The growing demands for energy storage systems,electric vehicles,and portable electronics have significantly pushed forward the need for safe and reliable lithium batteries.It is essential to design functional separat...The growing demands for energy storage systems,electric vehicles,and portable electronics have significantly pushed forward the need for safe and reliable lithium batteries.It is essential to design functional separators with improved mechanical and electrochemical characteristics.This review covers the improved mechanical and electrochemical performances as well as the advancements made in the design of separators utilizing a variety of techniques.In terms of electrolyte wettability and adhesion of the coating materials,we provide an overview of the current status of research on coated separators,in situ modified separators,and grafting modified separators,and elaborate additional performance parameters of interest.The characteristics of inorganics coated separators,organic framework coated separators and inorganic-organic coated separators from different fabrication methods are compared.Future directions regarding new modified materials,manufacturing process,quantitative analysis of adhesion and so on are proposed toward next-generation advanced lithium batteries.展开更多
The safety and performance of lithium-ion batteries(LIBs)largely depend on the structural design and performance characteristics of the separator.Commercial polyolefin separators suffer from problems such as poor ther...The safety and performance of lithium-ion batteries(LIBs)largely depend on the structural design and performance characteristics of the separator.Commercial polyolefin separators suffer from problems such as poor thermal stability,insufficient porosity,and inferior electrolyte wettability,which not only easily lead to battery safety issues but also significantly affect the ionic conductivity and energy density of the batteries.Herein,we have designed a facile,efficient and controllable methodology to develop a high-porosity poly(m-phenylene isophthalamide)(PMIA)separator with both excellent wettability and superior thermal resistance by a vapor-induced phase separation technique.Specifically,the PMIA separator undergoes a thermal shrinkage of less than 1%even after being treated at 200℃ for one hour,which greatly enhances the thermal safety of the battery.In addition,a continuous and interconnected high-porosity structure(porosity of 69%)is formed by utilizing a stable and controllable solvent exchange rate,thereby constructing abundant channels for the transportation of ions within the battery.Moreover,the amide groups in the PMIA molecular structure further confer the separator with excellent wettability,enabling it to possess outstanding electrolyte absorption capacity(electrolyte absorption rate of 270%).As a result,the Li||LFP full cell with PMIA separator exhibits excellent capacity and cycling stability,maintaining a reversible specific capacity of 105.6 mAh g^(-1)after 600 cycles at 5 C.And Li||NCM811 full cell with PMIA separator show no significant degradation(168.1 mAh g^(-1)at 0.5 C)after long-cycle at high temperature.These results indicate the potential of the PMIA separator for high thermal stability and high energy battery,and the scalability of this technology also provides new ideas and directions for the preparation of separators with superior comprehensive performance.展开更多
All-safe liquid-state lithium-ion batteries(ASLS-LIBs) is of great interest as they can potentially combine the safety of all-solid-state batteries with the high performance and low manufacturing cost of traditional l...All-safe liquid-state lithium-ion batteries(ASLS-LIBs) is of great interest as they can potentially combine the safety of all-solid-state batteries with the high performance and low manufacturing cost of traditional liquid-state LIBs. However, the practical success of ASLS-LIBs is bottlenecked by the lack of advanced separator technology that can simultaneously realize high performances in puncturing-tolerability,fire-resistance, and importantly, wetting-capability with non-flammable liquid-electrolytes. Here, we propose a concept of inorganic in-situ separator(IISS) by hybrid-sol physical crosslinking directly onto the electrode surface to address the above challenges. Particularly, the hybrid-sol is designed with silica nanoparticles as the building block and poly(vinylidene difluoride) nanoparticles as the crosslinking agent. The critical factors for controlling the IISS microstructures and properties have been systematically investigated. The advantages of the IISS have been confirmed by its fast wetting with various fireresistant liquid-electrolytes, customizable thickness and porous structures, robust interface with planar or three-dimensional(3D)-structured electrodes, and importantly, unexpected self-adaptability against puncturing. Enabled by the above merits, a fire-resistant ASLS-LIB is successfully assembled and demonstrated with stable electrochemical performance. This sol-crosslinked IISS may open an avenue for the studies on the next-generation separator technology, cell assembling, solid electrolyte processing as well as non-flammable secondary batteries.展开更多
The thermal stability of lithium-ion battery separators is a critical determinant of battery safety and performance,especially in the context of rapidly expanding applications in electric vehicles and energy storage s...The thermal stability of lithium-ion battery separators is a critical determinant of battery safety and performance,especially in the context of rapidly expanding applications in electric vehicles and energy storage systems.While traditional polyolefin separators(PP/PE)dominate the market due to their cost-effectiveness and mechanical robustness,their inherent poor thermal stability poses significant safety risks under high-temperature conditions.This review provides a comprehensive analysis of recent advancements in enhancing separator thermal stability through coating materials(metal,ceramic,inorganic)and novel high-temperature-resistant polymers(e.g.,PVDF copolymers,PI,PAN).Notably,we critically evaluate the trade-offs between thermal resilience and electrochemical performance,such as the unintended increase in electronic conductivity from metal coatings(e.g.,Cu,MOFs)and reduced electrolyte wettability in ceramic coatings(e.g.,Al_(2)O_(3)).Innovations in hybrid coatings(e.g.,BN/PAN composites,gradient-structured MOFs)and scalable manufacturing techniques(e.g.,roll-to-roll electrospinning)are highlighted as promising strategies to balance these competing demands.Furthermore,a comparative analysis of next-generation high-temperature-resistant separators underscores their ionic conductivity,mechanical strength,and scalability,offering actionable insights for material selection.The review concludes with forward-looking perspectives on integrating machine learning for material discovery,optimizing interfacial adhesion in ceramic coatings,and advancing semi-/all-solid-state batteries to address both thermal and electrochemical challenges.This work aims to bridge the gap between laboratory innovations and industrial applications,fostering safer and more efficient lithium battery technologies.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
Metal organic frameworks(MOFs)are crystalline materials with three-dimensional porous network structure.They are obtained by self-assembly of coordinate bond with metal ions as the nodes and organic ligands as the con...Metal organic frameworks(MOFs)are crystalline materials with three-dimensional porous network structure.They are obtained by self-assembly of coordinate bond with metal ions as the nodes and organic ligands as the connecting chains.MOFs have attracted extensive attention from researchers over the years due to their clear pore and rich topological structure.As the typical powder materials,a specific separator manufacturing process must be possessed when incorporating MOFs into lithium sulfur batteries separator.This mini review summarized the manufacturing process of MOFs separator for LSBs in recent years,and summed up the effects and mechanisms of separators prepared by various separator-forming processes on the performance of LSBs,the potential for industrialization of different separator manufacturing processes is also mentioned briefly.展开更多
