Despite their attractive features of high energy density,low cost,and safety,polysulfide/iodide flow batteries(SIFBs)are hampered by the sluggish kinetics of the iodide redox couple,which restricts overall performance...Despite their attractive features of high energy density,low cost,and safety,polysulfide/iodide flow batteries(SIFBs)are hampered by the sluggish kinetics of the iodide redox couple,which restricts overall performance.Multicomponent sulfides are demonstrated as promising catalysts for accelerating I^(-)/I_(3)^(-) redox reactions.Concurrently,the enhanced configurational entropy arising from multinary compositions drives synergistic effects among constituent elements,establishing a viable pathway to optimize catalytic performance.Building on these foundations,this work introduces a targeted orbital hybridization-optimized electron density strategy to enhance the catalytic activity.Implementing this concept,we developed an in-situ solvothermal synthesis process for an entropy-enhanced AgCuZnSnS_(4) loaded graphite felt(ACZTS/GF)electrode.The engineered electrode demonstrates exceptional electrocatalytic performance with improved bulk conductivity and interfacial charge transfer kinetics within a SIFB.The cell achieves a high energy efficiency of 88.5%at 20 mA·cm^(−2) with 10%state-of-charge.Furthermore,the battery delivers a maximum power density of 119.8 mW·cm^(−2) and exhibits excellent long-term cycling stability.These significant results stem from orbital hybridization-driven electronic state optimization and entropy effect-induced synergistic catalysis.展开更多
In lithium-sulfur batteries(LSBs),the limited utilization of sulfur and the sluggish kinetics of redox reaction significantly hinder their electrochemical performance,especially under high rates and high sulfur loadin...In lithium-sulfur batteries(LSBs),the limited utilization of sulfur and the sluggish kinetics of redox reaction significantly hinder their electrochemical performance,especially under high rates and high sulfur loadings.Here,we propose a novel separator structure with an interlayer composed of a vermiculite nanosheet combined with Ketjen Black(VMT@KB)for LSBs,facilitating efficient adsorption and rapid catalytic conversion toward lithium polysulfides(LiPSs).The VMT@KB nanosheets with an electrical double-layer structure and electronic conductivity are obtained through a high-temperature peeling process and Li^(+)exchange treatment in LiCl solution,followed by a mechanical combination process with KB.The results demonstrate that incorporating VMT@KB as an interlayer on a conventional separator enhances the conductivity and limits the LiPSs in the cathode region.The Li-S cell with VMT@KB interlayer shows satisfactory cycle and rate performance,especially in high sulfur loading.It exhibits a remarkable initial discharge capacity of 1225 mAh g^(-1)at 0.5 C and maintains a capacity of 816 mAh g^(-1)after 500 cycles.Besides,the discharge capacity remains 462 mAh g^(-1)even at 6 C.Moreover,the cell with high sulfur loading(8.2 mg cm^(-2))enables stable cycling for 100 cycles at 0.1 C with a discharge capacity of over1000 mAh g^(-1).展开更多
Owing to the advantages of high energy density,low cost,abundant sulfur reserves and environmentally friendly nature,lithium-sulfur batteries(LSBs)were considered as one of the potential candidates of energy storage d...Owing to the advantages of high energy density,low cost,abundant sulfur reserves and environmentally friendly nature,lithium-sulfur batteries(LSBs)were considered as one of the potential candidates of energy storage devices for the next generation.However,the significant challenges in this area stem from the sluggish reaction kinetics of the insoluble Li_(2)S product and the capacity degradation triggered by the severe shuttle effect of polysulfides.It has been firmly established through numerous studies that modifying separators is an effective approach to enhance the properties of LSBs by facilitating the catalytic kinetic conversion and chemical adsorption of lithium polysulfides(Li PSs).In this work,we report a straightforward method for fabrication of the phosphorus doped porous CeO_(2)(P-CeO_(2))as separator modifier to accelerate the catalytic kinetic conversion of polysulfides and effectively inhibit the shuttle effect in LSBs.Through coin batteries tests,P-CeO_(2)modified PP separator(P-CeO_(2)//PP)exhibits remarkable electrochemical performance.It demonstrates a high initial capacity of 1180 mAh/g at 0.5 C,surpassing the performance of the bare CeO_(2)//PP separator.Furthermore,the P-CeO_(2)//PP separator demonstrates enhanced cycling stability,with a low-capacity fading rate of only 0.048%per cycle over 1000 cycles at 2 C.In compared with bare CeO_(2)//PP,P-CeO_(2)//PP exhibits high redox peak current,enhanced adsorption property of Li_(2)S_(6)and early Li_(2)S precipitation.These results highlight the superior performance of the P-CeO_(2)//PP separator compared to the bare CeO_(2)//PP separator.Hence,this research presents a successful strategy for the modification of LIBs separator with improved electrochemical performance and cycle stability.展开更多
The intrinsic clustering behavior and kinetically sluggish conversion process of lithium polysulfides seriously limit the electrochemical reversibility of sulfur redox reactions in lithium-sulfur(Li-S)batteries.Here,w...The intrinsic clustering behavior and kinetically sluggish conversion process of lithium polysulfides seriously limit the electrochemical reversibility of sulfur redox reactions in lithium-sulfur(Li-S)batteries.Here,we introduce molybdenum pentachloride(MoCl_(5))into the electrolyte which could coordinate with lithium polysulfides and inhibit their intrinsic clustering behavior,subsequently serving as an improved mediator with the bi-functional catalytic effect for Li_(2)S deposition and activation.Moreover,the coordination bonding and accelerated conversion reaction can also greatly suppress the dissolution and shuttling of polysulfides.Consequently,such polysulfide complexes enable the Li-S coin cell to exhibit good longterm cycling stability with a capacity decay of 0.078%per cycle after 400 cycles at 2 C,and excellent rate performance with a discharge capacity of 589 mAh/g at 4 C.An area capacity of 3.94 mAh/cm^(2)is also achieved with a high sulfur loading of 4.5mg/cm^(2)at 0.2 C.Even at-20℃,the modified cell maintains standard discharge plateaus with low overpotential,delivering a high capacity of 741 mAh/g at 0.2 C after 80 cycles.The low-cost and convenient MoCl_(5)additive opens a new avenue for the effective regulation of polysulfides and significant enhancement in sulfur redox conversion.展开更多
