Lithium-sulfur (Li-S) batteries have gained great attention due to the high theoretical energy density and low cost,yet their further commercialization has been obstructed by the notorious shuttle effect and sluggish ...Lithium-sulfur (Li-S) batteries have gained great attention due to the high theoretical energy density and low cost,yet their further commercialization has been obstructed by the notorious shuttle effect and sluggish redox dynamics.Herein,we supply a strategy to optimize the electron structure of Ni_(2)P by concurrently introducing B-doped atoms and P vacancies in Ni_(2)P (Vp-B-Ni_(2)P),thereby enhancing the bidirectional sulfur conversion.The study indicates that the simultaneous introduction of B-doped atoms and P vacancies in Ni_(2)P causes the redistribution of electron around Ni atoms,bringing about the upward shift of d-band center of Ni atoms and effective d-p orbital hybridization between Ni atoms and sulfur species,thus strengthening the chemical anchoring for lithium polysulfides (LiPSs) as well as expediting the bidirectional conversion kinetics of sulfur species.Meanwhile,theoretical calculations reveal that the incorporation of B-doped atoms and P vacancies in Ni_(2)P selectively promotes Li2S dissolution and nucleation processes.Thus,the Li-S batteries with Vp-B-Ni_(2)P-separators present outstanding rate ability of 777 m A h g^(-1)at 5 C and high areal capacity of 8.03 mA h cm^(-2)under E/S of 5μL mg^(-1)and sulfur loading of 7.20 mg cm^(-2).This work elucidates that introducing heteroatom and vacancy in metal phosphide collaboratively regulates the electron structure to accelerate bidirectional sulfur conversion.展开更多
Lithium-sulfur(Li-S)chemistry reaction opens a new battery era with high energy density;meanwhile,multiple electrons migration leads to the complex phase transition of sulfur species.To manipulate the binding strength...Lithium-sulfur(Li-S)chemistry reaction opens a new battery era with high energy density;meanwhile,multiple electrons migration leads to the complex phase transition of sulfur species.To manipulate the binding strength of multiple key intermediates more efficiently,the bimetallic TiVC MXene is utilized to realize multi-dimensional catalysis.Based on the macroscopic three-dimensional(3D)structure using two-dimensional(2D)MXene architecture,electron conductivity and sulfur utilization are improved.Microscopically,Ti-V catalytic systems regulate multiple reaction intermediates through intermetallic synergies customized surface properties and atomic scale coordination,thereby improving electronic and ionic conductivity.In-situ Raman spectroscopy and electrochemical analysis show that the conversion rate of polysulfides was accelerated during the charge-discharge process.The Ti-V interaction exhibits unique catalytic activity and regulates multiple continuous processes of sulfur species phase transformation,which are essential for the excellent energy performance of Li-S batteries.This study not only clarifies the catalytic mechanism of Ti-V at different dimensions but also proposes a promising strategy for the design of advanced catalytic systems in energy storage technology.展开更多
A functional interlayer based on two-dimensional(2D)porous modified vermiculite nanosheets(PVS)was obtained by acid-etching vermiculite nanosheets.The as-obtained 2D porous nanosheets exhibited a high specific surface...A functional interlayer based on two-dimensional(2D)porous modified vermiculite nanosheets(PVS)was obtained by acid-etching vermiculite nanosheets.The as-obtained 2D porous nanosheets exhibited a high specific surface area of 427 m^(2)·g^(-1)and rich surface active sites,which help restrain polysulfides(LiPSs)through good physi-cal and chemical adsorption,while simultaneously accelerating the nucleation and dissolution kinetics of Li_(2)S,effec-tively suppressing the shuttle effect.The assembled lithium-sulfur batteries(LSBs)employing the PVS-based inter-layer delivered a high initial discharge capacity of 1386 mAh·g^(-1)at 0.1C(167.5 mAh·g^(-1)),long-term cycling stabil-ity,and good rate property.展开更多
Lithium-sulfur(Li-S)batteries have great promise for next-generation energy storage devices due to the high theoretical specific capacity(1675 mAh g^(-1))of sulfur with chemical conversion for charge storage.However,t...Lithium-sulfur(Li-S)batteries have great promise for next-generation energy storage devices due to the high theoretical specific capacity(1675 mAh g^(-1))of sulfur with chemical conversion for charge storage.However,their practical use is hindered by the slow redox kinetics of sulfur and the“shuttle effect”arising from dissolved lithium polysulfides(LiPSs).In recent years,various carbon-based materials have served as sulfur hosts and catalysts for accelerating sulfur conversion redox kinetics and alleviating LiPS shuttling.However,they often suffer from irreversible passivation and structural changes that destroy their long-term performance.We consider the main problems limiting their stability,including excessive LiPS adsorption,passivation by insulating Li2S,and surface reconstruction,and clarify how these factors lead to capacity fade.We then outline effective strategies for achieving long-term sulfur catalysis,focusing on functional carbon,such as designing suitable carbon-supported catalyst interfaces,creating well-distributed active sites,adding cocatalysts to improve electron transfer,and using carbon-based protective layers to suppress unwanted side reactions.Using this information should enable the development of stable,high-activity catalysts capable of long-term operation under practical conditions in Li-S batteries.展开更多
Lithium-sulfur batteries are considered as one of the potential solutions as integrating renewable energy systems for large-scale energy storage because of their high theoretical energy density(2600 Wh·kg^(-1))an...Lithium-sulfur batteries are considered as one of the potential solutions as integrating renewable energy systems for large-scale energy storage because of their high theoretical energy density(2600 Wh·kg^(-1))and specific capacity(1675 mAh·g^(-1)).Currently,various strategies have been proposed to overcome the technical barriers,e.g.,“shuttle effect”,capacity decay and volumetric change,which impede the successful commercialization of lithium-sulfur batteries.This paper reviews the applications of metal nitrides as the cathode hosts for high-performance lithium-sulfur batteries,summa-rizes the design strategies of different host materials,and discusses the relationship between the properties of metal nitrides and their electrochemical performances.Finally,reasonable suggestions for the design and development of metal nitrides,along with ideas to promote future breakthroughs,are proposed.We hope that this review could attract more attention to metal nitrides and their derivatives,and further promote the electrochemical performance of lithium-sulfur batteries.