricated and used as sulfur host firstly.Theoretical calculation and experiment results reveal that the in-situ introduction of MoP could tune the electronic structure,activate the basal plane of MoS_(2),and achieve the interfacial synergistic effects between adsorption(MoS_(2))and fast conversion(MoP).Such synergistic effects enable MoS_(2)/MoP@rGO to not only remarkably facilitate Li_(2)S deposition during the discharging process but also significantly accelerate the Li_(2)S dissolution during the charging process,demonstrating bidirectional promotion behaviors.Thus,the designed cathode delivers initial capacity of 919.5 mA·h·g^(−1)with capacity of 502.3 mA·h·g^(−1)remaining after 700 cycles at 0.5 C.Even under higher sulfur loading of 4.31 mg·cm^(−2)and lower electrolyte to sulfur(E/S)ratio of 8.21μL·mg^(−1),the MoS_(2)/MoP@rGO@S cathode could still achieve good capacity and cycle stability.This work provides a novel and efficient structural design strategy of sulfur hosts for high-performance Li–S energy storage systems.展开更多
Resolving low sulfur reaction activity and severe polysulfide dissolution remains challenging in metalsulfur batteries.Motivated by a theoretical prediction,herein,we strategically propose nitrogenvacancy tantalum nit...Resolving low sulfur reaction activity and severe polysulfide dissolution remains challenging in metalsulfur batteries.Motivated by a theoretical prediction,herein,we strategically propose nitrogenvacancy tantalum nitride(Ta3N5-x)impregnated inside the interconnected nanopores of nitrogendecorated carbon matrix as a new electrocatalyst for regulating sulfur redox reactions in roomtemperature sodium-sulfur batteries.Through a pore-constriction mechanism,the nitrogen vacancies are controllably constructed during the nucleation of Ta3N5-x.The defect manipulation on the local environment enables well-regulated Ta 5d-orbital energy level,not only modulating band structure toward enhanced intrinsic conductivity of Ta-based materials,but also promoting polysulfide stabilization and achieving bifunctional catalytic capability toward completely reversible polysulfide conversion.Moreover,the interconnected continuous Ta3N5-x-in-pore structure facilitates electron and sodium-ion transport and accommodates volume expansion of sulfur species while suppressing their shuttle behavior.Due to these attributes,the as-developed Ta3N5-x-based electrode achieves superior rate capability of 730 mAh g-1 at 3.35 A g-1,long-term cycling stability over 2000 cycles,and high areal capacity over 6 mAh cm-2 under high sulfur loading of 6.2 mg cm-2.This work not only presents a new sulfur electrocatalyst candidate for metal-sulfur batteries,but also sheds light on the controllable material design of defect structure in hopes of inspiring new ideas and directions for future research.展开更多
Lithium-sulfur(Li-S)batteries have gained significant success as next-generation energy sources,but the slow conversion speed of polysulfides and resultant notorious shuttle effect still limit its practical utilizatio...Lithium-sulfur(Li-S)batteries have gained significant success as next-generation energy sources,but the slow conversion speed of polysulfides and resultant notorious shuttle effect still limit its practical utilization.Metal nitrides(MNs)with high chemical affinity and remarkable catalytic activity have been verified as highly-efficient electrocatalysts in addressing these remaining challenges.However,there is a lack of comprehensive review that clarifying the detailed working principles of MNs in Li-S batteries.This study first summarizes the recent advances in the utilization of MNs for Li-S batteries,especially in sulfur hosts,separator coating layers,and interlayers.Typical MNs in each category were then introduced,by analyzing their material designs,catalytic effects,and modulation strategies.Important perspectives on the future developments of MN-based electrocatalysts and Li-S batteries are given,possible challenges and potential research directions are outlined.This work supplies precious insights into the use of MNs and their key roles in promoting the conversions of sulfur species.展开更多
With high energy density and low material cost,lithium sulfur batteries(LSBs)emerge quite expeditiously as a fascinating energy storage system over the past decade.Broad applications of LSBs ranging from electric vehi...With high energy density and low material cost,lithium sulfur batteries(LSBs)emerge quite expeditiously as a fascinating energy storage system over the past decade.Broad applications of LSBs ranging from electric vehicles to stationary grid storage seem rather bright in recent literatures.However,there still exist many pressing challenges to be addressed because we do not yet fully understand and control the electrode-electrolyte interface chemistries during battery operation,such as polysulide shuttling and poor utilization of active sulfur.Single-atom catalysts(SACs)pave new possibilities of tackling the tough issues due to their decent applicability in the atomic-level identification of structure-activity relationships and reaction mechanism,as well as their structural tunability with