Developing electrocatalysts to inhibit polysulfide shuttling and expedite sulfur species conversion is vital for the evolution of Lithium-sulfur(Li-S)batteries.This work provides a facile strategy to design an intimat...Developing electrocatalysts to inhibit polysulfide shuttling and expedite sulfur species conversion is vital for the evolution of Lithium-sulfur(Li-S)batteries.This work provides a facile strategy to design an intimate heterostructure of MIL-88A@CdS as a sulfur electrocatalyst combining high sulfur adsorption and accelerated polysulfide conversion.The MIL-88A can give a region of high-ordered polysulfide adsorption,whereas the CdS is an effective nanoreactor for the sulfur reduction reaction(SRR).Notedly,the significant size difference between MIL-88A and CdS enables the unique heterostructure interactions.The largesize MIL-88A ensures a uniform distribution of CdS nanoparticles as a substrate.This configuration facilitates control of the initial polysulfide adsorption position relative to its final deposition site as lithium sulfide.The heterostructure also demonstrates rapid transport and efficient conversion of lithium polysulfides.Consequently,the Li-S battery with MIL-88A@CdS heterostructure modified separator delivers exceptional performance,achieving an areal capacity exceeding 6 mAh cm^(−2),an excellent rate capability of 980 mAh g^(−1) at 5 C,and notable cycling stability in a 2 Ah pouch cell over 100 cycles.This work is significant for elucidating the relationship between heterostructure and electrocatalytic performance,providing great insights for material design aimed at highly efficient future electrocatalysts in practical applications.展开更多
Lithium-sulfur batteries are considered to be a new generation of high energy density batteries due to their non-toxicity,low cost and high theoretical specific capacity.However,the development of practical lithium-su...Lithium-sulfur batteries are considered to be a new generation of high energy density batteries due to their non-toxicity,low cost and high theoretical specific capacity.However,the development of practical lithium-sulfur batteries is seriously impeded by the sluggish multi-electron redox reaction of sulfur species and obstinate shuttle effect of polysulfides.In this study,a porous lanthanum oxychloride(LaOCl)nanofiber is designed as adsorbent and electrocatalyst of polysulfides to regulate the redox kinetics and suppress shuttling of sulfur species.Benefiting from the porous architecture and luxuriant active site of LaOCl nanofibers,the meliorative polarization effect and sulfur expansion can be accomplished.The LaOCl/S electrode exhibits an initial discharge specific capacity of 1112.3 mAh/g at 0.1 C and maintains a superior cycling performance with a slight decay of 0.02%per cycle over 1000 cycles at 1.0 C.Furthermore,even under a high sulfur loading of 4.6mg/cm^(2),the S cathode with LaOCl nanofibers still retains a high reversible areal capacity of 4.2 mAh/cm^(2)at 0.2 C and a stable cycling performance.Such a porous host expands the application of rare earth based catalysts in lithium-sulfur batteries and provides an alternative approach to facilitate the polysulfides conversion kinetics.展开更多
Shuttle effect of polysulfides overshadows the superiorities of lithium-sulfur batteries.Size-sieving effect could address this thorny trouble rely on size differ in polysulfides and lithium ions.However,clogged polys...Shuttle effect of polysulfides overshadows the superiorities of lithium-sulfur batteries.Size-sieving effect could address this thorny trouble rely on size differ in polysulfides and lithium ions.However,clogged polysulfides pose some challenges for cathode and are rarely recycled during charging/discharging.Herein,an amino functionalized titanium-organic framework is designed for modifying lithium-sulfur batteries separator to address the aforementioned challenges.Wherein,the introduction of amino narrows titanium-organic framework pore size,enabling functional separator to selectively modulate lithium ions and polysulfides migration using size-sieving effect,thereby completely suppressing polysulfides shuttle.Furthermore,the blocked polysulfides will be adsorbed on the separator surface by positively charged amino leveraging electrostatic adsorption,ensuring polysulfides to redistribute and reuse,and boosting active materials utilization.Significantly,the migration of lithium ions is not hindered since there are lithium ions transfer channels formed via Lewis acid-base interaction with the help of amino.Combined with these virtues,the lithium-sulfur batteries with amino functionalized titanium-organic framework modified separator enjoy an ultralow attenuation rate of 0.045%per cycle over 1000 cycles at 1.0C.Electrostatic adsorption and Lewis acid-base interaction cover deficiencies existing in the inhibition of polysulfides shuttle by size-sieving effect,providing fresh insight into the advancement of lithium-sulfur batteries.展开更多
Lithium-sulfur(Li-S)batteries with high energy density suffer from the soluble lithium polysulfide species,Traditional metal sulfides containing a single metal element used as electrocatalysts for Li-S batteries commo...Lithium-sulfur(Li-S)batteries with high energy density suffer from the soluble lithium polysulfide species,Traditional metal sulfides containing a single metal element used as electrocatalysts for Li-S batteries commonly have limited catalytic abilities to improve battery performance.Herein,based on the Hume-Rothery rule and solvothermal method,the high-entropy sulfide NiCoCuTiVS_(x)derived from Co_(9)S_(8)was designed and synthesized,to realize the combination of small local strain and excellent catalytic performance.With all five metal elements(Ni,Co,Cu,Ti,and V)capable of chemical interactions with soluble polysulfides,NiCoCuTiVS_(x)exhibited strong chemical confinement of polysulfides and promoted fast kinetics for polysulfides conversion.Consequently,the S/NiCoCuTiVS_(x)cathode can maintain a high discharge capacity of 968.9 mA h g^(-1)after 200 cycles at 0.5 C and its capacity retention is 1.3 times higher than that of S/Co_(9)S_(8).The improved cycle stability can be attributed to the synergistic effect originating from the multiple metal elements,coupled with the reduced nucleation and activation barriers of Li_(2)S.The present work opens a path to explore novel electrocatalyst materials based on high entropy materials for the achievement of advanced Li-S batteries.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