Zinc-based batteries have attracted widespread attention due to their inherent safety,notable cost-effectiveness and consistent performance,etc.However,the advancement of zinc-based battery technology encounters signi...Zinc-based batteries have attracted widespread attention due to their inherent safety,notable cost-effectiveness and consistent performance,etc.However,the advancement of zinc-based battery technology encounters significant challenges,including the formation of zinc dendrites and irreversible side reactions.Separators are vital in batteries due to their role in preventing electrode contact and facilitating rapid movement of ions within the electrolyte.The incorporation of cellulose in batteries enables uniform ion transport and a stable electricfield,attributed to its excellent hydrophilicity,strong mechanical strength,and abundant active sites.Herein,the latest research progress of cellulose-based separators on various zinc-based batteries is systematically summarized.To begin with,the accomplishments and inherent limitations of traditional sep-arators are clarified.Next,it underscores the advantages of cellulose-based materials in battery technology,thoroughly examining their utilization and merits as separators in zinc-based batteries.Lastly,the review offers prospective insights into the future trajectory of cellulose-based separators in zinc-based batteries.Through a comprehensive analysis of the present landscape,the review establishes a framework for the future design and enhancement of cellulose-based separators,thereby fostering the progression of associated industries.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
Severe lithium dendrite growth and elevated thermal runaway risks pose significant hurdles for fast-charging lithium metal batteries(LMBs)This study reports a polydopamine-functionalized hydroxyapatite/aramid(PDA@HA)h...Severe lithium dendrite growth and elevated thermal runaway risks pose significant hurdles for fast-charging lithium metal batteries(LMBs)This study reports a polydopamine-functionalized hydroxyapatite/aramid(PDA@HA)hybrid nanofibers separator to synchronously improve th fast-charging LMB's stability and safety.(1)The separator's surface,enriched with lithiophilic carbonyl and hydroxyl groups,accelerates Li~+ion desolvation,while electrophilic imine groups impede anion movement.This dual mechanism optimizes the Li^(+)-ion flux distribution on th anode,mitigating dendrite formation.(2)The polar PDA modification layer fosters the development of a Li_(3)N/LiF-rich solid electrolyt interface,further enhancing Li anode stability.Consequently,Li//Li symmetric cells with PDA@HA separators exhibit extended cycle life in L plating/stripping tests:5000 h at 1 mA cm^(-2)and 700 h at 20 mA cm^(-2),respectively,outperforming PP separators(80 h and 8 h).In LiFePO_(4)(LFP,^(2.1)mg cm^(-2))//Li full cell evaluation,the PDA@HA separator enables stable operation for 11,000 cycles at 18.2C with 87%capacity retention,significantly outperforming existing fast-charging LMB counterparts in literature.At a high LFP loading of 15.5 mg cm^(-2),the cel maintains 137.6 mAh g^(-1)(2.13 mAh cm^(-2))over 250 cycles at 3C,achieving 98%capacity retention.Moreover,the PDA@HA separato increases threshold temperature for thermal runaway and reduces the exothermic rate,intensifying the battery's thermal safety.This research underscores the importance of functional separator design in improving Li metal anode reversibility,fast-charging performance,and therma safety of LMBs.展开更多
Separators in supercapacitors(SCs)frequently suffer from high resistance and the risk of short circuits due to inadequate electrolyte wettability,depressed mechanical properties,and insufficient thermal stability.Here...Separators in supercapacitors(SCs)frequently suffer from high resistance and the risk of short circuits due to inadequate electrolyte wettability,depressed mechanical properties,and insufficient thermal stability.Here,we develop a high-performance regenerated cellulose separator with nano-cracked structures for SCs via a binary solvent of superbase-derived ionic liquid and dimethylsulfoxide(DMSO).The unique nano-cracks with an average width of 7.45 nm arise from the acceleration of cellulose molecular reassembly by DMSO-regulated hydrogen bonding,which endows the separator with high porosity(70.2%)and excellent electrolyte retention(329%).The outstanding thermal stability(273℃)and mechanical strength(70 MPa)enable the separator to maintain its structural integrity under high temperatures and external forces.With these benefits,the SC utilizing the cellulose separator enables a high specific capacitance of 93.6 F g^(−1) at 1.0 A g^(−1) and a remarkable capacitance retention of 99.5%after 10,000 cycles compared with the commercial NKK-MPF30AC and NKK-TF4030.The robust and high-wettability cellulose separator holds promise as a superior alternative to commercial separators for advanced SCs with enhanced performance and improved safety.展开更多
Poor Li plating reversibility and high thermal runaway risks are key challenges for fast charging lithiumion batteries with graphite anodes.Herein,a dielectric and fire-resistant separator based on hybrid nanofibers o...Poor Li plating reversibility and high thermal runaway risks are key challenges for fast charging lithiumion batteries with graphite anodes.Herein,a dielectric and fire-resistant separator based on hybrid nanofibers of barium sulfate(BS)and bacterial cellulose(BC)is developed to synchronously enhance the battery's fast charging and thermal-safety performances.The regulation mechanism of the dielectric BS/BC separator in enhancing the Li^(+)ion transport and Li plating reversibility is revealed.(1)The Max-Wagner polarization electric field of the dielectric BS/BC separator can accelerate the desolvation of solvated Li^(+)ions,enhancing their transport kinetics.(2)Moreover,due to the charge balancing effect,the dielectric BS/BC separator homogenizes the electric field/Li^(+)ion flux at the graphite anode-separator interface,facilitating uniform Li plating and suppressing Li dendrite growth.Consequently,the fast-charge graphite anode with the BS/BC separator shows higher Coulombic efficiency(99.0%vs.96.9%)and longer cycling lifespan(100 cycles vs.59 cycles)than that with the polypropylene(PP)separator in the constantlithiation cycling test at 2 mA cm^(-2).The high-loading LiFePO4(15.5 mg cm^(-2))//graphite(7.5 mg cm^(-2))full cell with the BS/BC separator exhibits excellent fast charging performance,retaining 70%of its capacity after 500 cycles at a high rate of 2C,which is significantly better than that of the cell with the PP separator(retaining only 27%of its capacity after 500 cycles).More importantly,the thermally stable BS/BC separator effectively elevates the critical temperature and reduces the heat release rate during thermal runaway,thereby significantly enhancing the battery's safety.展开更多