atomic precision.This review comprehensively summarizes the very recent advances in utilization of highly active SACs for LSBs by stating and discussing the related publications,which involves catalyst synthesis routes,battery pertormance,catalytic mechanisms,optimization strategies,and promises to achieve long-lite,high-energy LSBs.We see that endeavors to employ SACs to modify sulfur cathode have allowed efficient polysulfide conversion and confinement,leading to the minimization of shuttle effect.Parallel efforts are being devoted to extending the scope of SACs to cell separator and lithium metal anode in order to unlock the full potential of LSBs.We also obtain mechanistic insights into battery chemistries and nature of SACs in their strong interactions with polysulfides through advanced in situ characterizations documented.Overall,acceleration in the development of LSBs by introducing SACs is noticeable,and this cutting edge needs more attentions to further promoting the design of better LSBs.展开更多
开发具有多层次结构(包括多孔结构、杂化骨架和/或拓扑形貌)的超结构碳材料,对于满足电化学储能和转换系统中复杂催化反应的需求非常关键.在本文中,我们以钴纳米颗粒为催化位点,在杂化碳纳米管骨架表面可控接枝毛发状碳纳米管,开发了一...开发具有多层次结构(包括多孔结构、杂化骨架和/或拓扑形貌)的超结构碳材料,对于满足电化学储能和转换系统中复杂催化反应的需求非常关键.在本文中,我们以钴纳米颗粒为催化位点,在杂化碳纳米管骨架表面可控接枝毛发状碳纳米管,开发了一类层次化多孔的钴修饰碳纳米管瓶刷(Co/CNTBs).其中,精确的瓶刷状拓扑形貌和分级多孔结构能够有效地提供可及表/界面和高导电网络,钴修饰的杂化骨架可以促进硫的氧化还原反应动力学.因此,基于Co/CNTBs功能化隔膜的锂硫电池具有优异的倍率性能(在10 C下比容量为707 mA h g^(-1))和长效的循环稳定性.更重要的是,基于Co/CNTBs催化剂的高硫载量电池(6.72 mg cm^(-2))在0.1 C下循环100圈后仍具有4.81 mA h cm^(-2)的高面积容量.本工作为高性能超结构杂化碳材料的原位接枝合成策略带来了新的思路,有望用于众多具有挑战性的应用.展开更多
基金supported by the National Natural Science Foundation of China(21601089,21905140)the Six Talent Peaks Project of Jiangsu Province in China(2016-XCL-047)Jiangsu SpeciallyAppointed Professor program。
文摘Lithium-sulfur batteries(LSBs)are being recognized as potential successor to ubiquitous LIBs in daily life due to their higher theoretical energy density and lower cost effectiveness.However,the development of the LSB is beset with some tenacious issues,mainly including the insulation nature of the S or Li_(2)S(the discharged product),the unavoidable dissolution of the reaction intermediate products(mainly as lithium polysulfides(LiPSs)),and the subsequent LiPSs shuttling across the separator,resulting in the continuous loss of active material,anode passivation,and low coulombic efficiency.Containment methods by introducing the high-electrical conductivity host are commonly used in improving the electrochemical performances of LSBs.However,such prevalent technologies are in the price of reduced energy density since they require more addition of amount of host materials.Adding trace of catalysts that catalyze the redox reaction between S/Li_(2)S and Li_(2)Sn(3<n≤8),shows ingenious design,which not only accelerates the conversion reaction between the solid S species and dissolved S species,alleviating the shuttle effect,but also expedites the electron transport thus reducing the polarization of the electrode.In this review,the redox reaction process during Li-S chemistry are firstly highlighted.Recent developed catalysts,including transitionmetal oxides,chalcogenides,phosphides,nitrides,and carbides/borides are then outlined to better understand the role of catalyst additives during the polysulfide conversion.Finally,the critical issues,challenges,and perspectives are discussed to demonstrate the potential development of LSBs.
基金financially supported by National Natural Science Foundation of China(Nos.52164030 and 22179055)Natural Science Foundation of Jiangxi Province(Nos.20202ACBL204007 and 20224BAB204004)Program of Qingjiang Excellent Young Talents of Jiangxi University of Science and Technology(No.JXUSTQJYX2019010).
文摘Lithium-sulfur (Li-S) batteries are considered appealing power sources due to their high theoretical energy density (2600 Wh kg-1), low cost, and environmental friendliness. However, their widespread applicability is restricted by two scientific problems: sluggish sulfur reaction kinetics and severe polysulfide shuttle effects. Multifarious strategies have been developed to overcome these two obstacles and achieve high sulfur utilization and capacity retention. Among these strategies, the introduction of catalytic materials into the Li-S battery system can greatly accelerate sulfur conversion and effectively inhibit the polysulfide shuttle effects. Herein, we have comprehensively reviewed the recent progress of catalytic engineering for polysulfide conversion in high-performance lithium-sulfur batteries. First, various catalytic materials serve as sulfur hosts, functionalized separators, and electrolyte additives;the mechanisms by which these materials promote the conversion of polysulfides in Li-S batteries have been systematically summarized. The relationship of structure, preparation, property, advantages, and limitations of these catalytic materials are comprehensively presented. Subsequently, the advanced characterization techniques of these catalytic processes are discussed, shedding light on the fundamental understanding of catalytic effects for improved electrochemical performance. Furthermore, future design tactics for high-performance Li-S batteries are discussed.
