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
Lithium–sulfur(Li–S)batteries are supposed to be one of the most potential next-generation batteries owing to their high theoretical capacity and low cost.Nevertheless,the shuttle effect of firm multi-step two-elect...Lithium–sulfur(Li–S)batteries are supposed to be one of the most potential next-generation batteries owing to their high theoretical capacity and low cost.Nevertheless,the shuttle effect of firm multi-step two-electron reaction between sulfur and lithium in liquid electrolyte makes the capacity much smaller than the theoretical value.Many methods were proposed for inhibiting the shuttle effect of polysulfide,improving corresponding redox kinetics and enhancing the integral performance of Li–S batteries.Here,we will comprehensively and systematically summarize the strategies for inhibiting the shuttle effect from all components of Li–S batteries.First,the electrochemical principles/mechanism and origin of the shuttle effect are described in detail.Moreover,the efficient strategies,including boosting the sulfur conversion rate of sulfur,confining sulfur or lithium polysulfides(LPS)within cathode host,confining LPS in the shield layer,and preventing LPS from contacting the anode,will be discussed to suppress the shuttle effect.Then,recent advances in inhibition of shuttle effect in cathode,electrolyte,separator,and anode with the aforementioned strategies have been summarized to direct the further design of efficient materials for Li–S batteries.Finally,we present prospects for inhibition of the LPS shuttle and potential development directions in Li–S batteries.展开更多
Lithium-sulfur batteries(LSBs)have attracted the attention of more and more researchers due to the advantages of high energy density,environmental friendliness,and low production cost.However,the low electronic conduc...Lithium-sulfur batteries(LSBs)have attracted the attention of more and more researchers due to the advantages of high energy density,environmental friendliness,and low production cost.However,the low electronic conductivity of active material and shuttling effect of lithium polysulfides(LiPSs)limit the commercial development of LSBs.To solve these problems,we design a core-shell composite with nitrogen-doped carbon(NC)and two types of selenides(FeSe_(2)-NC@ZnSe-NC).The FeSe_(2)-NC@ZnSe-NC has a strong adsorption capacity,and can effectively adsorb LiPSs.At the same time,it also effectively alleviates the shuttling effect of LiPSs,and improves the utilization of the active substance during the charge/discharge reaction processes.The mechanism involved in FeSe_(2)-NC@ZnSe-NC is demonstrated by both experiments and density-functional theory(DFT)calculations.The electrochemical test results indicate that LSB with S/FeSe_(2)-NC@ZnSe-NC delivers an initial discharge capacity of 1260 mAh·g^(-1)at 0.2C.And after 500 cycles at 1C,the capacity decay rate per cycle is 0.031%,and the capacity retention rate is 85%.The FeSe_(2)-NC@ZnSe-NC core-shell structure verifies a rational strategy to construct an electrode material for high-performance LSBs.展开更多
Lithium-sulfur battery(LSB) has high energy density but is limited by the polysulfides shuttle and dendrite growth during cycling. Herein, a free-standing cellulose nanofiber(CNF) separator is designed and fabricated ...Lithium-sulfur battery(LSB) has high energy density but is limited by the polysulfides shuttle and dendrite growth during cycling. Herein, a free-standing cellulose nanofiber(CNF) separator is designed and fabricated in isopropanol/water suspension through vacuum filtration progress. CNFs with abundant polar oxygen-containing functional groups can chemically immobilize the polysulfides, and suppress the formation of the dendrites by controlling the surface morphology of the SEI on lithium metal in LSB. The isopropanol content in a suspension can fine-tune the pore structure of the membrane to achieve optimal electrochemical performance. The prepared separator displays integrated advantages of an ultrathin thickness(19 μm), lightweight(0.87 mg cm^(-2)), extremely high porosity(98.05%), and decent electrolyte affinity. As a result, the discharge capacity of the LSB with CNF separator at the first and 100 th cycle is 1.4 and 1.3 times that of PP separator, respectively. Our research provides an environmentalfriendly and facile strategy for the preparation of multifunctional separators for LSBs.展开更多
The polysulfides shuttle effect represents a great challenge in achieving high capacity and long lifespan of lithium/sulfur(Li/S)cells.A comprehensive understanding of the shuttle-related sulfur speciation and diffusi...The polysulfides shuttle effect represents a great challenge in achieving high capacity and long lifespan of lithium/sulfur(Li/S)cells.A comprehensive understanding of the shuttle-related sulfur speciation and diffusion process is vital for addressing this issue.Herein,we employed in situ/operando X-ray absorption spectroscopy(XAS)to trace the migration of polysulfides across the Li/S cells by precisely monitoring the sulfur chemical speciation at the cathodic electrolyte-separator and electrolyte-anode interfaces,respectively,in a real-time condition.After we adopted a shuttle-suppressing strategy by introducing an electrocatalytic layer of twinborn bismuth sulfide/bismuth oxide nanoclusters in a carbon matrix(BSOC),we found the Li/S cell showed greatly improved sulfur utilization and longer life span.The operando S Kedge XAS results revealed that the BSOC modification was bi-functional:trapping polysulfides and catalyzing conversion of sulfur species simultaneously.We elucidated that the polysulfide trapping-and-catalyzing effect of the BSOC electrocatalytic layer resulted in an effective lithium anode protection.Our results could offer potential stratagem for designing more advanced Li/S cells.展开更多
Rechargeable lithium-oxygen(Li-O_(2))batteries are the next generation energy storage devices due to their ultrahigh theoretical capacity.Redox mediators(RMs)are widely used as a homogenous electrocatalyst in non-aque...Rechargeable lithium-oxygen(Li-O_(2))batteries are the next generation energy storage devices due to their ultrahigh theoretical capacity.Redox mediators(RMs)are widely used as a homogenous electrocatalyst in non-aqueous Li-O_(2)batteries to enhance their discharge capacity and reduce charge overpotential.However,the shuttle effect of RMs in the electrolyte solution usually leads to corrosion of the Li metal anode and uneven Li deposition on the anode surface,resulting in unwanted consumption of electrocatalysts and deterioration of the cells.It is therefore necessary to take some measures to prevent the shuttle effect of RMs and fully utilize the soluble electrocatalysts.Herein,we summarize the strategies to suppress the RM shuttle effect reported in recent years,including electrolyte additives,protective separators and electrode modification.The mechanisms of these strategies are analyzed and their corresponding requirements are discussed.The electrochemical properties of Li-O_(2)batteries with different strategies are summarized and compared.The challenges and perspectives on preventing the shuttle effect of RMs are described for future study.This review provides guidance for achieving shuttle-free redox mediation and for designing Li-O_(2)cells with a long cycle life,high energy efficiency and highly reversible electrochemical reactions.展开更多