Metal phosphosulfides(MPS_(x)),especially BiPS_(4),have emerged as promising anode candidates for sodiumion batteries,distinguished by distinctive multinary redox chemistry,open tunnel-type structure,and high theoreti...Metal phosphosulfides(MPS_(x)),especially BiPS_(4),have emerged as promising anode candidates for sodiumion batteries,distinguished by distinctive multinary redox chemistry,open tunnel-type structure,and high theoretical capacity(>1000 m Ah g^(-1)).However,their practical implementation is fundamentally limited by polysulfide dissolution/shuttling and structural instability during prolonged cycling.Herein,we develop a groundbreaking two-stage metal-organic framework(MOF)-engineered compositing strategy through which Bi-MOF-derived BiPS_(4)/C pillars are robustly armored with conductive Ni-HHTP(HHTP=2,3,6,7,10,11-hexahydroxytriphenylene)nanorods.Density functional theory calculations reveal that this design achieves dual functionality:increased carrier density for enhanced charge transport dynamics and effective polysulfide adsorption to inhibit dissolution.The fabricated BiPS_(4)/C@Ni-HHTP composite delivers remarkable electrochemical properties,including high initial charge/discharge specific capacities of 1063.6/1181.3 mAh g^(-1)at 0.1 A g^(-1)and outstanding long-term stability with 99.2% capacity retention after 2000 cycles at 2 A g^(-1).Such superb performance stems from the perfect synergy of the inherent high-capacity redox behavior of BiPS_(4),the buffering effect of MOF-derived carbon,and the conductivity,adsorption sites and mechanical resilience of Ni-HHTP.This work establishes a new design paradigm for MPS_(x)materials,demonstrating how to simultaneously overcome conductivity limitations and shuttle effects in conversion-type electrodes.展开更多
The polysulfides shuttle effect,sluggish sulfur redox kinetics and the corrosion of the Li anode have become important factors limiting the commercial application of lithium-sulfur batteries(LSBs).Herein,the polyoxome...The polysulfides shuttle effect,sluggish sulfur redox kinetics and the corrosion of the Li anode have become important factors limiting the commercial application of lithium-sulfur batteries(LSBs).Herein,the polyoxometalate(POM)nanoclusters with high catalytic activity and cobalt selenide with strong polarity are initially complemented to construct a PMo_(12)/CoSe_(2)@NC/CNTs multifunctional separator that can simultaneously solve the above problems.A series of experimental and theoretical results demonstrate that the Keggin-type POM,H_(3)PMo_(12)O_(40)nH_(2)O(PMo_(12))nanoclusters could function as catalytic centers for sulfur-involved transformations,with the CoSe_(2)nanoparticles serving as adsorption sites for soluble polysulfides.Accordingly,the assembled battery with the PMo_(12)/CoSe_(2)@NC/CNTs modified separator achieves an initial discharge capacity of 1263.79 mA h g^(-1),maintaining 635.77 mA h g^(-1),with a capacity decay rate of 0.06%per cycle after 500 cycles at 3C.This work provides a strategic approach for incorporating POM nanoclusters with polar periodic nanomaterials in LSB separators,contributing to the development of multifunctional separator materials,thus promoting the advancement of energy storage systems.展开更多
Developing effective heterostructure strategies to mitigate the shuttling effect and accelerate lithium polysulfide(Li PS)conversion remains a critical challenge in lithium–sulfur(Li–S)batteries.Here,we report the f...Developing effective heterostructure strategies to mitigate the shuttling effect and accelerate lithium polysulfide(Li PS)conversion remains a critical challenge in lithium–sulfur(Li–S)batteries.Here,we report the first carbon–free VO_(2)–VS_(2)heterostructure material synthesized via in situ sulfurization,applied as a modifier on a commercial polypropylene(PP)separator(denoted as VO_(2)–VS_(2)@PP).The as–prepared VO_(2)–VS_(2)nanorods synergistically combine the high absorptivity of VO_(2)with the efficient catalytic properties of VS_(2),simultaneously enhancing Li PS anchoring and promoting its conversion.We systematically investigate the influence of material composition on battery performance,leveraging these functional attributes,Li–S cells incorporating VO_(2)–VS_(2)@PP exhibit exceptional cycle stability(over 500cycles at 1C),impressive rate performance(807 m Ah.g^(–1)at 5C),desirable reversibility(49.9%capacity retention after 300 cycles at 5C)and exceptional pouch cell performance(3.65 m Ah.cm^(–2)after 50 stable cycles at 0.1C).This study underscores the potential of tailored heterostructures in realizing high–performance Li–S batteries,offering new insights for next–generation energy storage solutions.展开更多
Solid-state polymer sodium batteries(SPSBs)are promising candidates for achieving higher energy density and safe energy storage.However,interface issues between oxide cathode and solid-state polymer electrolyte are a ...Solid-state polymer sodium batteries(SPSBs)are promising candidates for achieving higher energy density and safe energy storage.However,interface issues between oxide cathode and solid-state polymer electrolyte are a great challenge for their commercial application.In contrast,soft sulfur-based materials feature better interface contact and chemical compatibility.Herein,an interfacial compatible polysulfide Ti_(4)P_(8)S_(29) with robust Ti-S bonding and a highly active P-S unit is tailored as a high-performance cathode for SPSBs.The Ti_(4)P_(8)S_(29) cathode possesses a three-dimensional channel structure for offering ample Na+diffusion pathways.The assembled poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)-based SPSBs deliver a discharge capacity of 136 mAh·g^(-1)at 0.5C after 200 cycles.Furthermore,a discharge capacity of 88 mAh·g^(-1)is retained after 600 cycles at a high rate of 2C,surpassing many cathode materials in SPSBs.A dual-site redox of Ti^(4+)/Ti^(3+)and S^(-)/S^(2-)is verified by X-ray photoelectron spectroscopy(XPS)and cyclic voltammetry(CV)tests.Interestingly,a refined locally-ordered amorphous structure is unveiled by in situ and ex situ characterizations.The as-formed electrode structure with lots of open channels and isotropic properties are more beneficial for ion diffusion on the interface of electrode and solid-state polymer electrolytes(SPEs),leading to faster Na+diffusion kinetics.This work proposes a strategy of modulating open-channel to boost conversion kinetics in polysulfide cathode and opens a new pathway for designing high-performance SPSBs.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