In the novel fully dry converter gas recovery process,a novel circumfluent cyclone separator with an evaporation heating surface can simultaneously realize the dust removal and sensible heat recovery of converter gas....In the novel fully dry converter gas recovery process,a novel circumfluent cyclone separator with an evaporation heating surface can simultaneously realize the dust removal and sensible heat recovery of converter gas.For this equipment,the distributions of internal flow and wall heat transfer affect the efficiency of dust removal and sensible heat recovery.In this study,based on on-site operation tests,the distributions of internal flow and wall heat transfer in the circumfluent cyclone separator are studied by numerical simulation.The results indicate that the flow rate proportions in different regions of the circumfluent cyclone separator remain constant during the steelmaking process,approximately 80.1%of the converter gas flows through the cone chamber,and 15.4%of the converter gas flows through the annular chamber.The heat transfer rate proportions on the walls of different regions of the circumfluent cyclone separator remain constant during the steelmaking process,and the heat transfer rate proportions on the walls of the cone chamber,straight shell,shell head and outlet pipe are 40.2%,27.0%,17.6%and 15.2%,respectively.展开更多
Uncontrolled dendrite growth,sluggish reaction kinetics,and drastic side reactions on the anodeelectrolyte interface are the main obstacles that restrict the application prospect of aqueous zinc-ion batteries.Traditio...Uncontrolled dendrite growth,sluggish reaction kinetics,and drastic side reactions on the anodeelectrolyte interface are the main obstacles that restrict the application prospect of aqueous zinc-ion batteries.Traditional glass fiber(GF)separator with chemical inertness is almost ineffective in restricting these challenges.Herein,inspired by the ionic enrichment behavior of seaweed plants,a facile biomass species,anionic sodium alginate(SA),is purposely decorated on the commercial GF separator to tackle these issues towards Zn anode.Benefiting from the abundant zincophilic functional groups and superior mechanical strength properties,the as-obtained SA@GF separator could act as ion pump to boost the Zn^(2+)transference number(0.68),reduce the de-solvation energy barrier of hydrated Zn^(2+),and eliminate the undesired concentration polarization effect,which are verified by experimental tests,theoretical calculations,and finite element simulation,respectively.Based on these efficient modulation mechanisms,the SA@GF separator can synchronously achieve well-aligned Zn deposition and the suppression of parasitic side-reactions.Therefore,the Zn‖Zn coin cell integrated with SA@GF separator could yield a prolonged calendar lifespan over 1230 h(1 mA cm^(-2)and 1 mAh cm^(-2)),exhibiting favorable competitiveness with previously reported separator modification strategies.Impressively,the Zn-MnO_(2)full and pouch cell assembled with the SA@GF separator also delivered superior cycling stability and rate performance,further verifying its practical application effect.This work provides a new design philosophy to stabilize the Zn anode from the aspect of separator.展开更多
Lithium-ion batteries are used extensively in civil,military,and aerospace applications because of their high energy and power density.However,in practical applications,these batteries may encounter extreme cases char...Lithium-ion batteries are used extensively in civil,military,and aerospace applications because of their high energy and power density.However,in practical applications,these batteries may encounter extreme cases characterized by transient high impacts,which impose stringent requirements on their safety and reliability.In recent years,the failure mechanism associated with the short-circuiting of lithium-ion-battery separators under high dynamic impacts has been investigated thoroughly.Based on the separator impact failure mechanism,we prepared a porous polymer polyvinylidene fluoride(PVDF)separator by doping gas-phase SiO_(2)(fumed silica)additive.The gas-phase SiO_(2)has a unique three-dimensional cluster structure,which is impact resistant.The impact resistance of the battery separator was tested using a highdynamic-impact system.The voltage drop of the battery with 3%SiO_(2)content was 33.04%of that of the original PVDF battery.Material characterization of the separator was further explored by scanning electron microscope,static compression,and pore-size adsorption tests.The SiO_(2)with a special cluster structure was distributed uniformly on the surface of the separator and embedded in the inner walls of the pores.Under static compression,the current of the SiO_(2)-PVDF separator with 3%content rose at a lower rate than that of the PVDF separator,with a minimum current of 1.04 mA.After adding SiO_(2),the separator pore size increased from 5 to 20 nm.Also,we used COMSOL to conduct impact simulations of different separators.The calculation results showed that the deformation(9.98%)and internal electrode current(0.018 A)of the SiO_(2)-PVDF lithium-ion battery were lower than the deformation(23.09%)and internal electrode current(0.049 A)of the PVDF lithium-ion battery.The SiO_(2)-doped composite polymer separator with a special cluster structure plays a crucial role in enhancing the impact resistance of lithium-ion batteries.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
Lithium-sulfur(Li-S)batteries with attractive capacity give remarkable potential for prospective high-capacity application scenarios but suffer a fatal flaw of short cyclability before large-scale commercialization es...Lithium-sulfur(Li-S)batteries with attractive capacity give remarkable potential for prospective high-capacity application scenarios but suffer a fatal flaw of short cyclability before large-scale commercialization especially owing to polysulfide(Li_(2)S_(n))transmembrane shuttling.To efficiently restrain chronic Li_(2)S_(n) shuttle and expedite Li^(+)transfer,herein,a novel electriferous charge-mosaic S(TMC@Lys-Li)separator preparation approach is recommended.Interfacial polymerizations of lithiated lysine and trimesoyl chloride establish an electriferous charge-mosaic polyamide functional layer.Substituted Li within the charge-mosaic layer offers transition or replacement sites for smoothing Li^(+)migrations,which constructs efficient Li^(+)fast-transfer private channels and accelerates the Li^(+)transfer rate to 9.4 times.Negatively charged polyamide skeleton synchronously heightens Li_(2)S_(n) rejections by combining Donnan and steric effects.S(TMC@Lys-Li)replenishes Li for homogenizing Li nucleation and growth,endowing stable plating/stripping behaviors over 250 cycles for Li-Cu batteries.Assembled Li-S cells thus exhibit excellent specific capacity and cyclability at multiple application scenarios such as long periods,high areal capacity,and fast charge,holding 78.1%retention after 500 cycles at 1 C.The superior thermal stability and self-discharge of S(TMC@Lys-Li)dramatically strengthen battery thermal runaway resistance even at155℃,which ensures security for Li-S battery high-power and high-temperature operations.Above alluring features enable charge-mosaic separators to be potentially adopted in practical Li-S batteries demanding strict security,high-capacity density,and fast charge technology.展开更多