基金supported by the National Natural Science Foundation of China(No.52172214,52472220)。
文摘Modulating the electronic structure has emerged as an effective strategy for optimizing the adsorption and catalytic capabilities of electrocatalysts in lithium-sulfur(Li-S)batteries.However,the regulation of electronic structure involving spin-related charge transfer and orbital interactions has been largely underexplored in sulfur electrocatalysts.Herein,selenium-deficient bimetallic selenides embedded in a coaxial carbon layer(CoSe_(2-x)/ZnSe)were meticulously fabricated as electrocatalysts,aiming to modulate the electron spin state of Co catalytic sites to enhance the bidirectional lithium polysulfides(LiPSs)conversion kinetics and suppress the LiPSs shuttling effect.Density functional theory(DFT)calculations and experimental results indicate that the selenium vacancies at the CoSe_(2-x)/ZnSe heterointerfaces weaken the ligand fields and drive the Co 3d orbital electronic structure transition from low-spin to high-spin states.Such tailored spin state configuration generates more unpaired electrons and upshifts the dband center,thus accelerating the charge transfer and strengthening the orbital interactions between LiPSs and Co catalytic sites.As a consequence,the assembled Li-S batteries with CoSe_(2-x)/ZnSe electrocatalysts exhibit an ultralow average decay rate of 0.028%per cycle at 1 C over 1000 cycles.This work presents a novel strategy for manipulating ligand fields to realize electron spin state modulation in sulfur electrocatalysts.
基金supported by Singapore Ministry of Education Tier 2 Grant(No.MOE-T2EP10223-0006)Tier 1 Grant(No.RG91/23).
文摘The growing demand for efficient and sustainable energy storage technologies has spurred significant research into alternatives to traditional lithium-ion batteries.Benefiting from the high energy density and abundant,environmentally friendly properties of sulfur,metal−sulfur(M-S)batteries represent some of the most promising candidates for nextgeneration energy storage.1,2 Among them,lithium−sulfur(Li−S)and sodium−sulfur(Na−S)batteries have garnered attention due to their potential to surpass the performance of current energy storage technologies in terms of both energy capacity and cost-effectiveness,making them particularly attractive for applications in electric vehicles(EVs),gridscale energy storage,and portable electronics,where high energy density is a crucial factor.
基金supported by the National Natural Science Foundation of China(Grant No.52372281)the Fundamental Research Funds for the Central Universities(2232020G-07)+3 种基金the foundation of Shanghai Institute of Technology(grant no.YJ2022-37)the Graduate Student Innovation Fund of Donghua University(CUSF-DH-D-2022007)the State Key Laboratory of Advanced Fiber Materials(KF2517)the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning。
文摘Lithium-sulfur(Li-S)batteries promise high energy density but suffer from low conductivity,polysulfide shuttling,and sluggish conversion kinetics.The construction of heterointerfaces is an effective strategy for enhancing both polysulfide adsorption and conversion;however,the poor lattice compatibility in the heterointerface formed by different materials hinders interfacial charge transfer.In response to these challenges,herein,a biphasic homojunction of TiO_(2)enriched with oxygen vacancies and decorated with nitrogen-doped carbon nanotubes(B-TiO_(2-x)@NCNT)was designed to simultaneously enhance adsorption ability and catalytic activity.This homojunction interface composed of rutile(110)and anatase(101)plane exhibits excellent compatibility,and density functional theory(DFT)calculations reveal that this biphasic interface possesses a much higher binding energy to polysulfides compared to single-phase TiO_(2).Additionally,NCNTs are in situ grown on both interior and exterior surfaces of the hollow TiO_(2)nanospheres,facilitating rapid electron transfer for the encapsulated sulfur.The homojunction interface synergistically leverages the oxygen vacancies and highly conductive NCNTs to enhance the bidirectional catalytic activity for polysulfide conversion.Therefore,in this multifunctional sulfur-host,polysulfides are first strongly adsorbed at the homojunction interfaces and subsequently undergo smooth conversion,nucleation,and decomposition,completing a rapid sulfur redox cycle.The assembled Li-S battery delivered a high specific capacity of 1234.3 mAh g^(-1)at 0.2 C,long cycling stability for over 1000 cycles at 5 C with a low decay rate of 0.035%,and exciting areal capacity at a high sulfur loading of 5.6 mg cm^(-2)for 200cycles.
基金This work was supported in part by the National Natural Science Foundation of China(Nos.22109119,51972238 and U21A2081)the Natural Science Foundation of Zhejiang Province(Nos.LQ19B030006 and LQ22B030003)the Major Scientific and Technological Innovation Project of Wenzhou City(No.ZG2021013).