Aim Cysteine proteases are closely associated with many human and non-human pathological processes and are potential targets for metal ions especially Hg^2＋ and the related species. In the present work, on the basis ...Aim Cysteine proteases are closely associated with many human and non-human pathological processes and are potential targets for metal ions especially Hg^2＋ and the related species. In the present work, on the basis of to the general study on the effects of some metal ions on the activity of papain, a well-known representative of cysteine protease family, the inhibitory effects of Hg^2＋ and polysulfide complexes were studied. Results All the metal ions tested （Hg^2＋, Cu^2＋, Ag^＋, Au^3＋, Zn^2＋, Cd^2＋, Fe^3＋, Mn^2＋, Pb^2＋, Yb^3＋） inhibit the activity of papain anda good correlation between the inhibitory potency and softness-and-hardness was observed. Among the metals, Hg^2＋ was shown to be a potent inhibitor of papain with a Kiof 2 × 10^-7 mol·L^-1 among. Excessive amounts of glutathione and cysteine could reactivate the enzyme activity of papain deactivated by Hg^2＋. These evidences supported that Hg^2＋ might bind to the catalytic site of papain. Interestingly, Hg （Ⅱ） polysulfide complexes were for the first time found to inhibit papain with a Ki of 7 × 10^-6 mol·L^-1, whose potency is close to a well known mercury compound, thimerosal （Ki=2.7 × 10^-6）. In addition, Hg （Ⅱ） polysulfide complexes exhibit good permeability （ 1.9 × 10-5 cm· s^-1） to caco-2 monolayer. Conclusion These results suggested that mercury polysulfide complexes might be potential bioactive species in the interaction with cysteine proteases and other- SH-content proteins, providing a new clue to understand the mechanism of the toxicological and pharmacological actions of cinnabar and other insoluble mercury compounds.展开更多
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
The practical application of Li-S batteries is largely impeded by the“shuttle effect”generated at the cathode which results in a short life cycle of the battery.To address this issue,this work discloses a bimetallic...The practical application of Li-S batteries is largely impeded by the“shuttle effect”generated at the cathode which results in a short life cycle of the battery.To address this issue,this work discloses a bimetallic metal-organic framework(MOF)as a sulfur host material based on Al-MOF,commonly called(Al)MIL-53.To obtain a high-adsorption capacity to lithium polysulfides(Li_(2)S_(x),4≤x≤8),we present an effective strategy to incorporate sulfiphilic metal ion(Cu^(2+))with high-binding energy to Li_(2)S_(x)into the framework.Through a one-step hydrothermal method,Cu^(2+)is homogeneously dispersed in Al-MOF,producing a bimetallic Al/Cu-MOF as advanced cathode material.The macroscopic Li2S4 solution permeation test indicates that the Al/Cu-MOF has better adsorption capacity to lithium polysulfides than monometallic Al-MOF.The sulfur-transfusing process is executed via a melt-diffusion method to obtain the sulfur-containing Al/CuMOF(Al/Cu-MOF-S).The assembled Li-S batteries with Al/Cu-MOF-S yield improved cyclic performance,much better than that of monometallic AlMOF as sulfur host.It is shown that chemical immobilization is an effective method for polysulfide adsorption than physical confinement and the bimetallic Al/Cu-MOF,formed by incorporation of sulfiphilic Cu^(2+)into porous MOF,will provide a novel and powerful approach for efficient sulfur host materials.展开更多
The slow redox dynamics and dissolution of polysulfides in lithium-sulfur(Li-S)batteries result in poor rate performance and rapid decay of battery capacity,thus limiting their practical application.Ferroelectric bari...The slow redox dynamics and dissolution of polysulfides in lithium-sulfur(Li-S)batteries result in poor rate performance and rapid decay of battery capacity,thus limiting their practical application.Ferroelectric barium titanate(BT)nanoparticles have been reported to effectively improve the electrochemical performance of Li-S batteries due to the inherent self-polarization and high adsorption capacity of the BT nanoparticles towards polysulfides.Here in this paper,BT nanoparticles,behave as highly efficient electrocatalyst and demonstrate much higher redox dynamics towards the conversion reaction of polysulfides and Li2S than TiO2,as shown by both electrochemical measurements and density functional theory calculation.The coupling of the sulfur host of the hollow and graphitic carbon flakes(HGCF)and the BT nanoparticles(HGCF/S-BT)enable excellent electrochemical performance of Li-S batteries,delivering a0.047%capacity decay per cycle in 1000 cycles at 1 C,788 mAh g^-1 at 2 C and a reversible capacity of613 mAh g^-1 after 300 cycles at a current density of 0.5 C at a S loading of 3.4 mg cm^-2.HGCF/S-BT also shows great promise for practical application in flexible devices as demonstrated on the soft-packaged Li-S batteries.展开更多
As polar materials, transition-metal oxides have shown great potentials to improve the adsorption of lithium polysulfides in lithium-sulfur batteries. Herein, a MoO_2-ordered mesoporous carbon (M-OMC)hybrid was design...As polar materials, transition-metal oxides have shown great potentials to improve the adsorption of lithium polysulfides in lithium-sulfur batteries. Herein, a MoO_2-ordered mesoporous carbon (M-OMC)hybrid was designed as the sulfur host, in which MoO_2 is inlaid on the surface of ordered mesoporous carbons that can store active materials and provide fast electron transfer channel due to its ordered pore structure. The MoO_2 can effectively prevent the migration of polysulfides through the chemical adsorption and promote the conversion of polysulfides towards Li-sulfur battery.展开更多
Inhibiting the “shuttle effect” of soluble polysulfides and improving reaction kinetics are the key factors necessary for further exploration of high-performance Li-S batteries. Herein, an effective interface engine...Inhibiting the “shuttle effect” of soluble polysulfides and improving reaction kinetics are the key factors necessary for further exploration of high-performance Li-S batteries. Herein, an effective interface engineering strategy is reported, wherein nitriding of an Ni-based precursor is controlled to enhance Li-S cell regulation. The resulting in-situ formed NiO-Ni_(3)N heterostructure interface not only has a stronger polysulfide adsorption effect than that of monomeric NiO or Ni_(3)N but also has a faster Li ion diffusion ability than a simple physical mixture. More importantly, this approach couples the respective advantages of NiO and Ni_(3)N to reduce polarization and facilitate electron transfer during polysulfide reactions and synergistically catalyze polysulfide conversion. In addition, ultrafine nanoparticles are thought to effectively improve the use of additive materials. In summary, Li-S batteries based on this NiO-Ni_(3)N heterostructure have the features of long cycle stability, rapid charging-discharging, and good performance under high sulfur loading.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22171180,22461142137,and 22478242)the Shanghai Municipal Science and Technology Major Project,China.