Aqueous zinc-ion batteries encounter enormous challenges such as Zn dendrites and parasitic reactions.Separator modification is a highly effective strategy to address these issues.With the advantages of low cost,nonto...Aqueous zinc-ion batteries encounter enormous challenges such as Zn dendrites and parasitic reactions.Separator modification is a highly effective strategy to address these issues.With the advantages of low cost,nontoxicity,biodegradability,good film-forming ability,superior hydro phi licity,and rich functional groups,chitosan is an ideal matrix for constructing separators.However,the presence of positive charges within chitosan in weakly acidic electrolytes is unfavorable for dendrite inhibition.Herein,Schiff base reaction is introduced to modify chitosan matrix,transforming its charge polarity from positive to negative.Additionally,NbN with excellent zincophilicity is coated onto chitosan matrix,forming a Janus separator with low thickness of 19μm and considerably improved mechanical properties.The resultant separator can promote the transport of Zn^(2+)ions while triggering a repulsive shielding effect against anions,therefore dramatically enhancing Zn^(2+)ion transfer number from 0.28 to 0.49.This separator can also facilitate desolvation process,improve exchange current density,restrict two-dimensional Zn^(2+)ion diffusion,and enhance electrochemical kinetics,contributing to significantly inhibited dendrite growth,by-product formation,and hydrogen evolution.Consequently,stable and reversible Zn stripping/plating process is enabled for over 2500 h at 2 mA cm^(-2)and 2 mAh cm^(-2).And great rate capability and excellent cyclability can be achieved for full batteries even under harsh conditions.This work provides new insights into separator design for Zn-based batteries.展开更多
The uneven deposition and high reactivity of lithium-metal anode(LMA)lead to uncontrollable dendrite growth,low Coulombic efficiency,and safety concerns,hindering their commercialization.Here,a representative polar-ri...The uneven deposition and high reactivity of lithium-metal anode(LMA)lead to uncontrollable dendrite growth,low Coulombic efficiency,and safety concerns,hindering their commercialization.Here,a representative polar-rich-group triazine-based covalent organic framework(COF-TzDha)with a desolvation effect is designed as an interlayer for stable,dendrite-free LMA.The abundant triazine rings in COFTzDha as a donor effectively attract lithium ions,while the one-dimensional nanopore structure facilitates lithium-ion migration.The periodic arrangement of polar groups(-OH)in the backbone interacts with electrolyte components(DOL,DME,TFSI-)to form a hydrogen bonding network that slows solvent molecules transport.Therefore,COF-TzDha effectively desolvates lithium ions from the solvent sheath,promoting uniform lithium ion flux and Li plating/stripping.Theoretical calculations verify that COFTzDha with abundant adsorption sites and strong adsorption energy facilitates lithium ion desolvation.Consequently,the introduction of COF-TzDha obtains a high ion mobility(0.75).The Li|COF@PP|Li symmetric cell cycles stably for over 1200 h at 4 mA cm^(-2)/4.0 mA h cm^(-2).The Li|COF@PP|LiFePO_(4)full cell also displays highly stable cycling performance with 600 cycles(75.5%capacity retention,~100% Coulombic efficiency)at 1 C.This work verifies an effective strategy for inducing uniform Li deposition and achieving dendrite-free,stable LMA using a polar-rich-group COF interlayer with a desolvation effect.展开更多
Owing to the advantages of high energy density,low cost,abundant sulfur reserves and environmentally friendly nature,lithium-sulfur batteries(LSBs)were considered as one of the potential candidates of energy storage d...Owing to the advantages of high energy density,low cost,abundant sulfur reserves and environmentally friendly nature,lithium-sulfur batteries(LSBs)were considered as one of the potential candidates of energy storage devices for the next generation.However,the significant challenges in this area stem from the sluggish reaction kinetics of the insoluble Li_(2)S product and the capacity degradation triggered by the severe shuttle effect of polysulfides.It has been firmly established through numerous studies that modifying separators is an effective approach to enhance the properties of LSBs by facilitating the catalytic kinetic conversion and chemical adsorption of lithium polysulfides(Li PSs).In this work,we report a straightforward method for fabrication of the phosphorus doped porous CeO_(2)(P-CeO_(2))as separator modifier to accelerate the catalytic kinetic conversion of polysulfides and effectively inhibit the shuttle effect in LSBs.Through coin batteries tests,P-CeO_(2)modified PP separator(P-CeO_(2)//PP)exhibits remarkable electrochemical performance.It demonstrates a high initial capacity of 1180 mAh/g at 0.5 C,surpassing the performance of the bare CeO_(2)//PP separator.Furthermore,the P-CeO_(2)//PP separator demonstrates enhanced cycling stability,with a low-capacity fading rate of only 0.048%per cycle over 1000 cycles at 2 C.In compared with bare CeO_(2)//PP,P-CeO_(2)//PP exhibits high redox peak current,enhanced adsorption property of Li_(2)S_(6)and early Li_(2)S precipitation.These results highlight the superior performance of the P-CeO_(2)//PP separator compared to the bare CeO_(2)//PP separator.Hence,this research presents a successful strategy for the modification of LIBs separator with improved electrochemical performance and cycle stability.展开更多
Separator modification is an effective approach to suppress dendrite growth to realize high-energy sodium metal batteries(SMBs)in practical applications,however,its success is mainly subject to surface modification.He...Separator modification is an effective approach to suppress dendrite growth to realize high-energy sodium metal batteries(SMBs)in practical applications,however,its success is mainly subject to surface modification.Herein,a separator with multifunctional layers composed of N-doped mesoporous hollow carbon spheres(HCS)as the inner layer and sodium fluoride(NaF)as the outer layer on commercial polypropylene separator(PP)is proposed(PP@HCS-NaF)to achieve stable cycling in SMB.At the molecular level,the inner HCS layer with a high content of pyrrolic-N induces the uniform Na^(+)flux as a potential Na^(+)redistributor for homogenous deposition,whereas its hollow mesoporous structure offers nanoporous buffers and ion channels to regulate Na^(+)ion distribution and uniform deposition.The outer layer(NaF)constructs the NaF-enriched robust solid electrolyte interphase layer,significantly lowering the Na^(+)ions diffusion barrier.Benefiting from these merits,higher electrochemical performances are achieved with multifunctional double-layered PP@HCS-NaF separators compared with single-layered separators(i.e.PP@HCS or PP@NaF)in SMBs.The Na‖Cu half-cell with PP@HCS-NaF offers stable cycling(280 cycles)with a high CE(99.6%),and Na‖Na symmetric cells demonstrate extended lifespans for over 6000 h at 1 mA cm^(-2)with a progressively stable overpotential of 9 mV.Remarkably,in Na‖NVP full-cells,the PP@HCS-NaF separator grants a stable capacity of~81 mA h g^(-1)after 3500 cycles at 1 C and an impressive rate capability performance(~70 mA h g^(-1)at 15 C).展开更多
基金the Center of Lithium Battery Membrane Materials jointly established by School of Chemistry and Chemical Engineering of Huazhong University of Science and Technology and Shenzhen Senior Technology Material Co.Ltd.,the National Natural Science Foundation of China(52020105012,52303084)the Young Scientists Fund of Natural Science Foundation of Hubei Province(2023AFB220)for the support of this work.
文摘The growing demands for energy storage systems,electric vehicles,and portable electronics have significantly pushed forward the need for safe and reliable lithium batteries.It is essential to design functional separators with improved mechanical and electrochemical characteristics.This review covers the improved mechanical and electrochemical performances as well as the advancements made in the design of separators utilizing a variety of techniques.In terms of electrolyte wettability and adhesion of the coating materials,we provide an overview of the current status of research on coated separators,in situ modified separators,and grafting modified separators,and elaborate additional performance parameters of interest.The characteristics of inorganics coated separators,organic framework coated separators and inorganic-organic coated separators from different fabrication methods are compared.Future directions regarding new modified materials,manufacturing process,quantitative analysis of adhesion and so on are proposed toward next-generation advanced lithium batteries.