Polysulfide absorption in a micropore-rich structure has been reported to be capable of efficiently confining the shuttle effect for high-performance lithium-sulfur(Li–S)batteries.Here,a labyrinth maze-like spherical...Polysulfide absorption in a micropore-rich structure has been reported to be capable of efficiently confining the shuttle effect for high-performance lithium-sulfur(Li–S)batteries.Here,a labyrinth maze-like spherical honeycomb-like carbon with micropore-rich structure was synthesized,which is employed as a template host material of sulfur to study the shuttle effects.The results strongly confirm that a diffusion controlled process rather than an absorption resulted surface-controlled process occurs in an even micropore-rich cathode but still greatly inhibits the shuttle effect.Thus,the battery achieves a high initial discharge specific capacity of 1120 mAh g1 at 0.25 C and super cycling stability for 1635 cycles with only 0.035%capacity decay per cycle with 100%Coulombic efficiency.We would like to propose a new mechanism for shuttle effect inhibition in micropores.In terms of the diffusion control process in microporous paths of a labyrinth maze structure,polysulfides experience a long travel to realize continuous reductions of sulfur and polysulfides until formation of the final solid product.This efficiently prevents the polysulfides escaping to electrolyte.The labyrinth maze-like honeycomb structure also offers fast electron transfer and enhanced mass transport as well as robust mechanical strength retaining intact structure for long cycle life.This work sheds lights on new fundamental insights behind the shuttle effects with universal significance while demonstrating prominent merits of a robust labyrinth maze-like structure in high performance cathode for high-performance Li–S batteries.展开更多
Rechargeable aluminum-sulfur(Al-S)batteries have been considered as a highly potential energy storage system owing to the high theoretical capacity,good safety,abundant natural reserves,and low cost of Al and S.Howeve...Rechargeable aluminum-sulfur(Al-S)batteries have been considered as a highly potential energy storage system owing to the high theoretical capacity,good safety,abundant natural reserves,and low cost of Al and S.However,the research progress of Al-S batteries is limited by the slow kinetics and shuttle effect of soluble polysulfides intermediates.Herein,an interconnected free-standing interlayer of iron sin-gle atoms supported on porous nitrogen-doped carbon nanofibers(FeSAs-NCF)on the separator is developed and used as both catalyst and chemical barrier for Al-S batteries.The atomically dispersed iron active sites(Fe-N_(4))are clearly identified by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption near-edge structure.The Al-S battery with the FeSAs-NCF shows an improved specific capacity of 780 mAh g^(−1)and enhanced cycle stability.As evidenced by experimental and theoretical results,the atomically dispersed iron active centers on the separator can chemically adsorb the polysulfides and accelerate reaction kinetics to inhibit the shuttle effect and promote the reversible conversion between aluminum polysulfides,thus improving the electrochemical performance of the Al-S battery.This work provides a new way that can not only promote the conversion of aluminum sulfides but also suppress the shuttle effect in Al-S batteries.展开更多
According to a statistic,approximately 6 trillion cigarettes are smoked each year all over the world,which produces approximately 1.2 million tons of discarded cigarette butts.The discarded cigarette filters are non-b...According to a statistic,approximately 6 trillion cigarettes are smoked each year all over the world,which produces approximately 1.2 million tons of discarded cigarette butts.The discarded cigarette filters are non-biodegradable,thus they produce a mass of waste disposal and cause environmental pollution is-sue.For the purpose of transforming waste into wealth and reducing environmental pollution,nitrogen and sulfur co-doped carbon nanofiber/carbon black(N,S-CNF/CB)composite derived from the discarded cigarette filters is employed to modify glass fiber(GF)separator for the first time in this study.N,S-CNF improves binding ability towards sodium polysulfides(SPSs)by chemisorption.Non-polar CB limits the dissolution of SPSs in the liquid electrolyte by physisorption.The experiment and density functional theory calculation results indicate that a RT-Na/S battery with a N,S-CNF/CB+GF separator exhibits good cycling stability and rate performance.After 100 cycles at a low current rate of 0.1 C,a RT-Na/S battery with a sulfur mass fraction of 71%delivers a discharge capacity of 703 mAh g^(−1).In addition,at a high current rate of 0.5 C,a discharge capacity of 527 mAh g^(−1) is still maintained after 900 cycles with a very low capacity fading rate of 0.035%per cycle.展开更多
In practical lithium-sulfur batteries(LSBs),the shuttle effect and Li cycling coulombic efficiency(CE) are strongly affected by the physicochemical properties of solid electrolyte interphase(SEI).LiNO_(3) is widely us...In practical lithium-sulfur batteries(LSBs),the shuttle effect and Li cycling coulombic efficiency(CE) are strongly affected by the physicochemical properties of solid electrolyte interphase(SEI).LiNO_(3) is widely used as an additive in electrolytes to build a high-quality SEI,but its self-sacrificial nature limits the ability to mitigate the shuttle effect and stabilize Li anode during long-term cycling.To counteract LiNO_(3) consumption during long-term cycling without using a high initial concentration,inspired by sustainedrelease drugs,we encapsulated LiNO_(3) in lithiated Nafion polymer and added an electrolyte co-solvent(1,1,2,2-tetrafluoroethylene 2,2,2-trifluoromethyl ether) with poor LiNO_(3) solubility to construct highquality and durable F-and N-rich SEI.Theoretical calculations,experiments,multiphysics simulations,and in-situ observations confirmed that the F-and N-rich SEI can modulate lithium deposition behavior and allow persistent repair of SEI during prolonged cycling.Hence,the F-and N-rich SEI improves the Li anode cycling CE to 99.63% and alleviates the shuttle effect during long-term cycling.The lithium anode with sustainable F-and N-rich SEI shows a stable Li plating/stripping over 2000 h at 1 mA cm^(-2).As expected,Li‖S full cells with this SEI achieved a long lifespan of 250 cycles,far exceeding cells with a routine SEI.The Li‖S pouch cell based on F-and N-rich SEI also can achieve a high energy density of about300 Wh kg^(-1) at initial cycles.This strategy provides a novel design for high-quality and durable SEls in LSBs and may also be extendable to other alkali metal batteries.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
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