文摘To tackle undesirable shuttle reaction and sluggish reaction kinetics in lithium–sulfur(Li–S)batteries,we develop a porous and high-density oxygen-doped tantalum nitride nanostructure(nano-TaNO)as an efficient catalyst through delicate tailoring.Benefiting from well-defined interior and surface nanopore channels,the nano-TaNO favors abundant sulfur storage,easy electrolyte infiltration and good electrons/Li+transport.More importantly,high-density O dopant in nano-TaNO not only provides high conductivity,but also promotes polysulfide adsorption/conversion via Li–O chemical interactions and the generation of S3∗−radicals to activate additional evolution path from S8 to Li_(2)S.Consequently,the nano-TaNObased cathode exhibits excellent specific capacity and cyclability even under high sulfur loading condition.These interesting findings suggest the great potential of tantalum nitride and a high amount of anion doping engineering in manipulating intermediates and building high-performance Li−S rechargeable batteries.
基金supported by Natural Science Foundation of Hebei Province of China(Nos.B2021202028,B2020202052,B2019202277)Outstanding Youth Project of Guangdong Natural Science Foundation(No.2021B1515020051)+9 种基金State Key Laboratory of Reliability and Intelligence of Electrical Equipment(No.EERI_PI2020007)Hebei University of Technology,Chinathe Program for the Outstanding Young Talents of Hebei Province,China(YG.Z.)Chunhui Project of Ministry of Education of the People’s Republic of China(No.Z2017010)Department of Science and Technology of Guangdong Province(Nos.2020B0909030004,2019JC01L203)Guangdong Innovative and Entrepreneurial Team Program(No.2016ZT06C517)Science and Technology Program of Guangzhou(No.2019050001)Science and Technology Program of Zhaoqing(No.2019K038)project AP09259764“Engineering of Multifunctional Materials of Next Generation Batteries”from the Ministry of Education and Science of Kazakhstana research project FDCRP No.110119FD4504“Development of 3D solid state thin film materials for durable and safe Li-ion microbatteries”from Nazarbayev University。
文摘Extensive research has been devoted to lithium-sulfur(Li-S)batteries due to their overwhelming promises and advantages such as high theoretical capacity(1675 m Ah g^(-1)),extremely cost effectiveness and abundance and availability of sulfur.Nevertheless,a sluggish electrochemical kinetics of the battery limited by a slow conversion of lithium polysulfide(LiPSs)intermediates and Li PSs shuttle effect severely hinder its development towards industrial application.Herein,we designed the oxidized Nb2_(C)MXene with amorphous carbon(Nb_(2)O_(5)/C)composites as sulfur host using CO_(2)treatment to address the above issues.The Nb_(2)O_(5)/C composites with high conductivity are directly employed as sulfur hosts for Li-S battery capable to remarkably mitigate the shuttle phenomenon due to a combined effect of their Li PSs trapping ability and catalytic activity towards their accelerated conversion.Meanwhile,the unique layered structure of the composite facilitates ion transfer and accommodates the volume changes of the cathode during cycling.With this rational design,the resultant Li-S batteries exhibit superior electrochemical performance with a high initial specific capacity of 745 m Ah g^(-1)at 1.0 C and a reversible capacity of 620 m Ah g^(-1)at a high rate cycling at 3.0 C.
基金supported by the National Natural Science Foundation of China(Grant No.51902265,No.21905059,and No.22279103)the National Key Research and Development Program(2022YFE0121000)+2 种基金the Fundamental Research Funds for the Central Universities,the fellowship of the China Postdoctoral Science Foundation(2022M722596)the key research and development project of Shaanxi Province(2023-YBGY-302)the Innovation Foundation for Doctor Dissertation of Northwestern Polytechnical University(No.CX2021122).
文摘Thanks to the significantly higher energy density compared with universal commercialized Li-ion batteries,lithium–sulfur(Li–S)batteries are being investigated for use in prospective energy storage devices.However,the inadequate electrochemical kinetics of reactants and intermediates hinder commercial utilization.This limitation results in substantial capacity degradation and short battery lifespans,thereby impeding the battery's power export.Meanwhile,the capacity attenuation induced by the undesirable shuttle effect further hinders their industrialization.Considerable effort has been invested in developing electrocatalysts to fix lithium polysulfides and boost their conversion effectively.In the conventional process,the planar electrodes are prepared by slurry-casting,which limits the electron and ion transfer paths,especially when the thickness of the electrodes is relatively large.Compared with traditional manufacturing methods,direct ink writing(DIW)technology offers unique advantages in both geometry shaping and rapid prototyping,and even complex three-dimensional structures with high sulfur loading.Hence,this review presents a detailed description of the current developments in terms of Li–S batteries in DIW of metal-based electrocatalysts.A thorough exploration of the behavior chemistry of electrocatalysis is provided,and the adhibition of metal-based catalysts used for Li–S batteries is summarized from the aspect of material usage and performance enhancement.Then,the working principle of DIW technology and the requirements of used inks are presented,with a detailed focus on the latest advancements in DIW of metal-based catalysts in Li–S battery systems.Their challenges and prospects are discussed to guide their future development.