基金supported by the National Natural Science Foundation of China(52273059,52403046)the Science and Technology Plans of Tianjin(22JCYBJC01030)+1 种基金the Tianjin Research Innovation Project for Postgraduate Students(2022BKY145)partially supported by financial contributions from Yantai Tayho Advanced Materials Co.,Ltd。
文摘The safety and performance of lithium-ion batteries(LIBs)largely depend on the structural design and performance characteristics of the separator.Commercial polyolefin separators suffer from problems such as poor thermal stability,insufficient porosity,and inferior electrolyte wettability,which not only easily lead to battery safety issues but also significantly affect the ionic conductivity and energy density of the batteries.Herein,we have designed a facile,efficient and controllable methodology to develop a high-porosity poly(m-phenylene isophthalamide)(PMIA)separator with both excellent wettability and superior thermal resistance by a vapor-induced phase separation technique.Specifically,the PMIA separator undergoes a thermal shrinkage of less than 1%even after being treated at 200℃ for one hour,which greatly enhances the thermal safety of the battery.In addition,a continuous and interconnected high-porosity structure(porosity of 69%)is formed by utilizing a stable and controllable solvent exchange rate,thereby constructing abundant channels for the transportation of ions within the battery.Moreover,the amide groups in the PMIA molecular structure further confer the separator with excellent wettability,enabling it to possess outstanding electrolyte absorption capacity(electrolyte absorption rate of 270%).As a result,the Li||LFP full cell with PMIA separator exhibits excellent capacity and cycling stability,maintaining a reversible specific capacity of 105.6 mAh g^(-1)after 600 cycles at 5 C.And Li||NCM811 full cell with PMIA separator show no significant degradation(168.1 mAh g^(-1)at 0.5 C)after long-cycle at high temperature.These results indicate the potential of the PMIA separator for high thermal stability and high energy battery,and the scalability of this technology also provides new ideas and directions for the preparation of separators with superior comprehensive performance.
基金National Natural Science Foundation of China (52203123)Sichuan Science and Technology Program (2023NSFSC0991)+2 种基金State Key Laboratory of Polymer Materials Engineering (sklpme-2023-1-05 and sklpme-2024-2-04)Fundamental Research Funds for the Central UniversitiesThis research was also partially sponsored by the Double First-Class Construction Funds of Sichuan University。
文摘All-safe liquid-state lithium-ion batteries(ASLS-LIBs) is of great interest as they can potentially combine the safety of all-solid-state batteries with the high performance and low manufacturing cost of traditional liquid-state LIBs. However, the practical success of ASLS-LIBs is bottlenecked by the lack of advanced separator technology that can simultaneously realize high performances in puncturing-tolerability,fire-resistance, and importantly, wetting-capability with non-flammable liquid-electrolytes. Here, we propose a concept of inorganic in-situ separator(IISS) by hybrid-sol physical crosslinking directly onto the electrode surface to address the above challenges. Particularly, the hybrid-sol is designed with silica nanoparticles as the building block and poly(vinylidene difluoride) nanoparticles as the crosslinking agent. The critical factors for controlling the IISS microstructures and properties have been systematically investigated. The advantages of the IISS have been confirmed by its fast wetting with various fireresistant liquid-electrolytes, customizable thickness and porous structures, robust interface with planar or three-dimensional(3D)-structured electrodes, and importantly, unexpected self-adaptability against puncturing. Enabled by the above merits, a fire-resistant ASLS-LIB is successfully assembled and demonstrated with stable electrochemical performance. This sol-crosslinked IISS may open an avenue for the studies on the next-generation separator technology, cell assembling, solid electrolyte processing as well as non-flammable secondary batteries.
基金supported by Beijing Institute of Technology Student Innovation Training Program(BIT2024LH013).
文摘The thermal stability of lithium-ion battery separators is a critical determinant of battery safety and performance,especially in the context of rapidly expanding applications in electric vehicles and energy storage systems.While traditional polyolefin separators(PP/PE)dominate the market due to their cost-effectiveness and mechanical robustness,their inherent poor thermal stability poses significant safety risks under high-temperature conditions.This review provides a comprehensive analysis of recent advancements in enhancing separator thermal stability through coating materials(metal,ceramic,inorganic)and novel high-temperature-resistant polymers(e.g.,PVDF copolymers,PI,PAN).Notably,we critically evaluate the trade-offs between thermal resilience and electrochemical performance,such as the unintended increase in electronic conductivity from metal coatings(e.g.,Cu,MOFs)and reduced electrolyte wettability in ceramic coatings(e.g.,Al_(2)O_(3)).Innovations in hybrid coatings(e.g.,BN/PAN composites,gradient-structured MOFs)and scalable manufacturing techniques(e.g.,roll-to-roll electrospinning)are highlighted as promising strategies to balance these competing demands.Furthermore,a comparative analysis of next-generation high-temperature-resistant separators underscores their ionic conductivity,mechanical strength,and scalability,offering actionable insights for material selection.The review concludes with forward-looking perspectives on integrating machine learning for material discovery,optimizing interfacial adhesion in ceramic coatings,and advancing semi-/all-solid-state batteries to address both thermal and electrochemical challenges.This work aims to bridge the gap between laboratory innovations and industrial applications,fostering safer and more efficient lithium battery technologies.
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financially supported by the University Natural Science Research Key Project of Anhui Province(Nos.KJ2021A1091,2023AH051619)Innovation and Entrepreneurship Training Program for College Students(No.202310377030)Scientific Research Start Foundation Project of Chuzhou University(No.2022qd011)。
文摘Metal organic frameworks(MOFs)are crystalline materials with three-dimensional porous network structure.They are obtained by self-assembly of coordinate bond with metal ions as the nodes and organic ligands as the connecting chains.MOFs have attracted extensive attention from researchers over the years due to their clear pore and rich topological structure.As the typical powder materials,a specific separator manufacturing process must be possessed when incorporating MOFs into lithium sulfur batteries separator.This mini review summarized the manufacturing process of MOFs separator for LSBs in recent years,and summed up the effects and mechanisms of separators prepared by various separator-forming processes on the performance of LSBs,the potential for industrialization of different separator manufacturing processes is also mentioned briefly.
基金financially supported by National Natural Science Foundation of China(No.22304055)Central Guiding Local Science and Technology Development Fund Project(No.236Z4409G)+3 种基金Natural Science Foundation of Hebei Province(No.D2023209012,B2022209026)Youth Talent Program of Hebei Province Education Department(No.BJ2025032)Science and Technology Planning Project of Tangshan City(No.22130227H)Youth Scholars Promotion Plan of North China University of Science and Technology(No.QNTJ202306).
文摘Zinc-based batteries have attracted widespread attention due to their inherent safety,notable cost-effectiveness and consistent performance,etc.However,the advancement of zinc-based battery technology encounters significant challenges,including the formation of zinc dendrites and irreversible side reactions.Separators are vital in batteries due to their role in preventing electrode contact and facilitating rapid movement of ions within the electrolyte.The incorporation of cellulose in batteries enables uniform ion transport and a stable electricfield,attributed to its excellent hydrophilicity,strong mechanical strength,and abundant active sites.Herein,the latest research progress of cellulose-based separators on various zinc-based batteries is systematically summarized.To begin with,the accomplishments and inherent limitations of traditional sep-arators are clarified.Next,it underscores the advantages of cellulose-based materials in battery technology,thoroughly examining their utilization and merits as separators in zinc-based batteries.Lastly,the review offers prospective insights into the future trajectory of cellulose-based separators in zinc-based batteries.Through a comprehensive analysis of the present landscape,the review establishes a framework for the future design and enhancement of cellulose-based separators,thereby fostering the progression of associated industries.