Lithium-sulfur batteries(LSBs)have attracted widespread attention due to their high theoretical energy density.However,the dissolution of long-chain polysulfides into the electrolyte(the“shuttle effect”)leads to rap...Lithium-sulfur batteries(LSBs)have attracted widespread attention due to their high theoretical energy density.However,the dissolution of long-chain polysulfides into the electrolyte(the“shuttle effect”)leads to rapid capacity decay.Therefore,finding suitable materials to mitigate the shuttle effect of polysulfides is crucial for enhancing the electrochemical performance of lithium-sulfur batteries.In this study,LSBs’separator is modified with Ni_(3)V_(2)O_(8)nanoparticles@carboxylated carbon nanotubes(Ni_(3)V_(2)O_(8)@CNTs)composite.There are abundant oxygen vacancies in Ni_(3)V_(2)O_(8)@CNTs composite which plays a synergistic effect on shuttle effect.The Ni_(3)V_(2)O_(8)can tightly anchor soluble polysulfides through oxygen vacancies,while the CNTs not only facilitate the transport of ions and electrons but also weaken the migration of polysulfides,limiting shuttle effect.As a result,the cycling stability of LSBs using Ni_(3)V_(2)O_(8)@CNTs-modified separator has been significantly improved(with a capacity decay rate of only 0.0334%after 1500 cycles at 4.0C).This study proposes a strategy to design modified separator for high-performance LSBs.展开更多
Maximizing the fixing ability of polyselenides to reduce the shuttle effect in Li-Se batteries remains highly challenging.Single crystal metal-organic framework(MOF)-derived N-doped ordered hierarchically porous carbo...Maximizing the fixing ability of polyselenides to reduce the shuttle effect in Li-Se batteries remains highly challenging.Single crystal metal-organic framework(MOF)-derived N-doped ordered hierarchically porous carbon(SNOHPC)synthesized by a confined crystal growth and template-assisted method demonstrates excellent electrochemical performance as a host material for Li-Se battery.The large number of micropores inherited from the MOF structure provides large space and surface for Se loading and reaction sites,ensuring the high energy density of the battery.The insitu X-ray diffraction(XRD)technique is used to understand the reaction mechanism.The synergy of the interconnected three-scale-level micro-meso-macroporous structure and Ndoped polar sites can buffer the volume expansion,shorten the ion transportation with a very high diffusion coefficient of4.44×10cm^(2)sand accelerate the lithiation/delithiation reaction.Selenium is sufficiently reactive and the polyselenide intermediates are tightly fixed inside the carbon host material,thereby achieving excellent specific capacity,stability,and rate capability.Such a cathode exhibits a very high 2discharge/charge capacity of 658 and 683 mA h g,respectively,and retains a very high capacity of 367 mA h gafter 200 cycles at the current of 0.2 C.Even at the high current of 5 C,a very high discharge capacity of 230 mA h gis obtained.This work provides a new kind of high-performance porous materials with rational pore arrangement applicable for highly efficient energy storage.展开更多
Lithium-sulfur batteries(LSBs)have already developed into one of the most promising new-generation high-energy density electrochemical energy storage systems with outstanding features including high-energy density,low...Lithium-sulfur batteries(LSBs)have already developed into one of the most promising new-generation high-energy density electrochemical energy storage systems with outstanding features including high-energy density,low cost,and environmental friendliness.However,the development and commercialization path of LSBs still presents significant limitations and challenges,particularly the notorious shuttle effect triggered by soluble longchain lithium polysulfides(LiPSs),which inevitably leads to low utilization of cathode active sulfur and high battery capacity degradation,short cycle life,etc.Substantial research efforts have been conducted to develop various sulfur host materials capable of effectively restricting the shuttle effect.This review firstly introduces the fundamental electrochemical aspects of LSBs,followed by a comprehensive analysis of the mechanism underlying the shuttle effect in Li–S batteries and its profound influence on various battery components as well as the overall battery performance.Subsequently,recent advances and strategies are systematically reviewed,including physical confinement,chemisorption,and catalytic conversion of sulfur hosts for restricting LiPSs shuttle effects.The interplay mechanisms of sulfur hosts and LiPSs are discussed in detail and the structural advantages of different host materials are highlighted.Furthermore,key insights for the rational design of advanced host materials for LSBs are provided,and the upcoming challenges and the prospects for sulfur host materials in lithium-sulfur batteries are also explored.展开更多
Lithium sulfur(Li-S)battery is a kind of burgeoning energy storage system with high energy density.However,the electrolyte-soluble intermediate lithium polysulfides(Li PSs)undergo notorious shuttle effect,which seriou...Lithium sulfur(Li-S)battery is a kind of burgeoning energy storage system with high energy density.However,the electrolyte-soluble intermediate lithium polysulfides(Li PSs)undergo notorious shuttle effect,which seriously hinders the commercialization of Li-S batteries.Herein,a unique VSe_(2)/V_(2)C heterostructure with local built-in electric field was rationally engineered from V_(2)C parent via a facile thermal selenization process.It exquisitely synergizes the strong affinity of V_(2)C with the effective electrocatalytic activity of VSe_(2).More importantly,the local built-in electric field at the heterointerface can sufficiently promote the electron/ion transport ability and eventually boost the conversion kinetics of sulfur species.The Li-S battery equipped with VSe_(2)/V_(2)C-CNTs-PP separator achieved an outstanding initial specific capacity of 1439.1 m A h g^(-1)with a high capacity retention of 73%after 100 cycles at0.1 C.More impressively,a wonderful capacity of 571.6 mA h g^(-1)was effectively maintained after 600cycles at 2 C with a capacity decay rate of 0.07%.Even under a sulfur loading of 4.8 mg cm^(-2),areal capacity still can be up to 5.6 m A h cm^(-2).In-situ Raman tests explicitly illustrate the effectiveness of VSe_(2)/V_(2)C-CNTs modifier in restricting Li PSs shuttle.Combined with density functional theory calculations,the underlying mechanism of VSe_(2)/V_(2)C heterostructure for remedying Li PSs shuttling and conversion kinetics was deciphered.The strategy of constructing VSe_(2)/V_(2)C heterocatalyst in this work proposes a universal protocol to design metal selenide-based separator modifier for Li-S battery.Besides,it opens an efficient avenue for the separator engineering of Li-S batteries.展开更多