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(Li-S)batteries with high energy density and capacity have garnered significant research attention among various energy storage devices.However,the shuttle effect of polysulfides(LiPSs)remains a major ch...Lithium-sulfur(Li-S)batteries with high energy density and capacity have garnered significant research attention among various energy storage devices.However,the shuttle effect of polysulfides(LiPSs)remains a major challenge for their practical application.The design of battery separators has become a key aspect in addressing the challenge.MXenes,a promising two-dimensional(2D)material,offer exceptional conductivity,large surface area,high mechanical strength,and active sites for surface reactions.When assembled into layered films,MXenes form highly tunable two-dimensional channels ranging from a few angstroms to over 1 nm.These nanoconfined channels are instrumental in facilitating lithium-ion transport while effectively impeding the shuttle effect of LiPSs,which are essential for improving the specific capacity and cyclic stability of Li-S batteries.Substantial progress has been made in developing MXenes-based separators for Li-S batteries,yet there remains a research gap in summarizing advancements from the perspective of interlayer engineering.This entails maintaining the 2D nanochannels of layered MXenes-based separators while modulating the physicochemical environment within the MXenes interlayers through targeted modifications.This review highlights advancements in in situ modification of MXenes and their integration with 0D,1D,and 2D materials to construct laminated nanocomposite separators for Li-S batteries.The future development directions of MXenes-based materials in Li-S energy storage devices are also outlined,to drive further advancements in MXenes for Li-S battery separators.展开更多
Lithium-sulfur batteries have been developing in recent years and appear to offer an alternative to existing commercial batteries that can potentially replace them in the future.With their exceptional theoretical ener...Lithium-sulfur batteries have been developing in recent years and appear to offer an alternative to existing commercial batteries that can potentially replace them in the future.With their exceptional theoretical energy density,lower production costs,and affordable and environmentally friendly abundant raw materials,lithium-sulfur batteries have shown the ability to defeat counterparts in the race for rechargeable energy devices currently being developed.The lithium-sulfur batteries display extraordinary features,but they suffer from sulfur's non-conductivity,the shuttle effect that results from polysulfide dissolution,volumetric sulfur changes during charging,and dendrites at the anode,resulting in a decline in capacity and a short battery life.As a result of rigorous and innovative engineering designs,lithium-sulfur batteries have been developed to overcome their drawbacks and utilize their entire potential during the past decade.This review will pay particular attention to porous carbon-based matrix materials,especially graphene-based nanocomposites that are most commonly used in producing sulfur cathodes.We provide an in-depth perspective on the structural merits of graphene materials,the detailed mechanism by which they interact with sulfur,and essential strategies for designing high-performance cathodes for lithium-sulfur batteries.Finally,we discuss the significant challenges and prospects for developing lithium-sulfur batteries with high energy density and long cycle lives for the next-generation electric vehicles.展开更多
Lithium sulfide(Li_(2)S)is widely regarded as the next-generation cathode material for rechargeable batteries due to its satisfactory theoretical capacity and excellent compatibility with lithium-free anodes.However,t...Lithium sulfide(Li_(2)S)is widely regarded as the next-generation cathode material for rechargeable batteries due to its satisfactory theoretical capacity and excellent compatibility with lithium-free anodes.However,the large-scale applications of Li_(2)S cathodes are limited by the shuttle effect of soluble intermediate lithium polysulfides(LiPSs)and the sluggish redox kinetics of the interconversion between Li_(2)S and sulfur(S).Herein,we report novel nitrogen-doped carbon nanoflakes in-situ embedded with WN-Ni_(2)P heterostructures(WN-Ni_(2)P@NCN)as a multifunctional host to promote the cycling performance and reaction kinetics of Li_(2)S.After loading Li_(2)S,the WNNi_(2)P@NCN/Li_(2)S exhibits stable reversible capacity of 597mAh g^(-1)at 0.5 A g^(-1)over 150 cycles,and superior cycling stability over 800 cycles.The high reversible capacities,excellent cycling properties and superior reaction kinetics of WN-Ni_(2)P@NCN/Li_(2)S are attributed to the strong LiPSs fixation,remarkable catalytic activation and high electronic/ionic conductivity of the WN-Ni_(2)P@NCN framework,confirmed by the experiment and the density function theory calculation results.This work offers a new strategy for designing heterostructure nanoflakes with metal nitride and metal phosphide to facilitate the applications of advanced lithium-sulfur batteries.展开更多
Heteroatom doping has emerged as a powerful strategy to optimize the catalytic and adsorption abilities of electrocatalysts by regulating the electronic structure,thereby enabling the development of efficient electroc...Heteroatom doping has emerged as a powerful strategy to optimize the catalytic and adsorption abilities of electrocatalysts by regulating the electronic structure,thereby enabling the development of efficient electrocatalysts for lithium-sulfur(Li-S)batteries.However,the correlation between the properties of doped atoms and adsorptio n-catalytic ability,as well as the interconnection between adsorption strength and catalytic activity,remains underexplored.Herein,we employed halogen atoms(F,Cl,and Br)with different electronegativities to dope nickel phosphide(Ni_(2)P),aiming to modulate the adsorption properties toward lithium polysulfides(LiPSs).We systematically explored the relationship between the electronegativity of the doping atoms and the adsorption strength,followed by exploring the connection between adsorption and catalytic capabilities.Combined experimental and theoretical analyses reveal that doping halogen atoms effectively strengthens d-p orbital hybridization between Ni atoms and S atoms,thereby enhancing LiPSs anchoring and conversion.Specifically,the chemical adsorption capability is enhanced as the electronegativity of the doped atoms increases.Moreover,the catalytic activity presents a volcano-like trend with the enhancement of adsorption performance,wherein the activity initially increases and subsequently diminishes.Therefore,Cl-doped Ni_(2)P with moderate chemisorption ability exhibits optimal redox kinetics in bidirectional sulfur conversion.Consequently,the Li-S batteries with Cl-Ni_(2)P-separators deliver a high-rate capacity of 790 mAh g^(-1)at 5 C and achieve a remarkable areal capacity of 7.36 mAh cm^(-2)under practical conditions(sulfur loading:7.10 mg cm^(-2);electrolyte/sulfur(E/S)ratio:5μL mg^(-1)).This work uncovers the significance of achieving a balance between adsorption and catalytic capabilities,offering insights into designing efficient electrocatalysts for lithium-sulfur batteries.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