基金supported by National Natural Science Foundation of China(Nos.52472194,52101243)Natural Science Foundation of Guangdong Province,China(No.2023A1515012619)the Science and Technology Planning Project of Guangzhou(No.202201010565).
文摘Lithium-sulfur batteries(LSBs)are considered as the most promising energy storage technologies owing to their large theoretical energy density(2500Wh/kg)and specific capacity(1675 mAh/g).However,the heavy shuttle effect of polysulfides and the growth of lithium dendrites greatly hinder their further development and commercial application.In this paper,cobalt-molybdenum bimetallic carbides heterostructure(Co_(6)Mo_(6)C_(2)@Co@NC)was successfully prepared through chemical etching procedure of ZIF-67 precursor with sodium molybdate and the subsequent high temperature annealing process.The obtained dodecahedral Co_(6)Mo_(6)C_(2)@Co@NC with hollow and porous structure provides large specific surface area and plentiful active sites,which speeds up the chemisorption and catalytic conversion of polysulfides,thus mitigating the shuttle effect of polysulfides and the generation of lithium dendrites.When applied as the LSBs separator modifier layer,the cell with modified separator present excellent rate capability and durable cycling stability.In particular,the cell with Co_(6)Mo_(6)C_(2)@Co@NC/PP separator can maintain the high capacity of 738 mAh/g at the current density of 2 C and the specific capacity of 782.6 mAh/g after 300 cycles at 0.5 C,with the coulombic efficiency(CE)near to 100%.Moreover,the Co_(6)Mo_(6)C_(2)@Co@NC/PP battery exhibits the impressive capacity of 431 mAh/g in high sulfur loading(4.096 mg/cm^(2))at 0.5 C after 200 cycles.This work paves the way for the development of bimetallic carbides heterostructure multifunctional catalysts for durable Li-S battery applications and reveals the synergistic regulation of polysulfides and lithium dendrites through the optimization of the structure and composition.
基金the financial support provided by the National Natural Science Foundation of China (51932005, 22072164)the Liaoning Revitalization Talents Program (XLYC1807175)+3 种基金the Research Fund of Shenyang National Laboratory for Materials Sciencethe IMR Innovation Fund (2023PY10)the Natural Science Foundation of Liaoning Province (2023-BS-013)the Science and Technology Research Project of Education Department of Jilin Province (JJKH20210453KJ)。
文摘The shuttle effect derived from diffusion of lithium polysulfides(LiPSs) and sluggish redox kinetic bring about poor cycling stability and low utilization of sulfur,which have always been the key challenging issues for the commercial application of lithium-sulfur(Li-S) batteries.Rational design of cathode materials to catalyze Li_(2)S dissociation/nucleation processes is an appealing and valid strategy to develop high-energy practical Li-S batteries.Herein,considering the synergistic effect of bidirectional catalysis on LiPSs conversion and enhanced chemical immobilization for LiPSs by heteroatom doping,Pt nanoparticles loaded on nitrogen-doped carbon spheres(Pt/NCS composites) were constructed as cathode materials.According to the dynamic evolution of Pt catalysts and sulfur species,Pt~0 and Pt^(2+) species were identified as active species for the accelerated dissociation and nucleation of Li_(2)S,respectively.Meanwhile,in-situ Raman results demonstrated the expedited conversion of sulfur species resulted from bidirectional catalysis of active Pt species,corresponding to boosted redox kinetics.Consequently,Pt/NCS cathode exhibited improved long-term cyclability with high initial capacity,along with enhanced rate capability.This work provides a facile approach to construct cathode materials with bidirectional catalysis on Li_(2)S dissociation/nucleation,and sheds light on a more global understanding of the catalytic mechanism of metal catalysts during LiPSs conversion.
基金Financial supports from the National Natural Science Foundation of China(21935006 and 22008102)are gratefully acknowledged.