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supported by the National Natural Science Foundation of China(Grant No.52202328,52372099,52271222)the Shanghai Sailing Program(22YF1455500)。
文摘Severe lithium dendrite growth and elevated thermal runaway risks pose significant hurdles for fast-charging lithium metal batteries(LMBs)This study reports a polydopamine-functionalized hydroxyapatite/aramid(PDA@HA)hybrid nanofibers separator to synchronously improve th fast-charging LMB's stability and safety.(1)The separator's surface,enriched with lithiophilic carbonyl and hydroxyl groups,accelerates Li~+ion desolvation,while electrophilic imine groups impede anion movement.This dual mechanism optimizes the Li^(+)-ion flux distribution on th anode,mitigating dendrite formation.(2)The polar PDA modification layer fosters the development of a Li_(3)N/LiF-rich solid electrolyt interface,further enhancing Li anode stability.Consequently,Li//Li symmetric cells with PDA@HA separators exhibit extended cycle life in L plating/stripping tests:5000 h at 1 mA cm^(-2)and 700 h at 20 mA cm^(-2),respectively,outperforming PP separators(80 h and 8 h).In LiFePO_(4)(LFP,^(2.1)mg cm^(-2))//Li full cell evaluation,the PDA@HA separator enables stable operation for 11,000 cycles at 18.2C with 87%capacity retention,significantly outperforming existing fast-charging LMB counterparts in literature.At a high LFP loading of 15.5 mg cm^(-2),the cel maintains 137.6 mAh g^(-1)(2.13 mAh cm^(-2))over 250 cycles at 3C,achieving 98%capacity retention.Moreover,the PDA@HA separato increases threshold temperature for thermal runaway and reduces the exothermic rate,intensifying the battery's thermal safety.This research underscores the importance of functional separator design in improving Li metal anode reversibility,fast-charging performance,and therma safety of LMBs.
基金supported by the National Natural Science Foundation of China(No.U22A20422,22178028)the Program of Introducing Talents of Discipline to Universities(Project 111,B21022)the 5·5 Engineering Research&Innovation Team Project of Beijing Forestry University(No.BLRC2023B01)。
文摘Separators in supercapacitors(SCs)frequently suffer from high resistance and the risk of short circuits due to inadequate electrolyte wettability,depressed mechanical properties,and insufficient thermal stability.Here,we develop a high-performance regenerated cellulose separator with nano-cracked structures for SCs via a binary solvent of superbase-derived ionic liquid and dimethylsulfoxide(DMSO).The unique nano-cracks with an average width of 7.45 nm arise from the acceleration of cellulose molecular reassembly by DMSO-regulated hydrogen bonding,which endows the separator with high porosity(70.2%)and excellent electrolyte retention(329%).The outstanding thermal stability(273℃)and mechanical strength(70 MPa)enable the separator to maintain its structural integrity under high temperatures and external forces.With these benefits,the SC utilizing the cellulose separator enables a high specific capacitance of 93.6 F g^(−1) at 1.0 A g^(−1) and a remarkable capacitance retention of 99.5%after 10,000 cycles compared with the commercial NKK-MPF30AC and NKK-TF4030.The robust and high-wettability cellulose separator holds promise as a superior alternative to commercial separators for advanced SCs with enhanced performance and improved safety.
基金financially supported by the National Natural Science Foundation of China(Grant No.52202328,52372099)the Shanghai Sailing Program(22YF1455500).
文摘Poor Li plating reversibility and high thermal runaway risks are key challenges for fast charging lithiumion batteries with graphite anodes.Herein,a dielectric and fire-resistant separator based on hybrid nanofibers of barium sulfate(BS)and bacterial cellulose(BC)is developed to synchronously enhance the battery's fast charging and thermal-safety performances.The regulation mechanism of the dielectric BS/BC separator in enhancing the Li^(+)ion transport and Li plating reversibility is revealed.(1)The Max-Wagner polarization electric field of the dielectric BS/BC separator can accelerate the desolvation of solvated Li^(+)ions,enhancing their transport kinetics.(2)Moreover,due to the charge balancing effect,the dielectric BS/BC separator homogenizes the electric field/Li^(+)ion flux at the graphite anode-separator interface,facilitating uniform Li plating and suppressing Li dendrite growth.Consequently,the fast-charge graphite anode with the BS/BC separator shows higher Coulombic efficiency(99.0%vs.96.9%)and longer cycling lifespan(100 cycles vs.59 cycles)than that with the polypropylene(PP)separator in the constantlithiation cycling test at 2 mA cm^(-2).The high-loading LiFePO4(15.5 mg cm^(-2))//graphite(7.5 mg cm^(-2))full cell with the BS/BC separator exhibits excellent fast charging performance,retaining 70%of its capacity after 500 cycles at a high rate of 2C,which is significantly better than that of the cell with the PP separator(retaining only 27%of its capacity after 500 cycles).More importantly,the thermally stable BS/BC separator effectively elevates the critical temperature and reduces the heat release rate during thermal runaway,thereby significantly enhancing the battery's safety.
基金funded by the Strategic Priority Research Program of the Chinese Academy of Sciences,Grant Number XDA29020503.
文摘In the novel fully dry converter gas recovery process,a novel circumfluent cyclone separator with an evaporation heating surface can simultaneously realize the dust removal and sensible heat recovery of converter gas.For this equipment,the distributions of internal flow and wall heat transfer affect the efficiency of dust removal and sensible heat recovery.In this study,based on on-site operation tests,the distributions of internal flow and wall heat transfer in the circumfluent cyclone separator are studied by numerical simulation.The results indicate that the flow rate proportions in different regions of the circumfluent cyclone separator remain constant during the steelmaking process,approximately 80.1%of the converter gas flows through the cone chamber,and 15.4%of the converter gas flows through the annular chamber.The heat transfer rate proportions on the walls of different regions of the circumfluent cyclone separator remain constant during the steelmaking process,and the heat transfer rate proportions on the walls of the cone chamber,straight shell,shell head and outlet pipe are 40.2%,27.0%,17.6%and 15.2%,respectively.
基金supported by research grants from the National Natural Science Foundation of China(52173235,22008193,52106110)the Key Research and Development Project of Hainan Province(ZDYF2024SHFZ038)+2 种基金Venture&Innovation Support Program for Chongqing Overseas Returnees(CX2021018)Research Foundation of Chongqing University of Science and Technology(ckrc2021071)Numerical computations were performed on Hefei Advanced Computing Center.