Lithium-sulfur(Li-S)batteries hold great promise for next-generation energy storage,yet suffer from sluggish redox kinetics and polysulfide shuttling.Herein,a novel Ni_(3)S_(2)/Ni_(2)B heterostructure is developed to ...Lithium-sulfur(Li-S)batteries hold great promise for next-generation energy storage,yet suffer from sluggish redox kinetics and polysulfide shuttling.Herein,a novel Ni_(3)S_(2)/Ni_(2)B heterostructure is developed to improve sulfur electrochemistry by synergistically enhancing polysulfide fixation and catalytic conversions.Fabricated through mild sequential boronation and sulfurization,this hybrid nanocatalyst integrates the strong polysulfide adsorbability and high conductivity of Ni_(2)B with the high catalytic activity of Ni_(3)S_(2).More importantly,the as-constructed heterointerface inspires new,highly catalytic sites that smooth consecutive sulfur conversions with lower energy barriers,while the built-in electric fields promote directional charge transfer,collectively contributing to fast-kinetic and highly efficient sulfur redox reactions.As a result,Li-S cells incorporating the Ni_(3)S_(2)/Ni_(2)B nanocatalyst exhibit excellent cyclability,with minimal capacity decay of 0.017%per cycle over 900 cycles at 1 C and a superb rate capability of up to 5 C.Even under demanding conditions,such as a high sulfur loading of 5.0 mg cm^(-2)and a low electrolyte-to-sulfur(E/S)ratio of 4.8 mL g^(-1),high capacity and cyclability are maintained,highlighting the great potential of this unique heterointerface engineering in advancing high-performance and practically viable Li-S 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(Li-S)batteries are promising for high-energy-density storage,but their performance is limited by sluggish lithium polysulfide(LiPS)conversion kinetics.Here,we tackle this issue by synthesizing ultrafine...Lithium-sulfur(Li-S)batteries are promising for high-energy-density storage,but their performance is limited by sluggish lithium polysulfide(LiPS)conversion kinetics.Here,we tackle this issue by synthesizing ultrafine truncated octahedral TiO_(2) nanocrystals(P-O_(v)-TiO_(2)),featuring specific{101}facets and dual defects—phosphorus doping and oxygen vacancies.Acting as an efficient electrocatalyst in the separator,P-O_(v)-TiO_(2) exhibits superior catalytic properties,where oxygen vacancies modulate the electronic structure,enhancing electron enrichment and charge transfer;phosphorus doping tailors the d-band center of the catalyst,strengthening Ti-S interactions between the{101}facets and LiPSs.As a result,Li-S coin cells modified with P-O_(v)-TiO_(2) achieve a high specific capacity of 895 mAh g^(−1) at 5 C and exhibit a minimal decay rate of 0.14%per cycle over 200 cycles.Furthermore,Li-S pouch cells deliver a high capacity of 1004 mAh g^(−1) at 0.1 C under lean electrolyte conditions.This study elucidates the mechanisms of charge states on specific crystal planes and deepens our understanding of dual-defect engineering in Li-S electrochemistry,offering a promising approach for developing efficient and cost-effective catalysts for Li-S battery applications.展开更多
Global interest in lithium-sulfur batteries as one of the most promising energy storage technologies has been sparked by their low sulfur cathode cost,high gravimetric,volumetric energy densities,abundant resources,an...Global interest in lithium-sulfur batteries as one of the most promising energy storage technologies has been sparked by their low sulfur cathode cost,high gravimetric,volumetric energy densities,abundant resources,and environmental friendliness.However,their practical application is significantly impeded by several serious issues that arise at the cathode-electrolyte interface,such as interface structure degradation including the uneven deposition of Li_(2)S,unstable cathode-electrolyte interphase(CEI)layer and intermediate polysulfide shuttle effect.Thus,an optimized cathode-electrolyte interface along with optimized electrodes is required for overall improvement.Herein,we comprehensively outline the challenges and corresponding strategies,including electrolyte optimization to create a dense CEI layer,regulating the Li_(2)S deposition pattern,and inhibiting the shuttle effect with regard to the solid-liquid-solid pathway,the transformation from solid-liquid-solid to solid-solid pathway,and solid-solid pathway at the cathode-electrolyte interface.In order to spur more perceptive research and hasten the widespread use of lithium-sulfur batteries,viewpoints on designing a stable interface with a deep comprehension are also put forth.展开更多
Sluggish sulfur conversion kinetics pose an ongoing challenge in lithium-sulfur batteries(LSBs).Here,we present a solution through far-reaching long-range electronic regulation(LRER)on single-atom active sites.N-doped...Sluggish sulfur conversion kinetics pose an ongoing challenge in lithium-sulfur batteries(LSBs).Here,we present a solution through far-reaching long-range electronic regulation(LRER)on single-atom active sites.N-doped carbons(Co-NC)are implanted with densely-distributed Co single atoms,and supported on Ti_(3)C_(2)T_(x)MXene substrates to assemble 3D Co-NC/MXene catalyst.MXene effectively mediates interlayer charge transfer(~0.70|e|)contrasted with popular carbon materials(~0.06|e|)to produce LRER through surrounding carbon atoms.The synergy of LRER with near-range electronic regulation(NRER)tunes electronic structures,and enhances heterostructural stability,thus provoking desirous catalytic kinetics of Co single atoms in sulfur reduction.Thereby,the Co-NC/MXene/S cathodes exhibit impressive rate performance and excellent cycling stability(only 0.015%capacity decay per cycle over 600 cycles at 4 C)in LSBs,surpassing state-of-the-art sulfur cathodes.This work reveals the importance of LRER for improved catalysis,and provides new guidance to tailor heterostructures to achieve high-efficient catalysts in various process.展开更多