文摘Despite their attractive features of high energy density,low cost,and safety,polysulfide/iodide flow batteries(SIFBs)are hampered by the sluggish kinetics of the iodide redox couple,which restricts overall performance.Multicomponent sulfides are demonstrated as promising catalysts for accelerating I^(-)/I_(3)^(-) redox reactions.Concurrently,the enhanced configurational entropy arising from multinary compositions drives synergistic effects among constituent elements,establishing a viable pathway to optimize catalytic performance.Building on these foundations,this work introduces a targeted orbital hybridization-optimized electron density strategy to enhance the catalytic activity.Implementing this concept,we developed an in-situ solvothermal synthesis process for an entropy-enhanced AgCuZnSnS_(4) loaded graphite felt(ACZTS/GF)electrode.The engineered electrode demonstrates exceptional electrocatalytic performance with improved bulk conductivity and interfacial charge transfer kinetics within a SIFB.The cell achieves a high energy efficiency of 88.5%at 20 mA·cm^(−2) with 10%state-of-charge.Furthermore,the battery delivers a maximum power density of 119.8 mW·cm^(−2) and exhibits excellent long-term cycling stability.These significant results stem from orbital hybridization-driven electronic state optimization and entropy effect-induced synergistic catalysis.
基金financially supported by the National Natural Science Foundation of China(52172245)the Key Scientific and Technological Innovation Project of Shandong(2023CXGC010302)the Qingdao Flexible Materials Precision Die-cutting Technology Innovation Center。
文摘In lithium-sulfur batteries(LSBs),the limited utilization of sulfur and the sluggish kinetics of redox reaction significantly hinder their electrochemical performance,especially under high rates and high sulfur loadings.Here,we propose a novel separator structure with an interlayer composed of a vermiculite nanosheet combined with Ketjen Black(VMT@KB)for LSBs,facilitating efficient adsorption and rapid catalytic conversion toward lithium polysulfides(LiPSs).The VMT@KB nanosheets with an electrical double-layer structure and electronic conductivity are obtained through a high-temperature peeling process and Li^(+)exchange treatment in LiCl solution,followed by a mechanical combination process with KB.The results demonstrate that incorporating VMT@KB as an interlayer on a conventional separator enhances the conductivity and limits the LiPSs in the cathode region.The Li-S cell with VMT@KB interlayer shows satisfactory cycle and rate performance,especially in high sulfur loading.It exhibits a remarkable initial discharge capacity of 1225 mAh g^(-1)at 0.5 C and maintains a capacity of 816 mAh g^(-1)after 500 cycles.Besides,the discharge capacity remains 462 mAh g^(-1)even at 6 C.Moreover,the cell with high sulfur loading(8.2 mg cm^(-2))enables stable cycling for 100 cycles at 0.1 C with a discharge capacity of over1000 mAh g^(-1).
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Owing to the advantages of high energy density,low cost,abundant sulfur reserves and environmentally friendly nature,lithium-sulfur batteries(LSBs)were considered as one of the potential candidates of energy storage devices for the next generation.However,the significant challenges in this area stem from the sluggish reaction kinetics of the insoluble Li_(2)S product and the capacity degradation triggered by the severe shuttle effect of polysulfides.It has been firmly established through numerous studies that modifying separators is an effective approach to enhance the properties of LSBs by facilitating the catalytic kinetic conversion and chemical adsorption of lithium polysulfides(Li PSs).In this work,we report a straightforward method for fabrication of the phosphorus doped porous CeO_(2)(P-CeO_(2))as separator modifier to accelerate the catalytic kinetic conversion of polysulfides and effectively inhibit the shuttle effect in LSBs.Through coin batteries tests,P-CeO_(2)modified PP separator(P-CeO_(2)//PP)exhibits remarkable electrochemical performance.It demonstrates a high initial capacity of 1180 mAh/g at 0.5 C,surpassing the performance of the bare CeO_(2)//PP separator.Furthermore,the P-CeO_(2)//PP separator demonstrates enhanced cycling stability,with a low-capacity fading rate of only 0.048%per cycle over 1000 cycles at 2 C.In compared with bare CeO_(2)//PP,P-CeO_(2)//PP exhibits high redox peak current,enhanced adsorption property of Li_(2)S_(6)and early Li_(2)S precipitation.These results highlight the superior performance of the P-CeO_(2)//PP separator compared to the bare CeO_(2)//PP separator.Hence,this research presents a successful strategy for the modification of LIBs separator with improved electrochemical performance and cycle stability.
基金the National Natural Science Foundation of China(Nos.51904344,52172264)the Natural Science Foundation of Hunan Province of China(Nos.2021JJ10060 and 2022GK2033).
文摘The intrinsic clustering behavior and kinetically sluggish conversion process of lithium polysulfides seriously limit the electrochemical reversibility of sulfur redox reactions in lithium-sulfur(Li-S)batteries.Here,we introduce molybdenum pentachloride(MoCl_(5))into the electrolyte which could coordinate with lithium polysulfides and inhibit their intrinsic clustering behavior,subsequently serving as an improved mediator with the bi-functional catalytic effect for Li_(2)S deposition and activation.Moreover,the coordination bonding and accelerated conversion reaction can also greatly suppress the dissolution and shuttling of polysulfides.Consequently,such polysulfide complexes enable the Li-S coin cell to exhibit good longterm cycling stability with a capacity decay of 0.078%per cycle after 400 cycles at 2 C,and excellent rate performance with a discharge capacity of 589 mAh/g at 4 C.An area capacity of 3.94 mAh/cm^(2)is also achieved with a high sulfur loading of 4.5mg/cm^(2)at 0.2 C.Even at-20℃,the modified cell maintains standard discharge plateaus with low overpotential,delivering a high capacity of 741 mAh/g at 0.2 C after 80 cycles.The low-cost and convenient MoCl_(5)additive opens a new avenue for the effective regulation of polysulfides and significant enhancement in sulfur redox conversion.
基金supported by the Natural Science Foundation of China(22309179)the Natural Science Foundation of China(12404049)+4 种基金Natural Science Foundation of Ningxia(2023AAC01003)Guangdong Basic and Applied Basic Research Foundation(2021A1515110156,2022A1515010724,2023A1515110521,2023B1515120095,2024A1515011260)Science and Technology Program of Guangzhou(No.2019050001)the Outstanding Youth Project of Guangdong Natural Science Foundation(2021B1515020051)Dalian Revitalization Talents Program(No.2022RG01).