The commercialization of lithium-sulfur(Li-S)batteries faces several bottlenecks,and the major two of which are the shuttle effect of polysulfides and the wild growth of Li dendrites,responsible for fast capacity deca...The commercialization of lithium-sulfur(Li-S)batteries faces several bottlenecks,and the major two of which are the shuttle effect of polysulfides and the wild growth of Li dendrites,responsible for fast capacity decay and severe safety issues.As an essential component of Li-S batteries,the structure and properties of the separators are closely related to the above problems,and the exploration of multifunctional separators is highly sought-after.Herein,an integrated separator composited of defective graphene and polyimide(DG-PI)was innovatively fabricated by electrospinning combined with the laser-induced carbonization strategy.The all-in-one compact architecture with well-interconnected channels shows superior mechanical and thermal stability and wettability.More importantly,the PI nanofibers containing N–/O–functional groups can induce the uniform deposition of lithium on the anode surface,while the DG framework with abundant pentagonal/heptagonal rings and vacancies can strongly trap polysulfides and accelerate polysulfide transformation on the cathode side.The strong chemical interaction between the insulative PI layer and the conductive DG layer modulates the surface charge distribution of each other,leading to more prominent contributions to restraining lithium dendrites and shuttle effect.Therefore,the Li-S batteries based on the integrated DG-PI separators afford an excellent performance in protecting lithium anode(stable cycles of 200 h at 5 mA·cm^(−2))and good cycling stability with a low capacity decay of 0.05%per cycle after 700 cycles at 1 C.This work offers a new design concept of multifunctional Li-S battery separators and broadens the application scope of laser micro-nano fabrication technology.展开更多
Lithium-oxygen(Li-O_(2))batteries have a great potential in energy storage and conversion due to their ultra-high theoretical specific energy,but their applications are hindered by sluggish redox reaction kinetics in ...Lithium-oxygen(Li-O_(2))batteries have a great potential in energy storage and conversion due to their ultra-high theoretical specific energy,but their applications are hindered by sluggish redox reaction kinetics in the charge/discharge processes.Redox mediators(RMs),as soluble catalysts,are widely used to facilitate the electrochemical processes in the Li-O_(2)batteries.A drawback of RMs is the shuttle effect due to their solubility and mobility,which leads to the corrosion of a Li metal anode and the degradation of the electrochemical performance of the batteries.Herein,we synthesize a polymer-based composite protective separator containing molecular sieves.The nanopores with a diameter of 4Åin the zeolite powder(4A zeolite)are able to physically block the migration of 2,2,6,6-tetramethylpiperidinyloxy(TEMPO)molecules with a larger size;therefore,the shuttle effect of TEMPO is restrained.With the assistance of the zeolite molecular sieves,the cycle life of the Li-O_(2)batteries is significantly extended from~20 to 170 cycles at a current density of 250 mA·g^(-1)and a limited capacity of 500 mAh·g^(-1).Our work provides a highly effective approach to suppress the shuttle effects of RMs and boost the electrochemical performance of Li-O_(2)batteries.展开更多
Rechargeable aqueous zinc-iodine(Zn-I_(2))batteries are widely regarded as a promising contender for energy-storage devices,due to their intrinsic safety,low cost,and high capacity.However,the severe shuttle effect of...Rechargeable aqueous zinc-iodine(Zn-I_(2))batteries are widely regarded as a promising contender for energy-storage devices,due to their intrinsic safety,low cost,and high capacity.However,the severe shuttle effect of polyiodides and the large volume change of I_(2)cathode induce severe capacity loss and poor electrochemical reversibility,hindering their commercial applications.Herein,we report that the low-cost gelatinized starch(Gstarch)can be used as a bifunctional binder for Zn-I_(2)batteries to circumvent the above problems simultaneously.Based on both calculation and experimental data,it is demonstrated that the double-helix structure of G-starch with bothα-1,4-andα-1,6-glycosidic bonds can strongly interact with polyiodides to suppress the shuttle effect.Moreover,the G-starch with multiple hydrogen-bonded cross-linking networks exhibits a much-enhanced adhesion ability and can buffer the volume expansion of active materials.In contrast,the traditional carboxymethyl cellulose sodium-based aqueous binder lacks these capabilities.As a result,the G-starch binder enables the aqueous Zn-I_(2)battery to achieve a high reversible capacity of212.4 mAh·g^(-1)at 0.2 A·g^(-1)after 1000 cycles and ultralong-cycling life over 48,000 cycles with 135.4 mAh·g^(-1)and 89.6%capacity retention at 2 A·g^(-1).This work develops a simple yet efficient strategy to construct highperformance Zn-I_(2)batteries.展开更多
Metal-iodine batteries have attracted widespread attention due to their long cycle life,high energy density,remarkable charging capability and low self-discharge rate.Nevertheless,this development is hampered by the c...Metal-iodine batteries have attracted widespread attention due to their long cycle life,high energy density,remarkable charging capability and low self-discharge rate.Nevertheless,this development is hampered by the challenges of the iodine cathode and metal anode,including the hydrogen evolution reaction(HER),sluggish kinetics,shuttle effect of polyiodine ion at the cathode and dendrite formation,corrosion and passivation at the anode.This review summarizes recent developments in metaliodine batteries,including zinc-iodine batteries,lithiumiodine batteries,sodium-iodine batteries,etc.The challenges in the cathode,anode,electrolyte and separator of metal-iodine batteries are discussed,along with the corresponding design and synthesis strategies and specific methods to improve the electrochemical performance.Selecting appropriate cathode hosts,constructing surface protective layers,adding anode additives,making threedimensional anode designs and employing better electrolytes and functional separators to obstruct the production and shuttling of polyiodine ions are highlighted.Finally,future guidelines and directions for the development of metal-iodine batteries are proposed.展开更多
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support from the “Joint International Laboratory on Environmental and Energy Frontier Materials”“Innovation Research Team of High-Level Local Universities in Shanghai”support from the National Natural Science Foundation of China (22209103)
文摘Lithium–sulfur(Li–S)batteries are supposed to be one of the most potential next-generation batteries owing to their high theoretical capacity and low cost.Nevertheless,the shuttle effect of firm multi-step two-electron reaction between sulfur and lithium in liquid electrolyte makes the capacity much smaller than the theoretical value.Many methods were proposed for inhibiting the shuttle effect of polysulfide,improving corresponding redox kinetics and enhancing the integral performance of Li–S batteries.Here,we will comprehensively and systematically summarize the strategies for inhibiting the shuttle effect from all components of Li–S batteries.First,the electrochemical principles/mechanism and origin of the shuttle effect are described in detail.Moreover,the efficient strategies,including boosting the sulfur conversion rate of sulfur,confining sulfur or lithium polysulfides(LPS)within cathode host,confining LPS in the shield layer,and preventing LPS from contacting the anode,will be discussed to suppress the shuttle effect.Then,recent advances in inhibition of shuttle effect in cathode,electrolyte,separator,and anode with the aforementioned strategies have been summarized to direct the further design of efficient materials for Li–S batteries.Finally,we present prospects for inhibition of the LPS shuttle and potential development directions in Li–S batteries.