Lithium-sulfur batteries(LSBs)hold significant promise as advanced energy storage systems due to their high energy density,low cost,and environmental advantages.However,despite recent advancements,their practical ener...Lithium-sulfur batteries(LSBs)hold significant promise as advanced energy storage systems due to their high energy density,low cost,and environmental advantages.However,despite recent advancements,their practical energy density still falls short of the levels required for commercial viability.The energy density is critically dependent on both sulfur loading and the amount of electrolyte used.Highsulfur loading coupled with lean electrolyte conditions presents several challenges,including the insulating nature of sulfur and Li_(2)S,insufficient electrolyte absorption,degradation of the cathode structure,severe lithium polysulfide shuttling,slow redox reaction kinetics,and instability of the Li metal anode.MXenes-based materials,with their metallic conductivity,large polar surfaces,and abundant active sites,have been identified as promising electrocatalysts to improve the redox reactions in LSBs.This review focuses on the significance and challenges associated with high-sulfur loading and lean electrolytes in LSBs,highlighting recent advancements in MXenes-based electrocatalysts aimed at optimizing sulfur cathodes and lithium anodes.It provides a comprehensive discussion on MXenes as both active materials and substrates in LSBs,with the goal of enhancing understanding of the regulatory mechanisms that govern sulfur conversion reactions and lithium plating/stripping behavior.Finally,the review explores future opportunities for MXenes-based electrocatalysts,paving the way for the practical application of LSBs.展开更多
Active sulfur dissolution and shuttle effect of lithium polysulfides(LiPSs)are the main obstacles hindering the practical application of lithium-sulfur batteries(LSBs),which is primarily induced by the direct interact...Active sulfur dissolution and shuttle effect of lithium polysulfides(LiPSs)are the main obstacles hindering the practical application of lithium-sulfur batteries(LSBs),which is primarily induced by the direct interaction between sulfur-loading cathode and liquid electrolyte.The introduction of functional interlayer within the separator and cathode is an effective strategy to stabilize the electrode/electrolyte interface reaction and improve the utilization rate of active sulfur.Herein,conductive composite nanofabrics(CCN)with multifunctional groups are employed as the interlayer of sulfur-loading cathode,in which the PMIA/PAN supporting fibers offer robust mechanical strength and high thermostable performance,and gelatin/polypyrrole functional fibers ensure high electrical conductivity and strong chemical interaction for LiPSs.As demonstrated by the experimental data and material characterizations,the presence of CCN interlayer not only blocks the shuttle behavior of LiPSs,but also strengthens the interface stability of both Li anode and sulfur-loading cathode.Interestingly,the assembled LSBs with CCN interlayer can maintain stable capacity of 686 mAh/g after 200 cycles at 0.5 A/g.This work will provide new ideas for the elaborate design of functional in terlayers/se para tors for LSBs and lithium metal batteries.展开更多
The polysulfide shuttle effect critically hinders lithium-sulfur(Li-S)battery development,therefore,the design of heterogeneous interface engineering with“adsorption-catalysis”functions for polysulfide conversion ha...The polysulfide shuttle effect critically hinders lithium-sulfur(Li-S)battery development,therefore,the design of heterogeneous interface engineering with“adsorption-catalysis”functions for polysulfide conversion has garnered considerable attention.However,the exploration of the intricate relationship between key electronic properties and catalytic activity at such interfaces remains a challenge.Additionally,a comprehensive understanding of the thermodynamic growth mechanisms for heterostructure materials is lacking.Herein,a Ni-based homologous structure was precisely constructed via thermodynamic control,with a specific focus on optimizing the interface design.The theoretical results show that the heterostructures with adjustable composition realize the appropriate upward shift to the D-band,improving the affinity towards polysulfide,and further reducing the reaction energy barrier.On this basis,the relationship between interface design and the D-band center,as well as catalytic performance,was established.Specifically,M-Ni_(3)Fe/Ni_(3)ZnC_(0.7)accomplishes the electron enrichment at the interface,supporting the further diffusion of polysulfides,and lowering the Li-S bond energy,performing the bidirectional catalytic transformation of polysulfides.As a result,the Li-S batteries with the cathode of M-Ni_(3)Fe/Ni_(3)ZnC_(0.7)/S deliver rate performances of discharge capacity of 514 mA h g^(−1)at 5.0 C.This understanding of the D-band and interfacial design provides a framework for Li-S catalyst optimization.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
基金Institute of Technology Research Fund Program for Young Scholars21C Innovation Laboratory Contemporary Amperex Technology Co.,Limited,Ninde, 352100, China (21C–OP-202314)。
文摘Lithium-sulfur (Li-S) batteries have gained great attention due to the high theoretical energy density and low cost,yet their further commercialization has been obstructed by the notorious shuttle effect and sluggish redox dynamics.Herein,we supply a strategy to optimize the electron structure of Ni_(2)P by concurrently introducing B-doped atoms and P vacancies in Ni_(2)P (Vp-B-Ni_(2)P),thereby enhancing the bidirectional sulfur conversion.The study indicates that the simultaneous introduction of B-doped atoms and P vacancies in Ni_(2)P causes the redistribution of electron around Ni atoms,bringing about the upward shift of d-band center of Ni atoms and effective d-p orbital hybridization between Ni atoms and sulfur species,thus strengthening the chemical anchoring for lithium polysulfides (LiPSs) as well as expediting the bidirectional conversion kinetics of sulfur species.Meanwhile,theoretical calculations reveal that the incorporation of B-doped atoms and P vacancies in Ni_(2)P selectively promotes Li2S dissolution and nucleation processes.Thus,the Li-S batteries with Vp-B-Ni_(2)P-separators present outstanding rate ability of 777 m A h g^(-1)at 5 C and high areal capacity of 8.03 mA h cm^(-2)under E/S of 5μL mg^(-1)and sulfur loading of 7.20 mg cm^(-2).This work elucidates that introducing heteroatom and vacancy in metal phosphide collaboratively regulates the electron structure to accelerate bidirectional sulfur conversion.