文摘Uncontrolled dendrite growth,sluggish reaction kinetics,and drastic side reactions on the anodeelectrolyte interface are the main obstacles that restrict the application prospect of aqueous zinc-ion batteries.Traditional glass fiber(GF)separator with chemical inertness is almost ineffective in restricting these challenges.Herein,inspired by the ionic enrichment behavior of seaweed plants,a facile biomass species,anionic sodium alginate(SA),is purposely decorated on the commercial GF separator to tackle these issues towards Zn anode.Benefiting from the abundant zincophilic functional groups and superior mechanical strength properties,the as-obtained SA@GF separator could act as ion pump to boost the Zn^(2+)transference number(0.68),reduce the de-solvation energy barrier of hydrated Zn^(2+),and eliminate the undesired concentration polarization effect,which are verified by experimental tests,theoretical calculations,and finite element simulation,respectively.Based on these efficient modulation mechanisms,the SA@GF separator can synchronously achieve well-aligned Zn deposition and the suppression of parasitic side-reactions.Therefore,the Zn‖Zn coin cell integrated with SA@GF separator could yield a prolonged calendar lifespan over 1230 h(1 mA cm^(-2)and 1 mAh cm^(-2)),exhibiting favorable competitiveness with previously reported separator modification strategies.Impressively,the Zn-MnO_(2)full and pouch cell assembled with the SA@GF separator also delivered superior cycling stability and rate performance,further verifying its practical application effect.This work provides a new design philosophy to stabilize the Zn anode from the aspect of separator.
基金supported by the Young Elite Scientists Sponsorship Program by CAST(Grant No.2023QNRC001).
文摘Lithium-ion batteries are used extensively in civil,military,and aerospace applications because of their high energy and power density.However,in practical applications,these batteries may encounter extreme cases characterized by transient high impacts,which impose stringent requirements on their safety and reliability.In recent years,the failure mechanism associated with the short-circuiting of lithium-ion-battery separators under high dynamic impacts has been investigated thoroughly.Based on the separator impact failure mechanism,we prepared a porous polymer polyvinylidene fluoride(PVDF)separator by doping gas-phase SiO_(2)(fumed silica)additive.The gas-phase SiO_(2)has a unique three-dimensional cluster structure,which is impact resistant.The impact resistance of the battery separator was tested using a highdynamic-impact system.The voltage drop of the battery with 3%SiO_(2)content was 33.04%of that of the original PVDF battery.Material characterization of the separator was further explored by scanning electron microscope,static compression,and pore-size adsorption tests.The SiO_(2)with a special cluster structure was distributed uniformly on the surface of the separator and embedded in the inner walls of the pores.Under static compression,the current of the SiO_(2)-PVDF separator with 3%content rose at a lower rate than that of the PVDF separator,with a minimum current of 1.04 mA.After adding SiO_(2),the separator pore size increased from 5 to 20 nm.Also,we used COMSOL to conduct impact simulations of different separators.The calculation results showed that the deformation(9.98%)and internal electrode current(0.018 A)of the SiO_(2)-PVDF lithium-ion battery were lower than the deformation(23.09%)and internal electrode current(0.049 A)of the PVDF lithium-ion battery.The SiO_(2)-doped composite polymer separator with a special cluster structure plays a crucial role in enhancing the impact resistance of lithium-ion batteries.
基金supported by the National Natural Science Foundation of China(22201244,22374125,21971221 and 21773203)the Yangzhou University Interdisciplinary Research Foundation for Chemistry Discipline of Targeted Support(yzuxk202010)+2 种基金High-Level Entrepreneurial and Innovative Talents Program of Jiangsu‘Qing Lan Project’in Colleges and Universities of Jiangsu ProvinceLvyangjinfeng Talent Program of Yangzhou,China Postdoctoral Science Foundation(2022M722688)。
文摘The polysulfides shuttle effect,sluggish sulfur redox kinetics and the corrosion of the Li anode have become important factors limiting the commercial application of lithium-sulfur batteries(LSBs).Herein,the polyoxometalate(POM)nanoclusters with high catalytic activity and cobalt selenide with strong polarity are initially complemented to construct a PMo_(12)/CoSe_(2)@NC/CNTs multifunctional separator that can simultaneously solve the above problems.A series of experimental and theoretical results demonstrate that the Keggin-type POM,H_(3)PMo_(12)O_(40)nH_(2)O(PMo_(12))nanoclusters could function as catalytic centers for sulfur-involved transformations,with the CoSe_(2)nanoparticles serving as adsorption sites for soluble polysulfides.Accordingly,the assembled battery with the PMo_(12)/CoSe_(2)@NC/CNTs modified separator achieves an initial discharge capacity of 1263.79 mA h g^(-1),maintaining 635.77 mA h g^(-1),with a capacity decay rate of 0.06%per cycle after 500 cycles at 3C.This work provides a strategic approach for incorporating POM nanoclusters with polar periodic nanomaterials in LSB separators,contributing to the development of multifunctional separator materials,thus promoting the advancement of energy storage systems.
基金supported by the Natural Science Foundation of Shandong Province(ZR2022QB050)the Liaocheng University Doctoral Initial Fund(318052137)。
文摘Lithium-sulfur(Li-S)batteries with attractive capacity give remarkable potential for prospective high-capacity application scenarios but suffer a fatal flaw of short cyclability before large-scale commercialization especially owing to polysulfide(Li_(2)S_(n))transmembrane shuttling.To efficiently restrain chronic Li_(2)S_(n) shuttle and expedite Li^(+)transfer,herein,a novel electriferous charge-mosaic S(TMC@Lys-Li)separator preparation approach is recommended.Interfacial polymerizations of lithiated lysine and trimesoyl chloride establish an electriferous charge-mosaic polyamide functional layer.Substituted Li within the charge-mosaic layer offers transition or replacement sites for smoothing Li^(+)migrations,which constructs efficient Li^(+)fast-transfer private channels and accelerates the Li^(+)transfer rate to 9.4 times.Negatively charged polyamide skeleton synchronously heightens Li_(2)S_(n) rejections by combining Donnan and steric effects.S(TMC@Lys-Li)replenishes Li for homogenizing Li nucleation and growth,endowing stable plating/stripping behaviors over 250 cycles for Li-Cu batteries.Assembled Li-S cells thus exhibit excellent specific capacity and cyclability at multiple application scenarios such as long periods,high areal capacity,and fast charge,holding 78.1%retention after 500 cycles at 1 C.The superior thermal stability and self-discharge of S(TMC@Lys-Li)dramatically strengthen battery thermal runaway resistance even at155℃,which ensures security for Li-S battery high-power and high-temperature operations.Above alluring features enable charge-mosaic separators to be potentially adopted in practical Li-S batteries demanding strict security,high-capacity density,and fast charge technology.
基金the financial support from the Natural Science Foundation of Jiangsu Province(BK20231292)the Jiangsu Agricultural Science and Technology Innovation Fund(CX(24)3091)+2 种基金the National Natural Science Foundation of China(12464032)the Natural Science Foundation of Jiangxi Province(20232BAB201032)supported by the high performance computing university-level public platform of Jinggangshan University.