文摘Developing electrocatalysts to inhibit polysulfide shuttling and expedite sulfur species conversion is vital for the evolution of Lithium-sulfur(Li-S)batteries.This work provides a facile strategy to design an intimate heterostructure of MIL-88A@CdS as a sulfur electrocatalyst combining high sulfur adsorption and accelerated polysulfide conversion.The MIL-88A can give a region of high-ordered polysulfide adsorption,whereas the CdS is an effective nanoreactor for the sulfur reduction reaction(SRR).Notedly,the significant size difference between MIL-88A and CdS enables the unique heterostructure interactions.The largesize MIL-88A ensures a uniform distribution of CdS nanoparticles as a substrate.This configuration facilitates control of the initial polysulfide adsorption position relative to its final deposition site as lithium sulfide.The heterostructure also demonstrates rapid transport and efficient conversion of lithium polysulfides.Consequently,the Li-S battery with MIL-88A@CdS heterostructure modified separator delivers exceptional performance,achieving an areal capacity exceeding 6 mAh cm^(−2),an excellent rate capability of 980 mAh g^(−1) at 5 C,and notable cycling stability in a 2 Ah pouch cell over 100 cycles.This work is significant for elucidating the relationship between heterostructure and electrocatalytic performance,providing great insights for material design aimed at highly efficient future electrocatalysts in practical applications.
基金supported by the Scientific Research Program Funded by Education Department of Shaanxi Provincial Government(No.22JK0411)the Natural Science Basic Research Program of Shaanxi Province(No.2023-JC-QN-0165)the National Natural Science Foundation of China(No.21603109).
文摘Lithium-sulfur batteries are considered to be a new generation of high energy density batteries due to their non-toxicity,low cost and high theoretical specific capacity.However,the development of practical lithium-sulfur batteries is seriously impeded by the sluggish multi-electron redox reaction of sulfur species and obstinate shuttle effect of polysulfides.In this study,a porous lanthanum oxychloride(LaOCl)nanofiber is designed as adsorbent and electrocatalyst of polysulfides to regulate the redox kinetics and suppress shuttling of sulfur species.Benefiting from the porous architecture and luxuriant active site of LaOCl nanofibers,the meliorative polarization effect and sulfur expansion can be accomplished.The LaOCl/S electrode exhibits an initial discharge specific capacity of 1112.3 mAh/g at 0.1 C and maintains a superior cycling performance with a slight decay of 0.02%per cycle over 1000 cycles at 1.0 C.Furthermore,even under a high sulfur loading of 4.6mg/cm^(2),the S cathode with LaOCl nanofibers still retains a high reversible areal capacity of 4.2 mAh/cm^(2)at 0.2 C and a stable cycling performance.Such a porous host expands the application of rare earth based catalysts in lithium-sulfur batteries and provides an alternative approach to facilitate the polysulfides conversion kinetics.
基金supported by the National Natural Science Foundation of China(52463013 and 52073133)Key Talent Project Foundation of Gansu Province+3 种基金Joint fund between Shenyang National Laboratory for Materials ScienceState Key Laboratory of Advanced Processing and Recycling of Nonferrous Metals(18LHPY002)the Program for Hongliu Distinguished Young Scholars in Lanzhou University of Technologythe Incubation Program of Excellent Doctoral Dissertation–Lanzhou University of Technology
文摘Shuttle effect of polysulfides overshadows the superiorities of lithium-sulfur batteries.Size-sieving effect could address this thorny trouble rely on size differ in polysulfides and lithium ions.However,clogged polysulfides pose some challenges for cathode and are rarely recycled during charging/discharging.Herein,an amino functionalized titanium-organic framework is designed for modifying lithium-sulfur batteries separator to address the aforementioned challenges.Wherein,the introduction of amino narrows titanium-organic framework pore size,enabling functional separator to selectively modulate lithium ions and polysulfides migration using size-sieving effect,thereby completely suppressing polysulfides shuttle.Furthermore,the blocked polysulfides will be adsorbed on the separator surface by positively charged amino leveraging electrostatic adsorption,ensuring polysulfides to redistribute and reuse,and boosting active materials utilization.Significantly,the migration of lithium ions is not hindered since there are lithium ions transfer channels formed via Lewis acid-base interaction with the help of amino.Combined with these virtues,the lithium-sulfur batteries with amino functionalized titanium-organic framework modified separator enjoy an ultralow attenuation rate of 0.045%per cycle over 1000 cycles at 1.0C.Electrostatic adsorption and Lewis acid-base interaction cover deficiencies existing in the inhibition of polysulfides shuttle by size-sieving effect,providing fresh insight into the advancement of lithium-sulfur batteries.
基金financially supported by the National Natural Science Foundation of China(U22A20113,52261135543)。
文摘Lithium-sulfur(Li-S)batteries with high energy density suffer from the soluble lithium polysulfide species,Traditional metal sulfides containing a single metal element used as electrocatalysts for Li-S batteries commonly have limited catalytic abilities to improve battery performance.Herein,based on the Hume-Rothery rule and solvothermal method,the high-entropy sulfide NiCoCuTiVS_(x)derived from Co_(9)S_(8)was designed and synthesized,to realize the combination of small local strain and excellent catalytic performance.With all five metal elements(Ni,Co,Cu,Ti,and V)capable of chemical interactions with soluble polysulfides,NiCoCuTiVS_(x)exhibited strong chemical confinement of polysulfides and promoted fast kinetics for polysulfides conversion.Consequently,the S/NiCoCuTiVS_(x)cathode can maintain a high discharge capacity of 968.9 mA h g^(-1)after 200 cycles at 0.5 C and its capacity retention is 1.3 times higher than that of S/Co_(9)S_(8).The improved cycle stability can be attributed to the synergistic effect originating from the multiple metal elements,coupled with the reduced nucleation and activation barriers of Li_(2)S.The present work opens a path to explore novel electrocatalyst materials based on high entropy materials for the achievement of advanced Li-S batteries.
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Financial supports from the National Natural Science Foundation of China(Grant Number:22265018)the Key Project of Natural Science Foundation of Jiangxi Province(Grant Number:20232ACB204010)+1 种基金the Graduate Innovative Special Fund Projects of Jiangxi Province(Grant Number:YC2024-B034)the Jiangxi Province Key Laboratory of Lithiumion Battery Materials and Application(Grant Number:2024SSY05202)are gratefully acknowledged。
文摘Metal phosphosulfides(MPS_(x)),especially BiPS_(4),have emerged as promising anode candidates for sodiumion batteries,distinguished by distinctive multinary redox chemistry,open tunnel-type structure,and high theoretical capacity(>1000 m Ah g^(-1)).However,their practical implementation is fundamentally limited by polysulfide dissolution/shuttling and structural instability during prolonged cycling.Herein,we develop a groundbreaking two-stage metal-organic framework(MOF)-engineered compositing strategy through which Bi-MOF-derived BiPS_(4)/C pillars are robustly armored with conductive Ni-HHTP(HHTP=2,3,6,7,10,11-hexahydroxytriphenylene)nanorods.Density functional theory calculations reveal that this design achieves dual functionality:increased carrier density for enhanced charge transport dynamics and effective polysulfide adsorption to inhibit dissolution.The fabricated BiPS_(4)/C@Ni-HHTP composite delivers remarkable electrochemical properties,including high initial charge/discharge specific capacities of 1063.6/1181.3 mAh g^(-1)at 0.1 A g^(-1)and outstanding long-term stability with 99.2% capacity retention after 2000 cycles at 2 A g^(-1).Such superb performance stems from the perfect synergy of the inherent high-capacity redox behavior of BiPS_(4),the buffering effect of MOF-derived carbon,and the conductivity,adsorption sites and mechanical resilience of Ni-HHTP.This work establishes a new design paradigm for MPS_(x)materials,demonstrating how to simultaneously overcome conductivity limitations and shuttle effects in conversion-type electrodes.