基金the financial support provided by the National Natural Science Foundation of China(No.51932005)the Liaoning Revitalization Talents Program(No.XLYC1807175)+1 种基金the Development Plan of Science and Technology of Jilin Province,China(YDZJ202301ZYTS280)the Natural Science Foundation of Jilin Province(YDZJ202401316ZYTS)。
文摘Lithium-sulfur(Li-S)chemistry reaction opens a new battery era with high energy density;meanwhile,multiple electrons migration leads to the complex phase transition of sulfur species.To manipulate the binding strength of multiple key intermediates more efficiently,the bimetallic TiVC MXene is utilized to realize multi-dimensional catalysis.Based on the macroscopic three-dimensional(3D)structure using two-dimensional(2D)MXene architecture,electron conductivity and sulfur utilization are improved.Microscopically,Ti-V catalytic systems regulate multiple reaction intermediates through intermetallic synergies customized surface properties and atomic scale coordination,thereby improving electronic and ionic conductivity.In-situ Raman spectroscopy and electrochemical analysis show that the conversion rate of polysulfides was accelerated during the charge-discharge process.The Ti-V interaction exhibits unique catalytic activity and regulates multiple continuous processes of sulfur species phase transformation,which are essential for the excellent energy performance of Li-S batteries.This study not only clarifies the catalytic mechanism of Ti-V at different dimensions but also proposes a promising strategy for the design of advanced catalytic systems in energy storage technology.
文摘A functional interlayer based on two-dimensional(2D)porous modified vermiculite nanosheets(PVS)was obtained by acid-etching vermiculite nanosheets.The as-obtained 2D porous nanosheets exhibited a high specific surface area of 427 m^(2)·g^(-1)and rich surface active sites,which help restrain polysulfides(LiPSs)through good physi-cal and chemical adsorption,while simultaneously accelerating the nucleation and dissolution kinetics of Li_(2)S,effec-tively suppressing the shuttle effect.The assembled lithium-sulfur batteries(LSBs)employing the PVS-based inter-layer delivered a high initial discharge capacity of 1386 mAh·g^(-1)at 0.1C(167.5 mAh·g^(-1)),long-term cycling stabil-ity,and good rate property.
文摘Lithium-sulfur(Li-S)batteries have great promise for next-generation energy storage devices due to the high theoretical specific capacity(1675 mAh g^(-1))of sulfur with chemical conversion for charge storage.However,their practical use is hindered by the slow redox kinetics of sulfur and the“shuttle effect”arising from dissolved lithium polysulfides(LiPSs).In recent years,various carbon-based materials have served as sulfur hosts and catalysts for accelerating sulfur conversion redox kinetics and alleviating LiPS shuttling.However,they often suffer from irreversible passivation and structural changes that destroy their long-term performance.We consider the main problems limiting their stability,including excessive LiPS adsorption,passivation by insulating Li2S,and surface reconstruction,and clarify how these factors lead to capacity fade.We then outline effective strategies for achieving long-term sulfur catalysis,focusing on functional carbon,such as designing suitable carbon-supported catalyst interfaces,creating well-distributed active sites,adding cocatalysts to improve electron transfer,and using carbon-based protective layers to suppress unwanted side reactions.Using this information should enable the development of stable,high-activity catalysts capable of long-term operation under practical conditions in Li-S batteries.
文摘Lithium-sulfur batteries are considered as one of the potential solutions as integrating renewable energy systems for large-scale energy storage because of their high theoretical energy density(2600 Wh·kg^(-1))and specific capacity(1675 mAh·g^(-1)).Currently,various strategies have been proposed to overcome the technical barriers,e.g.,“shuttle effect”,capacity decay and volumetric change,which impede the successful commercialization of lithium-sulfur batteries.This paper reviews the applications of metal nitrides as the cathode hosts for high-performance lithium-sulfur batteries,summa-rizes the design strategies of different host materials,and discusses the relationship between the properties of metal nitrides and their electrochemical performances.Finally,reasonable suggestions for the design and development of metal nitrides,along with ideas to promote future breakthroughs,are proposed.We hope that this review could attract more attention to metal nitrides and their derivatives,and further promote the electrochemical performance of lithium-sulfur batteries.
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 Beijing Natural Science Foundation(Nos.2232037 and 2242035)the National Natural Science Foundation of China(Nos.22005012,22105012 and 51803183)+1 种基金Chunhui Plan Cooperative Project of Ministry of Education(No.202201298)the China Postdoctoral Science Foundation Funded Project(No.2023M733520).