文摘The exploration of new catalytic hosts is highly important to tackle the sluggish electrochemical kinetics of sulfur redox for achieving high energy density of lithium–sulfur batteries.Herein,for the first time,we present high-entropy oxide(HEO,(Mg_(0.2)Mn_(0.2)Ni_(0.2)Co_(0.2)Zn_(0.2))Fe_(2)O_(4))nanofibers as catalytic host of sulfur.The HEO nanofibers show a synergistic effect among multiple metal cations in spinel structure that enables strong chemical confinement of soluble polysulfides and fast kinetics for polysulfide conversion.Consequently,the S/HEO composite displays the high gravimetric capacity of 1368.7 mAh g^(−1) at 0.1 C rate,excellent rate capability with the discharge capacity of 632.1 mAh g^(−1) at 5 C rate,and desirable cycle stability.Furthermore,the S/HEO composite shows desirable sulfur utilization and good cycle stability under a harsh operating condition of high sulfur loading(4.6 mg cm^(−2))or low electrolyte/sulfur ratio(5μL mg^(−1)).More impressively,the high volumetric capacity of 2627.9 mAh cm^(−3) is achieved simultaneously for the S/HEO composite due to the high tap density of 1.92 g cm^(−3),nearly 2.5 times of the conventional sulfur/carbon composite.Therefore,based on high-entropy oxide materials,this work affords a fresh concept of elevating the gravimetric/volumetric capacities of sulfur cathodes for lithium–sulfur batteries.
基金The authors acknowledge funding from National Natural Science Foundation of China(No.51861165101).
文摘Lithium-sulfur(Li-S)batteries are promising candidates for next-generation energy storage systems owing to their high energy density and low cost.However,critical challenges including severe shuttling of lithium polysulfides(LiPSs)and sluggish redox kinetics limit the practical application of Li-S batteries.Carbon nitrides(C_(x)N_(y)),represented by graphitic carbon nitride(g-C_(3)N_(4)),provide new opportunities for overcoming these challenges.With a graphene-like structure and high pyridinic-N content,g-C_(3)N_(4) can effectively immobilize LiPSs and enhance the redox kinetics of S species.In addition,its structure and properties including electronic conductivity and catalytic activity can be regulated by simple methods that facilitate its application in Li-S batteries.Here,the recent progress of applying C_(x)N_(y)-based materials including the optimized g-C_(3)N_(4),g-C_(3)N_(4)-based composites,and other novel C_(x)N_(y) materials is systematically reviewed in Li-S batteries,with a focus on the structure-activity relationship.The limitations of existing C_(x)N_(y)-based materials are identified,and the perspectives on the rational design of advanced C_(x)N_(y)-based materials are provided for high-performance Li-S batteries.
基金supported by the National Key Research and Development Program of China(No.2020YFB1713500)the Student Research Training Plan of Henan University of Science and Technology(No.2020026)the National Undergraduate Innovation and Entrepreneurship Training Program(Nos.202010464031,202110464005)。
文摘Lithium–sulfur(Li-S)batteries are regarded as one of the most promising energy storage devices because of their low cost,high energy density,and environmental friendliness.However,Li-S batteries suffer from sluggish reaction kinetics and serious“shuttle effect”of lithium polysulfides(LiPSs),which causes rapid decay of battery capacity and prevent their practical application.To address these problems,introducing single-atom catalysts(SACs)is an effective method to improve the electrochemical performance of Li-S batteries,due to their high catalytic efficiency and definite active sites for LiPSs.In this paper,we summarized the latest developments in enhancing the electrochemical performance of cathode for Li-S batteries through introducing different SACs.Furthermore,we briefly introduced the catalytic mechanism of SACs and discussed the strategies of synthesizing SACs,including the spatial confinement strategy and the coordination design strategy.Finally,the challenges and prospects in this field are proposed.We believe that this review would help to design and fabricate high-performance Li-S batteries via introducing SACs and boost their practical application.
基金financially Australian Research Council (DE210101157 and FT190100058)。
文摘Lithium-sulfur(Li-S) batteries are promising for high energy-storage applications but suffer from sluggish conversion reaction kinetics and substantial lithium sulfide(Li_(2)S) oxidation barrier,especially under high sulfur loadings.Here,we report a Li cation-doped tungsten oxide(Li_(x)WO_(x)) electrocatalyst that efficiently accelerates the S■HLi_(2)S interconversion kinetics.The incorporation of Li dopants into WO_(x) cationic vacancies enables bidirectional electrocatalytic activity for both polysulfide reduction and Li_(2)S oxidation,along with enhanced Li^(+) diffusion.In conjunction with theoretical calculations,it is discovered that the improved electrocatalytic activity originates from the Li dopant-induced geometric and electronic structural optimization of the Li_(x)WO_(x),which promotes the anchoring of sulfur species at favourable adsorption sites while facilitating the charge transfer kinetics.Consequently,Li-S cells with the Li_(x)WO_(x) bidirectional electrocatalyst show stable cycling performance and high sulfur utilization under high sulfur loadings.Our approach provides insights into cation engineering as an effective electrocatalyst design strategy for advancing high-performance Li-S batteries.