基金financially supported by the National Natural Science Foundation of China(No.52130101)the Project of Science and Technology Development Plan of Jilin Province in China(Nos.20210402058GH and 20220201114GX)。
文摘Lithium-sulfur batteries(LSBs)have attracted the attention of more and more researchers due to the advantages of high energy density,environmental friendliness,and low production cost.However,the low electronic conductivity of active material and shuttling effect of lithium polysulfides(LiPSs)limit the commercial development of LSBs.To solve these problems,we design a core-shell composite with nitrogen-doped carbon(NC)and two types of selenides(FeSe_(2)-NC@ZnSe-NC).The FeSe_(2)-NC@ZnSe-NC has a strong adsorption capacity,and can effectively adsorb LiPSs.At the same time,it also effectively alleviates the shuttling effect of LiPSs,and improves the utilization of the active substance during the charge/discharge reaction processes.The mechanism involved in FeSe_(2)-NC@ZnSe-NC is demonstrated by both experiments and density-functional theory(DFT)calculations.The electrochemical test results indicate that LSB with S/FeSe_(2)-NC@ZnSe-NC delivers an initial discharge capacity of 1260 mAh·g^(-1)at 0.2C.And after 500 cycles at 1C,the capacity decay rate per cycle is 0.031%,and the capacity retention rate is 85%.The FeSe_(2)-NC@ZnSe-NC core-shell structure verifies a rational strategy to construct an electrode material for high-performance LSBs.
基金supported by the National Key Research and Development Program(2018YFB1501500)the National Science Foundation for Excellent Young Scholars of China(21922815)+2 种基金the National Key Research and Development(R&D)Program of China(2020YFB1505800)the Research and Development Project of Key Core and Common Technology of Shanxi Province(2020XXX014)the Fundamental Research Program of Shanxi Province(20210302123008,20210302124101)。
文摘Lithium-sulfur battery(LSB) has high energy density but is limited by the polysulfides shuttle and dendrite growth during cycling. Herein, a free-standing cellulose nanofiber(CNF) separator is designed and fabricated in isopropanol/water suspension through vacuum filtration progress. CNFs with abundant polar oxygen-containing functional groups can chemically immobilize the polysulfides, and suppress the formation of the dendrites by controlling the surface morphology of the SEI on lithium metal in LSB. The isopropanol content in a suspension can fine-tune the pore structure of the membrane to achieve optimal electrochemical performance. The prepared separator displays integrated advantages of an ultrathin thickness(19 μm), lightweight(0.87 mg cm^(-2)), extremely high porosity(98.05%), and decent electrolyte affinity. As a result, the discharge capacity of the LSB with CNF separator at the first and 100 th cycle is 1.4 and 1.3 times that of PP separator, respectively. Our research provides an environmentalfriendly and facile strategy for the preparation of multifunctional separators for LSBs.
基金financially supported by the National Key R&D Program of China(2016YFB0100100)the National Natural Science Foundation of China(Nos.21433013,U1832218)the support from China Scholarship Council
文摘The polysulfides shuttle effect represents a great challenge in achieving high capacity and long lifespan of lithium/sulfur(Li/S)cells.A comprehensive understanding of the shuttle-related sulfur speciation and diffusion process is vital for addressing this issue.Herein,we employed in situ/operando X-ray absorption spectroscopy(XAS)to trace the migration of polysulfides across the Li/S cells by precisely monitoring the sulfur chemical speciation at the cathodic electrolyte-separator and electrolyte-anode interfaces,respectively,in a real-time condition.After we adopted a shuttle-suppressing strategy by introducing an electrocatalytic layer of twinborn bismuth sulfide/bismuth oxide nanoclusters in a carbon matrix(BSOC),we found the Li/S cell showed greatly improved sulfur utilization and longer life span.The operando S Kedge XAS results revealed that the BSOC modification was bi-functional:trapping polysulfides and catalyzing conversion of sulfur species simultaneously.We elucidated that the polysulfide trapping-and-catalyzing effect of the BSOC electrocatalytic layer resulted in an effective lithium anode protection.Our results could offer potential stratagem for designing more advanced Li/S cells.
基金financially supported by the Tsinghua-Foshan Innovation Special Fund(Grant No.2018THFS0409)the China Postdoctoral Science Foundation(Grant No.2019M650668)the National Key Research and Development Program of China(Grant No.2016YFA0201003)。
文摘Rechargeable lithium-oxygen(Li-O_(2))batteries are the next generation energy storage devices due to their ultrahigh theoretical capacity.Redox mediators(RMs)are widely used as a homogenous electrocatalyst in non-aqueous Li-O_(2)batteries to enhance their discharge capacity and reduce charge overpotential.However,the shuttle effect of RMs in the electrolyte solution usually leads to corrosion of the Li metal anode and uneven Li deposition on the anode surface,resulting in unwanted consumption of electrocatalysts and deterioration of the cells.It is therefore necessary to take some measures to prevent the shuttle effect of RMs and fully utilize the soluble electrocatalysts.Herein,we summarize the strategies to suppress the RM shuttle effect reported in recent years,including electrolyte additives,protective separators and electrode modification.The mechanisms of these strategies are analyzed and their corresponding requirements are discussed.The electrochemical properties of Li-O_(2)batteries with different strategies are summarized and compared.The challenges and perspectives on preventing the shuttle effect of RMs are described for future study.This review provides guidance for achieving shuttle-free redox mediation and for designing Li-O_(2)cells with a long cycle life,high energy efficiency and highly reversible electrochemical reactions.
基金Supplementary data to this article can be found online at https://doi.org/10.1016/j.matre.2022.100159.