文摘Lithium-sulfur(Li-S)batteries with high energy density and capacity have garnered significant research attention among various energy storage devices.However,the shuttle effect of polysulfides(LiPSs)remains a major challenge for their practical application.The design of battery separators has become a key aspect in addressing the challenge.MXenes,a promising two-dimensional(2D)material,offer exceptional conductivity,large surface area,high mechanical strength,and active sites for surface reactions.When assembled into layered films,MXenes form highly tunable two-dimensional channels ranging from a few angstroms to over 1 nm.These nanoconfined channels are instrumental in facilitating lithium-ion transport while effectively impeding the shuttle effect of LiPSs,which are essential for improving the specific capacity and cyclic stability of Li-S batteries.Substantial progress has been made in developing MXenes-based separators for Li-S batteries,yet there remains a research gap in summarizing advancements from the perspective of interlayer engineering.This entails maintaining the 2D nanochannels of layered MXenes-based separators while modulating the physicochemical environment within the MXenes interlayers through targeted modifications.This review highlights advancements in in situ modification of MXenes and their integration with 0D,1D,and 2D materials to construct laminated nanocomposite separators for Li-S batteries.The future development directions of MXenes-based materials in Li-S energy storage devices are also outlined,to drive further advancements in MXenes for Li-S battery separators.
基金funded by the Alfaisal University grant number 726174.
文摘Lithium-sulfur batteries have been developing in recent years and appear to offer an alternative to existing commercial batteries that can potentially replace them in the future.With their exceptional theoretical energy density,lower production costs,and affordable and environmentally friendly abundant raw materials,lithium-sulfur batteries have shown the ability to defeat counterparts in the race for rechargeable energy devices currently being developed.The lithium-sulfur batteries display extraordinary features,but they suffer from sulfur's non-conductivity,the shuttle effect that results from polysulfide dissolution,volumetric sulfur changes during charging,and dendrites at the anode,resulting in a decline in capacity and a short battery life.As a result of rigorous and innovative engineering designs,lithium-sulfur batteries have been developed to overcome their drawbacks and utilize their entire potential during the past decade.This review will pay particular attention to porous carbon-based matrix materials,especially graphene-based nanocomposites that are most commonly used in producing sulfur cathodes.We provide an in-depth perspective on the structural merits of graphene materials,the detailed mechanism by which they interact with sulfur,and essential strategies for designing high-performance cathodes for lithium-sulfur batteries.Finally,we discuss the significant challenges and prospects for developing lithium-sulfur batteries with high energy density and long cycle lives for the next-generation electric vehicles.
基金financially supported by the National Key R&D Program of China(No.2022YFB2502000)the National Natural Science Foundation of China(Nos.51902079,52072342,52377216 and 52102324)+3 种基金Anhui Provincial Natural Science Foundation(Nos.2008085QE271 and 2208085ME108)Excellent Research and Innovation Team of Anhui Universities(No.2022AH010096)Natural Science Research Project for Anhui Universities(No.2024AH051519)Hefei Institutes of Physical Science,Chinese Academy of Sciences Director's Fund(Nos.BJPY2023B04,YZJJ-GGZX-2022-01 and YZJJ202102)
文摘Lithium sulfide(Li_(2)S)is widely regarded as the next-generation cathode material for rechargeable batteries due to its satisfactory theoretical capacity and excellent compatibility with lithium-free anodes.However,the large-scale applications of Li_(2)S cathodes are limited by the shuttle effect of soluble intermediate lithium polysulfides(LiPSs)and the sluggish redox kinetics of the interconversion between Li_(2)S and sulfur(S).Herein,we report novel nitrogen-doped carbon nanoflakes in-situ embedded with WN-Ni_(2)P heterostructures(WN-Ni_(2)P@NCN)as a multifunctional host to promote the cycling performance and reaction kinetics of Li_(2)S.After loading Li_(2)S,the WNNi_(2)P@NCN/Li_(2)S exhibits stable reversible capacity of 597mAh g^(-1)at 0.5 A g^(-1)over 150 cycles,and superior cycling stability over 800 cycles.The high reversible capacities,excellent cycling properties and superior reaction kinetics of WN-Ni_(2)P@NCN/Li_(2)S are attributed to the strong LiPSs fixation,remarkable catalytic activation and high electronic/ionic conductivity of the WN-Ni_(2)P@NCN framework,confirmed by the experiment and the density function theory calculation results.This work offers a new strategy for designing heterostructure nanoflakes with metal nitride and metal phosphide to facilitate the applications of advanced lithium-sulfur batteries.
基金supported by the Beijing Institute of Technology Research Fund Program for Young Scholars and 21C Innovation Laboratory Contemporary Amperex Technology Co.,Limited,Ninde,352100,China(21C-OP-202314)。
文摘Heteroatom doping has emerged as a powerful strategy to optimize the catalytic and adsorption abilities of electrocatalysts by regulating the electronic structure,thereby enabling the development of efficient electrocatalysts for lithium-sulfur(Li-S)batteries.However,the correlation between the properties of doped atoms and adsorptio n-catalytic ability,as well as the interconnection between adsorption strength and catalytic activity,remains underexplored.Herein,we employed halogen atoms(F,Cl,and Br)with different electronegativities to dope nickel phosphide(Ni_(2)P),aiming to modulate the adsorption properties toward lithium polysulfides(LiPSs).We systematically explored the relationship between the electronegativity of the doping atoms and the adsorption strength,followed by exploring the connection between adsorption and catalytic capabilities.Combined experimental and theoretical analyses reveal that doping halogen atoms effectively strengthens d-p orbital hybridization between Ni atoms and S atoms,thereby enhancing LiPSs anchoring and conversion.Specifically,the chemical adsorption capability is enhanced as the electronegativity of the doped atoms increases.Moreover,the catalytic activity presents a volcano-like trend with the enhancement of adsorption performance,wherein the activity initially increases and subsequently diminishes.Therefore,Cl-doped Ni_(2)P with moderate chemisorption ability exhibits optimal redox kinetics in bidirectional sulfur conversion.Consequently,the Li-S batteries with Cl-Ni_(2)P-separators deliver a high-rate capacity of 790 mAh g^(-1)at 5 C and achieve a remarkable areal capacity of 7.36 mAh cm^(-2)under practical conditions(sulfur loading:7.10 mg cm^(-2);electrolyte/sulfur(E/S)ratio:5μL mg^(-1)).This work uncovers the significance of achieving a balance between adsorption and catalytic capabilities,offering insights into designing efficient electrocatalysts for lithium-sulfur batteries.