文摘Aqueous zinc-ion batteries encounter enormous challenges such as Zn dendrites and parasitic reactions.Separator modification is a highly effective strategy to address these issues.With the advantages of low cost,nontoxicity,biodegradability,good film-forming ability,superior hydro phi licity,and rich functional groups,chitosan is an ideal matrix for constructing separators.However,the presence of positive charges within chitosan in weakly acidic electrolytes is unfavorable for dendrite inhibition.Herein,Schiff base reaction is introduced to modify chitosan matrix,transforming its charge polarity from positive to negative.Additionally,NbN with excellent zincophilicity is coated onto chitosan matrix,forming a Janus separator with low thickness of 19μm and considerably improved mechanical properties.The resultant separator can promote the transport of Zn^(2+)ions while triggering a repulsive shielding effect against anions,therefore dramatically enhancing Zn^(2+)ion transfer number from 0.28 to 0.49.This separator can also facilitate desolvation process,improve exchange current density,restrict two-dimensional Zn^(2+)ion diffusion,and enhance electrochemical kinetics,contributing to significantly inhibited dendrite growth,by-product formation,and hydrogen evolution.Consequently,stable and reversible Zn stripping/plating process is enabled for over 2500 h at 2 mA cm^(-2)and 2 mAh cm^(-2).And great rate capability and excellent cyclability can be achieved for full batteries even under harsh conditions.This work provides new insights into separator design for Zn-based batteries.
基金supported by the National Natural Science Foundation of China(No.51972066)the Natural Science Foundation of Guangdong Province of China(No.2024A1515012499)。
文摘The uneven deposition and high reactivity of lithium-metal anode(LMA)lead to uncontrollable dendrite growth,low Coulombic efficiency,and safety concerns,hindering their commercialization.Here,a representative polar-rich-group triazine-based covalent organic framework(COF-TzDha)with a desolvation effect is designed as an interlayer for stable,dendrite-free LMA.The abundant triazine rings in COFTzDha as a donor effectively attract lithium ions,while the one-dimensional nanopore structure facilitates lithium-ion migration.The periodic arrangement of polar groups(-OH)in the backbone interacts with electrolyte components(DOL,DME,TFSI-)to form a hydrogen bonding network that slows solvent molecules transport.Therefore,COF-TzDha effectively desolvates lithium ions from the solvent sheath,promoting uniform lithium ion flux and Li plating/stripping.Theoretical calculations verify that COFTzDha with abundant adsorption sites and strong adsorption energy facilitates lithium ion desolvation.Consequently,the introduction of COF-TzDha obtains a high ion mobility(0.75).The Li|COF@PP|Li symmetric cell cycles stably for over 1200 h at 4 mA cm^(-2)/4.0 mA h cm^(-2).The Li|COF@PP|LiFePO_(4)full cell also displays highly stable cycling performance with 600 cycles(75.5%capacity retention,~100% Coulombic efficiency)at 1 C.This work verifies an effective strategy for inducing uniform Li deposition and achieving dendrite-free,stable LMA using a polar-rich-group COF interlayer with a desolvation effect.
基金supported by National Natural Science Foundation of China(Nos.52472194,52101243)Natural Science Foundation of Guangdong Province,China(No.2023A1515012619)the Science and Technology Planning Project of Guangzhou(No.202201010565)。
文摘Owing to the advantages of high energy density,low cost,abundant sulfur reserves and environmentally friendly nature,lithium-sulfur batteries(LSBs)were considered as one of the potential candidates of energy storage devices for the next generation.However,the significant challenges in this area stem from the sluggish reaction kinetics of the insoluble Li_(2)S product and the capacity degradation triggered by the severe shuttle effect of polysulfides.It has been firmly established through numerous studies that modifying separators is an effective approach to enhance the properties of LSBs by facilitating the catalytic kinetic conversion and chemical adsorption of lithium polysulfides(Li PSs).In this work,we report a straightforward method for fabrication of the phosphorus doped porous CeO_(2)(P-CeO_(2))as separator modifier to accelerate the catalytic kinetic conversion of polysulfides and effectively inhibit the shuttle effect in LSBs.Through coin batteries tests,P-CeO_(2)modified PP separator(P-CeO_(2)//PP)exhibits remarkable electrochemical performance.It demonstrates a high initial capacity of 1180 mAh/g at 0.5 C,surpassing the performance of the bare CeO_(2)//PP separator.Furthermore,the P-CeO_(2)//PP separator demonstrates enhanced cycling stability,with a low-capacity fading rate of only 0.048%per cycle over 1000 cycles at 2 C.In compared with bare CeO_(2)//PP,P-CeO_(2)//PP exhibits high redox peak current,enhanced adsorption property of Li_(2)S_(6)and early Li_(2)S precipitation.These results highlight the superior performance of the P-CeO_(2)//PP separator compared to the bare CeO_(2)//PP separator.Hence,this research presents a successful strategy for the modification of LIBs separator with improved electrochemical performance and cycle stability.
基金supported by the National Natural Science Foundation of China(Grant Number 22350410379)Zhejiang Provincial Natural Science Foundation of China(LZ23B030003)+1 种基金the Fundamental Research Funds for the Central Universities(226-202400075)Ten Thousand Talent Program of Zhejiang Province.
文摘Separator modification is an effective approach to suppress dendrite growth to realize high-energy sodium metal batteries(SMBs)in practical applications,however,its success is mainly subject to surface modification.Herein,a separator with multifunctional layers composed of N-doped mesoporous hollow carbon spheres(HCS)as the inner layer and sodium fluoride(NaF)as the outer layer on commercial polypropylene separator(PP)is proposed(PP@HCS-NaF)to achieve stable cycling in SMB.At the molecular level,the inner HCS layer with a high content of pyrrolic-N induces the uniform Na^(+)flux as a potential Na^(+)redistributor for homogenous deposition,whereas its hollow mesoporous structure offers nanoporous buffers and ion channels to regulate Na^(+)ion distribution and uniform deposition.The outer layer(NaF)constructs the NaF-enriched robust solid electrolyte interphase layer,significantly lowering the Na^(+)ions diffusion barrier.Benefiting from these merits,higher electrochemical performances are achieved with multifunctional double-layered PP@HCS-NaF separators compared with single-layered separators(i.e.PP@HCS or PP@NaF)in SMBs.The Na‖Cu half-cell with PP@HCS-NaF offers stable cycling(280 cycles)with a high CE(99.6%),and Na‖Na symmetric cells demonstrate extended lifespans for over 6000 h at 1 mA cm^(-2)with a progressively stable overpotential of 9 mV.Remarkably,in Na‖NVP full-cells,the PP@HCS-NaF separator grants a stable capacity of~81 mA h g^(-1)after 3500 cycles at 1 C and an impressive rate capability performance(~70 mA h g^(-1)at 15 C).