文摘Polysulfide absorption in a micropore-rich structure has been reported to be capable of efficiently confining the shuttle effect for high-performance lithium-sulfur(Li–S)batteries.Here,a labyrinth maze-like spherical honeycomb-like carbon with micropore-rich structure was synthesized,which is employed as a template host material of sulfur to study the shuttle effects.The results strongly confirm that a diffusion controlled process rather than an absorption resulted surface-controlled process occurs in an even micropore-rich cathode but still greatly inhibits the shuttle effect.Thus,the battery achieves a high initial discharge specific capacity of 1120 mAh g1 at 0.25 C and super cycling stability for 1635 cycles with only 0.035%capacity decay per cycle with 100%Coulombic efficiency.We would like to propose a new mechanism for shuttle effect inhibition in micropores.In terms of the diffusion control process in microporous paths of a labyrinth maze structure,polysulfides experience a long travel to realize continuous reductions of sulfur and polysulfides until formation of the final solid product.This efficiently prevents the polysulfides escaping to electrolyte.The labyrinth maze-like honeycomb structure also offers fast electron transfer and enhanced mass transport as well as robust mechanical strength retaining intact structure for long cycle life.This work sheds lights on new fundamental insights behind the shuttle effects with universal significance while demonstrating prominent merits of a robust labyrinth maze-like structure in high performance cathode for high-performance Li–S batteries.
基金financially supported by the National Natural Science Foundation of China (No.51874197)Natural Science Foundation of Shanghai (Nos.21ZR1429400,22ZR1429700)
文摘Rechargeable aluminum-sulfur(Al-S)batteries have been considered as a highly potential energy storage system owing to the high theoretical capacity,good safety,abundant natural reserves,and low cost of Al and S.However,the research progress of Al-S batteries is limited by the slow kinetics and shuttle effect of soluble polysulfides intermediates.Herein,an interconnected free-standing interlayer of iron sin-gle atoms supported on porous nitrogen-doped carbon nanofibers(FeSAs-NCF)on the separator is developed and used as both catalyst and chemical barrier for Al-S batteries.The atomically dispersed iron active sites(Fe-N_(4))are clearly identified by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption near-edge structure.The Al-S battery with the FeSAs-NCF shows an improved specific capacity of 780 mAh g^(−1)and enhanced cycle stability.As evidenced by experimental and theoretical results,the atomically dispersed iron active centers on the separator can chemically adsorb the polysulfides and accelerate reaction kinetics to inhibit the shuttle effect and promote the reversible conversion between aluminum polysulfides,thus improving the electrochemical performance of the Al-S battery.This work provides a new way that can not only promote the conversion of aluminum sulfides but also suppress the shuttle effect in Al-S batteries.
基金supported by the National Natural Science Foundation of China(Nos.51631004 and 52130101)the Basic Construction Fund in Jilin Province Budget for 2019(No.2019C042-8).
文摘According to a statistic,approximately 6 trillion cigarettes are smoked each year all over the world,which produces approximately 1.2 million tons of discarded cigarette butts.The discarded cigarette filters are non-biodegradable,thus they produce a mass of waste disposal and cause environmental pollution is-sue.For the purpose of transforming waste into wealth and reducing environmental pollution,nitrogen and sulfur co-doped carbon nanofiber/carbon black(N,S-CNF/CB)composite derived from the discarded cigarette filters is employed to modify glass fiber(GF)separator for the first time in this study.N,S-CNF improves binding ability towards sodium polysulfides(SPSs)by chemisorption.Non-polar CB limits the dissolution of SPSs in the liquid electrolyte by physisorption.The experiment and density functional theory calculation results indicate that a RT-Na/S battery with a N,S-CNF/CB+GF separator exhibits good cycling stability and rate performance.After 100 cycles at a low current rate of 0.1 C,a RT-Na/S battery with a sulfur mass fraction of 71%delivers a discharge capacity of 703 mAh g^(−1).In addition,at a high current rate of 0.5 C,a discharge capacity of 527 mAh g^(−1) is still maintained after 900 cycles with a very low capacity fading rate of 0.035%per cycle.
基金partially supported by grants from the National Natural Science Foundation of China (52072099, 52102228)Team program of the Natural Science Foundation of Heilongjiang Province, China (TD2021E005)+1 种基金The National general entrepreneurial practice program (202210231088S)The National general innovation training program (202210231076)。
文摘In practical lithium-sulfur batteries(LSBs),the shuttle effect and Li cycling coulombic efficiency(CE) are strongly affected by the physicochemical properties of solid electrolyte interphase(SEI).LiNO_(3) is widely used as an additive in electrolytes to build a high-quality SEI,but its self-sacrificial nature limits the ability to mitigate the shuttle effect and stabilize Li anode during long-term cycling.To counteract LiNO_(3) consumption during long-term cycling without using a high initial concentration,inspired by sustainedrelease drugs,we encapsulated LiNO_(3) in lithiated Nafion polymer and added an electrolyte co-solvent(1,1,2,2-tetrafluoroethylene 2,2,2-trifluoromethyl ether) with poor LiNO_(3) solubility to construct highquality and durable F-and N-rich SEI.Theoretical calculations,experiments,multiphysics simulations,and in-situ observations confirmed that the F-and N-rich SEI can modulate lithium deposition behavior and allow persistent repair of SEI during prolonged cycling.Hence,the F-and N-rich SEI improves the Li anode cycling CE to 99.63% and alleviates the shuttle effect during long-term cycling.The lithium anode with sustainable F-and N-rich SEI shows a stable Li plating/stripping over 2000 h at 1 mA cm^(-2).As expected,Li‖S full cells with this SEI achieved a long lifespan of 250 cycles,far exceeding cells with a routine SEI.The Li‖S pouch cell based on F-and N-rich SEI also can achieve a high energy density of about300 Wh kg^(-1) at initial cycles.This strategy provides a novel design for high-quality and durable SEls in LSBs and may also be extendable to other alkali metal batteries.
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.
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 Key Research and Development Projects of Anhui Province(No.202304a05020031).