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(22379069,22109072)the Fundamental Research Funds for the Central Universities(30922010304)。
文摘Lithium-sulfur(Li-S)batteries hold great promise for next-generation energy storage,yet suffer from sluggish redox kinetics and polysulfide shuttling.Herein,a novel Ni_(3)S_(2)/Ni_(2)B heterostructure is developed to improve sulfur electrochemistry by synergistically enhancing polysulfide fixation and catalytic conversions.Fabricated through mild sequential boronation and sulfurization,this hybrid nanocatalyst integrates the strong polysulfide adsorbability and high conductivity of Ni_(2)B with the high catalytic activity of Ni_(3)S_(2).More importantly,the as-constructed heterointerface inspires new,highly catalytic sites that smooth consecutive sulfur conversions with lower energy barriers,while the built-in electric fields promote directional charge transfer,collectively contributing to fast-kinetic and highly efficient sulfur redox reactions.As a result,Li-S cells incorporating the Ni_(3)S_(2)/Ni_(2)B nanocatalyst exhibit excellent cyclability,with minimal capacity decay of 0.017%per cycle over 900 cycles at 1 C and a superb rate capability of up to 5 C.Even under demanding conditions,such as a high sulfur loading of 5.0 mg cm^(-2)and a low electrolyte-to-sulfur(E/S)ratio of 4.8 mL g^(-1),high capacity and cyclability are maintained,highlighting the great potential of this unique heterointerface engineering in advancing high-performance and practically viable Li-S 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 the Hebei Province Key R&D Technology Project(23314401D)2023 Hebei Province High-level Talent Team Construction Special Project(235A4401D)+6 种基金Hebei North University Youth Fund Project(XJ2024013)School-level Cultivation Research Project of Hebei North University(XJPY2024025)First Batch of School-level Scientific Research Projects of Hebei North University in 2023(B2023405004)Hebei North University High-level Talent Research Start-up Fund(BSJJ202303,BSJJ202313,BSJJ202421)Science and Technology Research Project of Higher Education Institutions in Hebei Province(QN2023222)Central Guided Local Science and Technology Development Funding Program(236Z4401G)Natural Science Foundation of Hebei Province(B2022405005).
文摘Lithium-sulfur(Li-S)batteries are promising for high-energy-density storage,but their performance is limited by sluggish lithium polysulfide(LiPS)conversion kinetics.Here,we tackle this issue by synthesizing ultrafine truncated octahedral TiO_(2) nanocrystals(P-O_(v)-TiO_(2)),featuring specific{101}facets and dual defects—phosphorus doping and oxygen vacancies.Acting as an efficient electrocatalyst in the separator,P-O_(v)-TiO_(2) exhibits superior catalytic properties,where oxygen vacancies modulate the electronic structure,enhancing electron enrichment and charge transfer;phosphorus doping tailors the d-band center of the catalyst,strengthening Ti-S interactions between the{101}facets and LiPSs.As a result,Li-S coin cells modified with P-O_(v)-TiO_(2) achieve a high specific capacity of 895 mAh g^(−1) at 5 C and exhibit a minimal decay rate of 0.14%per cycle over 200 cycles.Furthermore,Li-S pouch cells deliver a high capacity of 1004 mAh g^(−1) at 0.1 C under lean electrolyte conditions.This study elucidates the mechanisms of charge states on specific crystal planes and deepens our understanding of dual-defect engineering in Li-S electrochemistry,offering a promising approach for developing efficient and cost-effective catalysts for Li-S battery applications.
基金supported by the National Natural Science Foundation of China(Grant Nos.52102302,22409161 and 52472249)the Young Talent Support Plan of Xi’an Jiaotong University(Grant No.DQ6J011)+4 种基金the Natural Science Foundation of Shaanxi Province(2023-JC-QN-0115)the China Postdoctoral Science Foundation(2022M712499)Beilin District Science and Technology Plan(GX2328)the support from Young Elite Scientists Sponsorship Program by Chinese Association for Science and Technologythe“High-Level Talent Introduction Plan”of Shaanxi Province and Siyuan Scholar of Xi’an Jiaotong University。
文摘Global interest in lithium-sulfur batteries as one of the most promising energy storage technologies has been sparked by their low sulfur cathode cost,high gravimetric,volumetric energy densities,abundant resources,and environmental friendliness.However,their practical application is significantly impeded by several serious issues that arise at the cathode-electrolyte interface,such as interface structure degradation including the uneven deposition of Li_(2)S,unstable cathode-electrolyte interphase(CEI)layer and intermediate polysulfide shuttle effect.Thus,an optimized cathode-electrolyte interface along with optimized electrodes is required for overall improvement.Herein,we comprehensively outline the challenges and corresponding strategies,including electrolyte optimization to create a dense CEI layer,regulating the Li_(2)S deposition pattern,and inhibiting the shuttle effect with regard to the solid-liquid-solid pathway,the transformation from solid-liquid-solid to solid-solid pathway,and solid-solid pathway at the cathode-electrolyte interface.In order to spur more perceptive research and hasten the widespread use of lithium-sulfur batteries,viewpoints on designing a stable interface with a deep comprehension are also put forth.