基金supported by the National Natural Science Foundation of China(22201244,22374125,21971221 and 21773203)the Yangzhou University Interdisciplinary Research Foundation for Chemistry Discipline of Targeted Support(yzuxk202010)+2 种基金High-Level Entrepreneurial and Innovative Talents Program of Jiangsu‘Qing Lan Project’in Colleges and Universities of Jiangsu ProvinceLvyangjinfeng Talent Program of Yangzhou,China Postdoctoral Science Foundation(2022M722688)。
文摘The polysulfides shuttle effect,sluggish sulfur redox kinetics and the corrosion of the Li anode have become important factors limiting the commercial application of lithium-sulfur batteries(LSBs).Herein,the polyoxometalate(POM)nanoclusters with high catalytic activity and cobalt selenide with strong polarity are initially complemented to construct a PMo_(12)/CoSe_(2)@NC/CNTs multifunctional separator that can simultaneously solve the above problems.A series of experimental and theoretical results demonstrate that the Keggin-type POM,H_(3)PMo_(12)O_(40)nH_(2)O(PMo_(12))nanoclusters could function as catalytic centers for sulfur-involved transformations,with the CoSe_(2)nanoparticles serving as adsorption sites for soluble polysulfides.Accordingly,the assembled battery with the PMo_(12)/CoSe_(2)@NC/CNTs modified separator achieves an initial discharge capacity of 1263.79 mA h g^(-1),maintaining 635.77 mA h g^(-1),with a capacity decay rate of 0.06%per cycle after 500 cycles at 3C.This work provides a strategic approach for incorporating POM nanoclusters with polar periodic nanomaterials in LSB separators,contributing to the development of multifunctional separator materials,thus promoting the advancement of energy storage systems.
基金financially supported by Jilin province science and technology department(No.20230402059GH)Changchun Science and Technology Bureau(No.23YQ11)+4 种基金Jilin Province Science and Technology Department major science and technology project(Nos.20220301004GX and 20220301005GX)Key Subject Construction of Physical Chemistry of Northeast Normal University(No.2412022XK004)the National Natural Science Foundation of China(No.22102020)the Swedish Foundation for International Cooperation in Research and Higher Education(No.KO2017-7351)Swedish Energy Agency(No.P2020-90216)。
文摘Developing effective heterostructure strategies to mitigate the shuttling effect and accelerate lithium polysulfide(Li PS)conversion remains a critical challenge in lithium–sulfur(Li–S)batteries.Here,we report the first carbon–free VO_(2)–VS_(2)heterostructure material synthesized via in situ sulfurization,applied as a modifier on a commercial polypropylene(PP)separator(denoted as VO_(2)–VS_(2)@PP).The as–prepared VO_(2)–VS_(2)nanorods synergistically combine the high absorptivity of VO_(2)with the efficient catalytic properties of VS_(2),simultaneously enhancing Li PS anchoring and promoting its conversion.We systematically investigate the influence of material composition on battery performance,leveraging these functional attributes,Li–S cells incorporating VO_(2)–VS_(2)@PP exhibit exceptional cycle stability(over 500cycles at 1C),impressive rate performance(807 m Ah.g^(–1)at 5C),desirable reversibility(49.9%capacity retention after 300 cycles at 5C)and exceptional pouch cell performance(3.65 m Ah.cm^(–2)after 50 stable cycles at 0.1C).This study underscores the potential of tailored heterostructures in realizing high–performance Li–S batteries,offering new insights for next–generation energy storage solutions.
基金supported by the National Key Research and Development Program of China(No.2019YFA0210600)the National Natural Science Foundation of China(Nos.51922103 and 51972326)+1 种基金the Natural Science Foundation of Jiangxi Province(Nos.20224BAB204002 and GJJ211320)Jingdezhen Science and Technology Bureau(No.20212GYZD009-15)。
文摘Solid-state polymer sodium batteries(SPSBs)are promising candidates for achieving higher energy density and safe energy storage.However,interface issues between oxide cathode and solid-state polymer electrolyte are a great challenge for their commercial application.In contrast,soft sulfur-based materials feature better interface contact and chemical compatibility.Herein,an interfacial compatible polysulfide Ti_(4)P_(8)S_(29) with robust Ti-S bonding and a highly active P-S unit is tailored as a high-performance cathode for SPSBs.The Ti_(4)P_(8)S_(29) cathode possesses a three-dimensional channel structure for offering ample Na+diffusion pathways.The assembled poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)-based SPSBs deliver a discharge capacity of 136 mAh·g^(-1)at 0.5C after 200 cycles.Furthermore,a discharge capacity of 88 mAh·g^(-1)is retained after 600 cycles at a high rate of 2C,surpassing many cathode materials in SPSBs.A dual-site redox of Ti^(4+)/Ti^(3+)and S^(-)/S^(2-)is verified by X-ray photoelectron spectroscopy(XPS)and cyclic voltammetry(CV)tests.Interestingly,a refined locally-ordered amorphous structure is unveiled by in situ and ex situ characterizations.The as-formed electrode structure with lots of open channels and isotropic properties are more beneficial for ion diffusion on the interface of electrode and solid-state polymer electrolytes(SPEs),leading to faster Na+diffusion kinetics.This work proposes a strategy of modulating open-channel to boost conversion kinetics in polysulfide cathode and opens a new pathway for designing high-performance SPSBs.
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.