文摘Lithium-sulfur batteries(LSBs)have attracted widespread attention due to their high theoretical energy density.However,the dissolution of long-chain polysulfides into the electrolyte(the“shuttle effect”)leads to rapid capacity decay.Therefore,finding suitable materials to mitigate the shuttle effect of polysulfides is crucial for enhancing the electrochemical performance of lithium-sulfur batteries.In this study,LSBs’separator is modified with Ni_(3)V_(2)O_(8)nanoparticles@carboxylated carbon nanotubes(Ni_(3)V_(2)O_(8)@CNTs)composite.There are abundant oxygen vacancies in Ni_(3)V_(2)O_(8)@CNTs composite which plays a synergistic effect on shuttle effect.The Ni_(3)V_(2)O_(8)can tightly anchor soluble polysulfides through oxygen vacancies,while the CNTs not only facilitate the transport of ions and electrons but also weaken the migration of polysulfides,limiting shuttle effect.As a result,the cycling stability of LSBs using Ni_(3)V_(2)O_(8)@CNTs-modified separator has been significantly improved(with a capacity decay rate of only 0.0334%after 1500 cycles at 4.0C).This study proposes a strategy to design modified separator for high-performance LSBs.
基金the financial support from the China Scholarship Council(201809370046)a scholarship from the Laboratory of Inorganic Materials Chemistry Universitéde Namur+4 种基金supported by the National Postdoctoral Program(2020M672782)the National Natural Science Foundation of China(U1663225)Changjiang Scholars and Innovative Research Team in University(IRT_15R52)the Program of Introducing Talents of Discipline to Universities-Plan 111(B20002)from the Ministry of Science and Technology and the Ministry of Education of Chinathe National Key R&D Program of China(2016YFA0202602)。
文摘Maximizing the fixing ability of polyselenides to reduce the shuttle effect in Li-Se batteries remains highly challenging.Single crystal metal-organic framework(MOF)-derived N-doped ordered hierarchically porous carbon(SNOHPC)synthesized by a confined crystal growth and template-assisted method demonstrates excellent electrochemical performance as a host material for Li-Se battery.The large number of micropores inherited from the MOF structure provides large space and surface for Se loading and reaction sites,ensuring the high energy density of the battery.The insitu X-ray diffraction(XRD)technique is used to understand the reaction mechanism.The synergy of the interconnected three-scale-level micro-meso-macroporous structure and Ndoped polar sites can buffer the volume expansion,shorten the ion transportation with a very high diffusion coefficient of4.44×10cm^(2)sand accelerate the lithiation/delithiation reaction.Selenium is sufficiently reactive and the polyselenide intermediates are tightly fixed inside the carbon host material,thereby achieving excellent specific capacity,stability,and rate capability.Such a cathode exhibits a very high 2discharge/charge capacity of 658 and 683 mA h g,respectively,and retains a very high capacity of 367 mA h gafter 200 cycles at the current of 0.2 C.Even at the high current of 5 C,a very high discharge capacity of 230 mA h gis obtained.This work provides a new kind of high-performance porous materials with rational pore arrangement applicable for highly efficient energy storage.
基金supported by the National Natural Science Foundation of China(Nos.52105575&52205593)the Fundamental Research Funds for the Central Universities(No.QTZX23063)+1 种基金the Proof of Concept Foundation of Xidian University Hangzhou Institute of Technology(Nos.GNYZ2023YL0302&GNYZ2023QC0401)the Aeronautical Science Foundation of China(No.2022Z073081001)。
文摘Lithium-sulfur batteries(LSBs)have already developed into one of the most promising new-generation high-energy density electrochemical energy storage systems with outstanding features including high-energy density,low cost,and environmental friendliness.However,the development and commercialization path of LSBs still presents significant limitations and challenges,particularly the notorious shuttle effect triggered by soluble longchain lithium polysulfides(LiPSs),which inevitably leads to low utilization of cathode active sulfur and high battery capacity degradation,short cycle life,etc.Substantial research efforts have been conducted to develop various sulfur host materials capable of effectively restricting the shuttle effect.This review firstly introduces the fundamental electrochemical aspects of LSBs,followed by a comprehensive analysis of the mechanism underlying the shuttle effect in Li–S batteries and its profound influence on various battery components as well as the overall battery performance.Subsequently,recent advances and strategies are systematically reviewed,including physical confinement,chemisorption,and catalytic conversion of sulfur hosts for restricting LiPSs shuttle effects.The interplay mechanisms of sulfur hosts and LiPSs are discussed in detail and the structural advantages of different host materials are highlighted.Furthermore,key insights for the rational design of advanced host materials for LSBs are provided,and the upcoming challenges and the prospects for sulfur host materials in lithium-sulfur batteries are also explored.
基金supported by the National Natural Science Foundation of China(No.52072099)the Joint Guidance Project of the Natural Science Foundation of Heilongjiang Province,China(No.LH2022E093)the Team Program of the Natural Science Foundation of Heilongjiang Province,China(No.TD2021E005)。
文摘Lithium sulfur(Li-S)battery is a kind of burgeoning energy storage system with high energy density.However,the electrolyte-soluble intermediate lithium polysulfides(Li PSs)undergo notorious shuttle effect,which seriously hinders the commercialization of Li-S batteries.Herein,a unique VSe_(2)/V_(2)C heterostructure with local built-in electric field was rationally engineered from V_(2)C parent via a facile thermal selenization process.It exquisitely synergizes the strong affinity of V_(2)C with the effective electrocatalytic activity of VSe_(2).More importantly,the local built-in electric field at the heterointerface can sufficiently promote the electron/ion transport ability and eventually boost the conversion kinetics of sulfur species.The Li-S battery equipped with VSe_(2)/V_(2)C-CNTs-PP separator achieved an outstanding initial specific capacity of 1439.1 m A h g^(-1)with a high capacity retention of 73%after 100 cycles at0.1 C.More impressively,a wonderful capacity of 571.6 mA h g^(-1)was effectively maintained after 600cycles at 2 C with a capacity decay rate of 0.07%.Even under a sulfur loading of 4.8 mg cm^(-2),areal capacity still can be up to 5.6 m A h cm^(-2).In-situ Raman tests explicitly illustrate the effectiveness of VSe_(2)/V_(2)C-CNTs modifier in restricting Li PSs shuttle.Combined with density functional theory calculations,the underlying mechanism of VSe_(2)/V_(2)C heterostructure for remedying Li PSs shuttling and conversion kinetics was deciphered.The strategy of constructing VSe_(2)/V_(2)C heterocatalyst in this work proposes a universal protocol to design metal selenide-based separator modifier for Li-S battery.Besides,it opens an efficient avenue for the separator engineering of Li-S batteries.