基金supported by the National Natural Science Foundation of China(Nos.21573059,12274118 and 22208088)Henan Center for Outstanding Overseas Scientists(No.GZS2023007)Special Project for Fundamental Research in University of Henan Province(No.22ZX013)。
文摘Sluggish sulfur conversion kinetics pose an ongoing challenge in lithium-sulfur batteries(LSBs).Here,we present a solution through far-reaching long-range electronic regulation(LRER)on single-atom active sites.N-doped carbons(Co-NC)are implanted with densely-distributed Co single atoms,and supported on Ti_(3)C_(2)T_(x)MXene substrates to assemble 3D Co-NC/MXene catalyst.MXene effectively mediates interlayer charge transfer(~0.70|e|)contrasted with popular carbon materials(~0.06|e|)to produce LRER through surrounding carbon atoms.The synergy of LRER with near-range electronic regulation(NRER)tunes electronic structures,and enhances heterostructural stability,thus provoking desirous catalytic kinetics of Co single atoms in sulfur reduction.Thereby,the Co-NC/MXene/S cathodes exhibit impressive rate performance and excellent cycling stability(only 0.015%capacity decay per cycle over 600 cycles at 4 C)in LSBs,surpassing state-of-the-art sulfur cathodes.This work reveals the importance of LRER for improved catalysis,and provides new guidance to tailor heterostructures to achieve high-efficient catalysts in various process.
基金supported by the Research Funding of Hangzhou International Innovation Institute of Beihang University(Grant No.2024KQ102 and 2024KQ131)the National Natural Science Foundation of China(Grant No.524B2020,51925202,U22A20141,52432004,U23A20575,52472183,and 22379039).
文摘Lithium-sulfur batteries(LSBs)hold significant promise as advanced energy storage systems due to their high energy density,low cost,and environmental advantages.However,despite recent advancements,their practical energy density still falls short of the levels required for commercial viability.The energy density is critically dependent on both sulfur loading and the amount of electrolyte used.Highsulfur loading coupled with lean electrolyte conditions presents several challenges,including the insulating nature of sulfur and Li_(2)S,insufficient electrolyte absorption,degradation of the cathode structure,severe lithium polysulfide shuttling,slow redox reaction kinetics,and instability of the Li metal anode.MXenes-based materials,with their metallic conductivity,large polar surfaces,and abundant active sites,have been identified as promising electrocatalysts to improve the redox reactions in LSBs.This review focuses on the significance and challenges associated with high-sulfur loading and lean electrolytes in LSBs,highlighting recent advancements in MXenes-based electrocatalysts aimed at optimizing sulfur cathodes and lithium anodes.It provides a comprehensive discussion on MXenes as both active materials and substrates in LSBs,with the goal of enhancing understanding of the regulatory mechanisms that govern sulfur conversion reactions and lithium plating/stripping behavior.Finally,the review explores future opportunities for MXenes-based electrocatalysts,paving the way for the practical application of LSBs.
基金supported by National Natural Science Foundation of China(No.22309029)Guangdong Basic and Applied Basic Research Foundation(No.2021A1515110089)+2 种基金Dongguan Social Development Technology Foundation(No.20231800907933)Collaborative Innovation Center of Marine Science and Technology of Hainan University(No.XTCX2022HYC14)Start-up Research Foundation of Hainan University(No.KYQD(ZR)-23069)。
文摘Active sulfur dissolution and shuttle effect of lithium polysulfides(LiPSs)are the main obstacles hindering the practical application of lithium-sulfur batteries(LSBs),which is primarily induced by the direct interaction between sulfur-loading cathode and liquid electrolyte.The introduction of functional interlayer within the separator and cathode is an effective strategy to stabilize the electrode/electrolyte interface reaction and improve the utilization rate of active sulfur.Herein,conductive composite nanofabrics(CCN)with multifunctional groups are employed as the interlayer of sulfur-loading cathode,in which the PMIA/PAN supporting fibers offer robust mechanical strength and high thermostable performance,and gelatin/polypyrrole functional fibers ensure high electrical conductivity and strong chemical interaction for LiPSs.As demonstrated by the experimental data and material characterizations,the presence of CCN interlayer not only blocks the shuttle behavior of LiPSs,but also strengthens the interface stability of both Li anode and sulfur-loading cathode.Interestingly,the assembled LSBs with CCN interlayer can maintain stable capacity of 686 mAh/g after 200 cycles at 0.5 A/g.This work will provide new ideas for the elaborate design of functional in terlayers/se para tors for LSBs and lithium metal batteries.
基金supported financially by the National Natural Science Foundation of China(52172242,22109135,52371237)the Science&Technology Talents Lifting Project of Hunan Province(2023TJ-Z32)+2 种基金the Hunan Provincial Education Office Foundation of China(20B570,23B0126)the Natural Science Foundation of Hunan Province(2021JJ30659,2022JJ40423)the Postgraduate Scientific Research Innovation Project of Hunan Province(QL20230146).
文摘The polysulfide shuttle effect critically hinders lithium-sulfur(Li-S)battery development,therefore,the design of heterogeneous interface engineering with“adsorption-catalysis”functions for polysulfide conversion has garnered considerable attention.However,the exploration of the intricate relationship between key electronic properties and catalytic activity at such interfaces remains a challenge.Additionally,a comprehensive understanding of the thermodynamic growth mechanisms for heterostructure materials is lacking.Herein,a Ni-based homologous structure was precisely constructed via thermodynamic control,with a specific focus on optimizing the interface design.The theoretical results show that the heterostructures with adjustable composition realize the appropriate upward shift to the D-band,improving the affinity towards polysulfide,and further reducing the reaction energy barrier.On this basis,the relationship between interface design and the D-band center,as well as catalytic performance,was established.Specifically,M-Ni_(3)Fe/Ni_(3)ZnC_(0.7)accomplishes the electron enrichment at the interface,supporting the further diffusion of polysulfides,and lowering the Li-S bond energy,performing the bidirectional catalytic transformation of polysulfides.As a result,the Li-S batteries with the cathode of M-Ni_(3)Fe/Ni_(3)ZnC_(0.7)/S deliver rate performances of discharge capacity of 514 mA h g^(−1)at 5.0 C.This understanding of the D-band and interfacial design provides a framework for Li-S catalyst optimization.
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.