基金supported by the National Natural Science Foundation of China(Nos.NSFC 51772060,51672059,and 51621091)the Heilongjiang Touyan Team Program,and the Fundamental Research Funds for the Central Universities(Grant No.HIT.OCEF.2021003)。
文摘Designing electrochemical catalysts has become a research hotspot due to their accelerating the polysulfide conversion of the sulfur cathode to inhibit the“shuttle effect”in lithium-sulfur batteries.However,it is still a great challenge to design the heterogeneous selective electrochemical catalyst for inhibiting the“shuttle effect”.Herein,nickel cobalt phosphide and cobalt phosphide as the heterogeneous catalyst active sites embedded in the nitrogen-doped hollow carbon nanocages(NiCoP@CoP/NC)are reported,used for multi-step and multi-phase sulfur electrode reaction,and it is found that metal-sulfur d-p hybridization can effectively indicate the intrinsic catalytic activity of metal site.Division of labor and cooperation of the bi-active NiCoP@CoP as heterogeneous catalysts propel the stepwise polysulfide conversion.NiCoP and CoP sites preferentially accelerate the long-chain polysulfide conversion reaction(S_(8)■LiPSs)and the short-chain polysulfide conversion reactions(LiPSs■Li_(2)S),respectively.Moreover,the hollow and porous N-doped carbon structure can successfully suppress the volume effect and improve the conductivity of the sulfur cathode.The unique design can obtain an effective inhibition of the shuttle effect and rapid electrode reaction.As a result,Li-S batteries demonstrate a high initial capacity of 1063 mAh g^(-1) and a low-capacity decay of 0.04% per cycle within 1000 cycles.Our work provides a feasible idea for the design of host materials in Li-S batteries.
基金supported by the National Natural Science Foundation of China(Grant Nos.51772060,51672059,52372041,52302087,51621091)Heilongjiang Touyan Team Program,and the Fundamental Research Funds for the Central Universities(Grant No.HIT.OCEF.2021003).
文摘Heterostructure engineering for sulfur hosts is an effective way to achieve interfacial synergistic effects on suppressing the“shuttle effect”of polysulfides and thus improve electrochemical performance of lithium–sulfur(Li–S)batteries.Rational selection and design of different components into heterostructures is vital to enhance the synergistic effect.Herein,MoS_(2)/MoP Mott–Schottky heterostructure nanoparticles decorated on reduced graphene oxide(MoS_(2)/MoP@rGO)are fabricated and used as sulfur host firstly.Theoretical calculation and experiment results reveal that the in-situ introduction of MoP could tune the electronic structure,activate the basal plane of MoS_(2),and achieve the interfacial synergistic effects between adsorption(MoS_(2))and fast conversion(MoP).Such synergistic effects enable MoS_(2)/MoP@rGO to not only remarkably facilitate Li_(2)S deposition during the discharging process but also significantly accelerate the Li_(2)S dissolution during the charging process,demonstrating bidirectional promotion behaviors.Thus,the designed cathode delivers initial capacity of 919.5 mA·h·g^(−1)with capacity of 502.3 mA·h·g^(−1)remaining after 700 cycles at 0.5 C.Even under higher sulfur loading of 4.31 mg·cm^(−2)and lower electrolyte to sulfur(E/S)ratio of 8.21μL·mg^(−1),the MoS_(2)/MoP@rGO@S cathode could still achieve good capacity and cycle stability.This work provides a novel and efficient structural design strategy of sulfur hosts for high-performance Li–S energy storage systems.
基金support from University of Waterloo,Waterloo Institute for Nanotechnology,and Natural Sciences and Engineering Research Council of Canada(NSERC).This work was also supported by the Outstanding Youth Project of Guangdong Natural Science Foundation(2021B1515020051)Department of Science and Technology of Guangdong Province(2019JC01L203 and 2020B0909030004)+1 种基金the Natural Science Foundation of Ningxia(2023AAC01003)the Foundation of State Key Laboratory of High Efficiency Utilization of Coal and Green Chemical Engineering(2022-K79).
文摘Resolving low sulfur reaction activity and severe polysulfide dissolution remains challenging in metalsulfur batteries.Motivated by a theoretical prediction,herein,we strategically propose nitrogenvacancy tantalum nitride(Ta3N5-x)impregnated inside the interconnected nanopores of nitrogendecorated carbon matrix as a new electrocatalyst for regulating sulfur redox reactions in roomtemperature sodium-sulfur batteries.Through a pore-constriction mechanism,the nitrogen vacancies are controllably constructed during the nucleation of Ta3N5-x.The defect manipulation on the local environment enables well-regulated Ta 5d-orbital energy level,not only modulating band structure toward enhanced intrinsic conductivity of Ta-based materials,but also promoting polysulfide stabilization and achieving bifunctional catalytic capability toward completely reversible polysulfide conversion.Moreover,the interconnected continuous Ta3N5-x-in-pore structure facilitates electron and sodium-ion transport and accommodates volume expansion of sulfur species while suppressing their shuttle behavior.Due to these attributes,the as-developed Ta3N5-x-based electrode achieves superior rate capability of 730 mAh g-1 at 3.35 A g-1,long-term cycling stability over 2000 cycles,and high areal capacity over 6 mAh cm-2 under high sulfur loading of 6.2 mg cm-2.This work not only presents a new sulfur electrocatalyst candidate for metal-sulfur batteries,but also sheds light on the controllable material design of defect structure in hopes of inspiring new ideas and directions for future research.