基金the National Natural Science Foundation of China(Nos.22005341 and 22138013)the Shandong Provincial Natural Science Foundation(Nos.ZR2020QB128 and ZR2020ZD08)+2 种基金the Taishan Scholar Project(No.tsqnz20221121)the Major Scientific and Technological Innovation Project of Shandong Province(No.2020CXGC010402)the Independent Innovation Research Project of China University of Petroleum(No.22CX06026A).
文摘The commercialization of lithium-sulfur(Li-S)batteries faces several bottlenecks,and the major two of which are the shuttle effect of polysulfides and the wild growth of Li dendrites,responsible for fast capacity decay and severe safety issues.As an essential component of Li-S batteries,the structure and properties of the separators are closely related to the above problems,and the exploration of multifunctional separators is highly sought-after.Herein,an integrated separator composited of defective graphene and polyimide(DG-PI)was innovatively fabricated by electrospinning combined with the laser-induced carbonization strategy.The all-in-one compact architecture with well-interconnected channels shows superior mechanical and thermal stability and wettability.More importantly,the PI nanofibers containing N–/O–functional groups can induce the uniform deposition of lithium on the anode surface,while the DG framework with abundant pentagonal/heptagonal rings and vacancies can strongly trap polysulfides and accelerate polysulfide transformation on the cathode side.The strong chemical interaction between the insulative PI layer and the conductive DG layer modulates the surface charge distribution of each other,leading to more prominent contributions to restraining lithium dendrites and shuttle effect.Therefore,the Li-S batteries based on the integrated DG-PI separators afford an excellent performance in protecting lithium anode(stable cycles of 200 h at 5 mA·cm^(−2))and good cycling stability with a low capacity decay of 0.05%per cycle after 700 cycles at 1 C.This work offers a new design concept of multifunctional Li-S battery separators and broadens the application scope of laser micro-nano fabrication technology.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.U21A2080 and 51788104)Beijing Natural Science Foundation(No.L223008)National Key Research and Development Program of China(No.2022YFB2404403).
文摘Lithium-oxygen(Li-O_(2))batteries have a great potential in energy storage and conversion due to their ultra-high theoretical specific energy,but their applications are hindered by sluggish redox reaction kinetics in the charge/discharge processes.Redox mediators(RMs),as soluble catalysts,are widely used to facilitate the electrochemical processes in the Li-O_(2)batteries.A drawback of RMs is the shuttle effect due to their solubility and mobility,which leads to the corrosion of a Li metal anode and the degradation of the electrochemical performance of the batteries.Herein,we synthesize a polymer-based composite protective separator containing molecular sieves.The nanopores with a diameter of 4Åin the zeolite powder(4A zeolite)are able to physically block the migration of 2,2,6,6-tetramethylpiperidinyloxy(TEMPO)molecules with a larger size;therefore,the shuttle effect of TEMPO is restrained.With the assistance of the zeolite molecular sieves,the cycle life of the Li-O_(2)batteries is significantly extended from~20 to 170 cycles at a current density of 250 mA·g^(-1)and a limited capacity of 500 mAh·g^(-1).Our work provides a highly effective approach to suppress the shuttle effects of RMs and boost the electrochemical performance of Li-O_(2)batteries.
基金financially supported by the National Natural Science Foundation of China(Nos.22379038 and 22075067)the Natural Science Foundation of Tianjin City(No.23JCYBJC00330)+3 种基金the Science Research Project of Hebei Education Department(No.JZX2024015)the Young Elite Scientists Sponsorship Program by CAST(No.2021QNRC001)Shijiazhuang Science and Technology Plan Project(No.241791357A)the Excellent Youth Research Innovation Team of Hebei University(No.QNTD202410)。
文摘Rechargeable aqueous zinc-iodine(Zn-I_(2))batteries are widely regarded as a promising contender for energy-storage devices,due to their intrinsic safety,low cost,and high capacity.However,the severe shuttle effect of polyiodides and the large volume change of I_(2)cathode induce severe capacity loss and poor electrochemical reversibility,hindering their commercial applications.Herein,we report that the low-cost gelatinized starch(Gstarch)can be used as a bifunctional binder for Zn-I_(2)batteries to circumvent the above problems simultaneously.Based on both calculation and experimental data,it is demonstrated that the double-helix structure of G-starch with bothα-1,4-andα-1,6-glycosidic bonds can strongly interact with polyiodides to suppress the shuttle effect.Moreover,the G-starch with multiple hydrogen-bonded cross-linking networks exhibits a much-enhanced adhesion ability and can buffer the volume expansion of active materials.In contrast,the traditional carboxymethyl cellulose sodium-based aqueous binder lacks these capabilities.As a result,the G-starch binder enables the aqueous Zn-I_(2)battery to achieve a high reversible capacity of212.4 mAh·g^(-1)at 0.2 A·g^(-1)after 1000 cycles and ultralong-cycling life over 48,000 cycles with 135.4 mAh·g^(-1)and 89.6%capacity retention at 2 A·g^(-1).This work develops a simple yet efficient strategy to construct highperformance Zn-I_(2)batteries.
基金supported by the National Natural Science Foundation of China(No.52371240)the Natural Science Foundation of Jiangsu Province(No.BK20230556)+2 种基金China Postdoctoral Science Foundation(No.2022M722686)Jiangsu Funding Program for Excellent Postdoctoral Talent(No.2023ZB701)The Big Data Computing Center of Southeast University.
文摘Metal-iodine batteries have attracted widespread attention due to their long cycle life,high energy density,remarkable charging capability and low self-discharge rate.Nevertheless,this development is hampered by the challenges of the iodine cathode and metal anode,including the hydrogen evolution reaction(HER),sluggish kinetics,shuttle effect of polyiodine ion at the cathode and dendrite formation,corrosion and passivation at the anode.This review summarizes recent developments in metaliodine batteries,including zinc-iodine batteries,lithiumiodine batteries,sodium-iodine batteries,etc.The challenges in the cathode,anode,electrolyte and separator of metal-iodine batteries are discussed,along with the corresponding design and synthesis strategies and specific methods to improve the electrochemical performance.Selecting appropriate cathode hosts,constructing surface protective layers,adding anode additives,making threedimensional anode designs and employing better electrolytes and functional separators to obstruct the production and shuttling of polyiodine ions are highlighted.Finally,future guidelines and directions for the development of metal-iodine batteries are proposed.