文摘Aim Cysteine proteases are closely associated with many human and non-human pathological processes and are potential targets for metal ions especially Hg^2＋ and the related species. In the present work, on the basis of to the general study on the effects of some metal ions on the activity of papain, a well-known representative of cysteine protease family, the inhibitory effects of Hg^2＋ and polysulfide complexes were studied. Results All the metal ions tested （Hg^2＋, Cu^2＋, Ag^＋, Au^3＋, Zn^2＋, Cd^2＋, Fe^3＋, Mn^2＋, Pb^2＋, Yb^3＋） inhibit the activity of papain anda good correlation between the inhibitory potency and softness-and-hardness was observed. Among the metals, Hg^2＋ was shown to be a potent inhibitor of papain with a Kiof 2 × 10^-7 mol·L^-1 among. Excessive amounts of glutathione and cysteine could reactivate the enzyme activity of papain deactivated by Hg^2＋. These evidences supported that Hg^2＋ might bind to the catalytic site of papain. Interestingly, Hg （Ⅱ） polysulfide complexes were for the first time found to inhibit papain with a Ki of 7 × 10^-6 mol·L^-1, whose potency is close to a well known mercury compound, thimerosal （Ki=2.7 × 10^-6）. In addition, Hg （Ⅱ） polysulfide complexes exhibit good permeability （ 1.9 × 10-5 cm· s^-1） to caco-2 monolayer. Conclusion These results suggested that mercury polysulfide complexes might be potential bioactive species in the interaction with cysteine proteases and other- SH-content proteins, providing a new clue to understand the mechanism of the toxicological and pharmacological actions of cinnabar and other insoluble mercury compounds.
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supported by the National Natural Science Foundation of China(U1904215)Natural Science Foundation of Jiangsu Province(BK20200044)+1 种基金Changjiang scholars program of the Ministry of Education(Q2018270)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX20_2805).
文摘The practical application of Li-S batteries is largely impeded by the“shuttle effect”generated at the cathode which results in a short life cycle of the battery.To address this issue,this work discloses a bimetallic metal-organic framework(MOF)as a sulfur host material based on Al-MOF,commonly called(Al)MIL-53.To obtain a high-adsorption capacity to lithium polysulfides(Li_(2)S_(x),4≤x≤8),we present an effective strategy to incorporate sulfiphilic metal ion(Cu^(2+))with high-binding energy to Li_(2)S_(x)into the framework.Through a one-step hydrothermal method,Cu^(2+)is homogeneously dispersed in Al-MOF,producing a bimetallic Al/Cu-MOF as advanced cathode material.The macroscopic Li2S4 solution permeation test indicates that the Al/Cu-MOF has better adsorption capacity to lithium polysulfides than monometallic Al-MOF.The sulfur-transfusing process is executed via a melt-diffusion method to obtain the sulfur-containing Al/CuMOF(Al/Cu-MOF-S).The assembled Li-S batteries with Al/Cu-MOF-S yield improved cyclic performance,much better than that of monometallic AlMOF as sulfur host.It is shown that chemical immobilization is an effective method for polysulfide adsorption than physical confinement and the bimetallic Al/Cu-MOF,formed by incorporation of sulfiphilic Cu^(2+)into porous MOF,will provide a novel and powerful approach for efficient sulfur host materials.
基金supported by the Fundamental Research Funds for Central Universities(SCUT No.2019ZD22)Guangdong Innovative and Entrepreneurial Research Team Program(No.2016ZT06N569)。
文摘The slow redox dynamics and dissolution of polysulfides in lithium-sulfur(Li-S)batteries result in poor rate performance and rapid decay of battery capacity,thus limiting their practical application.Ferroelectric barium titanate(BT)nanoparticles have been reported to effectively improve the electrochemical performance of Li-S batteries due to the inherent self-polarization and high adsorption capacity of the BT nanoparticles towards polysulfides.Here in this paper,BT nanoparticles,behave as highly efficient electrocatalyst and demonstrate much higher redox dynamics towards the conversion reaction of polysulfides and Li2S than TiO2,as shown by both electrochemical measurements and density functional theory calculation.The coupling of the sulfur host of the hollow and graphitic carbon flakes(HGCF)and the BT nanoparticles(HGCF/S-BT)enable excellent electrochemical performance of Li-S batteries,delivering a0.047%capacity decay per cycle in 1000 cycles at 1 C,788 mAh g^-1 at 2 C and a reversible capacity of613 mAh g^-1 after 300 cycles at a current density of 0.5 C at a S loading of 3.4 mg cm^-2.HGCF/S-BT also shows great promise for practical application in flexible devices as demonstrated on the soft-packaged Li-S batteries.
基金supported by the National Natural Science Foundation of China(Nos. U1710109 and 51702182)Shenzhen Basic Research Project(No.JCYJ20150529164918734)
文摘As polar materials, transition-metal oxides have shown great potentials to improve the adsorption of lithium polysulfides in lithium-sulfur batteries. Herein, a MoO_2-ordered mesoporous carbon (M-OMC)hybrid was designed as the sulfur host, in which MoO_2 is inlaid on the surface of ordered mesoporous carbons that can store active materials and provide fast electron transfer channel due to its ordered pore structure. The MoO_2 can effectively prevent the migration of polysulfides through the chemical adsorption and promote the conversion of polysulfides towards Li-sulfur battery.
基金financial support of the Youth Project of the Provincial Natural Science Foundation of Anhui(No. 2008085QE267)the Doctoral Research Initiation Foundation of Anhui Normal University (No. 751973)+2 种基金the National Natural Science Foundation of China (No. 51972162)the Fundamental Research Funds for the Central Universities (No. 0213-14380196)the Science and Technology Project of Nanchang (No. 2017-SJSYS-008)。
文摘Inhibiting the “shuttle effect” of soluble polysulfides and improving reaction kinetics are the key factors necessary for further exploration of high-performance Li-S batteries. Herein, an effective interface engineering strategy is reported, wherein nitriding of an Ni-based precursor is controlled to enhance Li-S cell regulation. The resulting in-situ formed NiO-Ni_(3)N heterostructure interface not only has a stronger polysulfide adsorption effect than that of monomeric NiO or Ni_(3)N but also has a faster Li ion diffusion ability than a simple physical mixture. More importantly, this approach couples the respective advantages of NiO and Ni_(3)N to reduce polarization and facilitate electron transfer during polysulfide reactions and synergistically catalyze polysulfide conversion. In addition, ultrafine nanoparticles are thought to effectively improve the use of additive materials. In summary, Li-S batteries based on this NiO-Ni_(3)N heterostructure have the features of long cycle stability, rapid charging-discharging, and good performance under high sulfur loading.