基金support from the National Natural Science Foundation of China(No.22379001)the Natural Science Research Project of Anhui Province Education Department(No.2022AH030046)+2 种基金the Open Fund from the State Key Laboratory of Coordination Chemistry(SKLCC2502)the Project of High-End Talent Introduction and Cultivation of Anhui Provincethe Project of Top Young Talents of Anhui University of Technology.
文摘Lithium-sulfur(Li-S)batteries have gained significant success as next-generation energy sources,but the slow conversion speed of polysulfides and resultant notorious shuttle effect still limit its practical utilization.Metal nitrides(MNs)with high chemical affinity and remarkable catalytic activity have been verified as highly-efficient electrocatalysts in addressing these remaining challenges.However,there is a lack of comprehensive review that clarifying the detailed working principles of MNs in Li-S batteries.This study first summarizes the recent advances in the utilization of MNs for Li-S batteries,especially in sulfur hosts,separator coating layers,and interlayers.Typical MNs in each category were then introduced,by analyzing their material designs,catalytic effects,and modulation strategies.Important perspectives on the future developments of MN-based electrocatalysts and Li-S batteries are given,possible challenges and potential research directions are outlined.This work supplies precious insights into the use of MNs and their key roles in promoting the conversions of sulfur species.
基金the National Key R&D Program of China(No.2018YFA0702003)the National Natural Science Foundation of China(Nos.21890383,21671117,21871159)+1 种基金the China Postdoctoral Science Foundation(No.2019M660607)Z.C.Z.acknowledges support from the Shuimu Isinghua Scholar Program.
文摘With high energy density and low material cost,lithium sulfur batteries(LSBs)emerge quite expeditiously as a fascinating energy storage system over the past decade.Broad applications of LSBs ranging from electric vehicles to stationary grid storage seem rather bright in recent literatures.However,there still exist many pressing challenges to be addressed because we do not yet fully understand and control the electrode-electrolyte interface chemistries during battery operation,such as polysulide shuttling and poor utilization of active sulfur.Single-atom catalysts(SACs)pave new possibilities of tackling the tough issues due to their decent applicability in the atomic-level identification of structure-activity relationships and reaction mechanism,as well as their structural tunability with atomic precision.This review comprehensively summarizes the very recent advances in utilization of highly active SACs for LSBs by stating and discussing the related publications,which involves catalyst synthesis routes,battery pertormance,catalytic mechanisms,optimization strategies,and promises to achieve long-lite,high-energy LSBs.We see that endeavors to employ SACs to modify sulfur cathode have allowed efficient polysulfide conversion and confinement,leading to the minimization of shuttle effect.Parallel efforts are being devoted to extending the scope of SACs to cell separator and lithium metal anode in order to unlock the full potential of LSBs.We also obtain mechanistic insights into battery chemistries and nature of SACs in their strong interactions with polysulfides through advanced in situ characterizations documented.Overall,acceleration in the development of LSBs by introducing SACs is noticeable,and this cutting edge needs more attentions to further promoting the design of better LSBs.
基金supported by the National Natural Science Foundation of China(51872336,51925308,and 52172061)the National Key Research and Development Program of China(2021YFF0500600)+3 种基金the Pearl River Talent Plan of Guangdong(2017GC010612)the Natural Science Foundation of Guangdong(2021A1515011617)the Fundamental Research Funds for the Central Universities(20lgzd18)the Science and Technology Program of Guangzhou(202102021111 and 202002020041)。
文摘开发具有多层次结构(包括多孔结构、杂化骨架和/或拓扑形貌)的超结构碳材料,对于满足电化学储能和转换系统中复杂催化反应的需求非常关键.在本文中,我们以钴纳米颗粒为催化位点,在杂化碳纳米管骨架表面可控接枝毛发状碳纳米管,开发了一类层次化多孔的钴修饰碳纳米管瓶刷(Co/CNTBs).其中,精确的瓶刷状拓扑形貌和分级多孔结构能够有效地提供可及表/界面和高导电网络,钴修饰的杂化骨架可以促进硫的氧化还原反应动力学.因此,基于Co/CNTBs功能化隔膜的锂硫电池具有优异的倍率性能(在10 C下比容量为707 mA h g^(-1))和长效的循环稳定性.更重要的是,基于Co/CNTBs催化剂的高硫载量电池(6.72 mg cm^(-2))在0.1 C下循环100圈后仍具有4.81 mA h cm^(-2)的高面积容量.本工作为高性能超结构杂化碳材料的原位接枝合成策略带来了新的思路,有望用于众多具有挑战性的应用.
