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
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
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
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
Attention toward aqueous zinc-ion battery has soared recently due to its operation safety and environmental benignity.Nonetheless,dendrite formation and side reactions occurred at the anode side greatly hinder its pra...Attention toward aqueous zinc-ion battery has soared recently due to its operation safety and environmental benignity.Nonetheless,dendrite formation and side reactions occurred at the anode side greatly hinder its practical application.Herein,we adopt direct plasma-enhanced chemical vapor deposition strategy to in situ grow N-doped carbon(NC)over commercial glass fiber separator targeting a highly stabilized Zn anode.The strong zincophilicity of such a new separator would reduce the nucleation overpotential of Zn and enhance the Zn-ion transference number,thereby alleviating side reactions.Symmetric cells equipped with NC-modified separator harvest a stable cycling for more than 1,100 h under 1 mA·cm^(−2)/1 mAh·cm^(−2).With the assistance of NC,the depth of discharge of Zn anode reaches as high as 42.7%.When assembled into full cells,the zinc-ion battery based on NC-modified separator could maintain 79%of its initial capacity(251 mAh·g^(−1))at 5 A·g^(−1) after 1,000 cycles.展开更多
An unstable solid electrolyte interphase(SEI)and chaotic lithium ion fux are key impediments to commercial high-energy-density lithium batteries because of the uncontrolled growth of rigid lithium dendrites,which woul...An unstable solid electrolyte interphase(SEI)and chaotic lithium ion fux are key impediments to commercial high-energy-density lithium batteries because of the uncontrolled growth of rigid lithium dendrites,which would pierce through the conventional polypropylene(PP)separator,causing short circuit and safety issues.Herein,the homogenization of lithium ion fux and the generation of stable SEI layers on lithium anodes were achieved via coating a fuorine-functionalized Ti_(3)C_(2)(F-Ti_(3)C_(2))nanosheets on PP separator(F-Ti_(3)C_(2)@PP).F-Ti_(3)C_(2)nanosheets provide abundant ions pathways to homogeneously manipulate lithium ion fux and increase the Young’s modulus and electrolyte wettability of the separators.In addition,F species derived from the F-Ti_(3)C_(2)nanosheets would promote the formation of Li F-rich SEI film.The synergistic effect contribute to the uniform lithium deposition.Symmetric Li|Li,asymmetric Li|Cu and full Li|Li Fe PO4cells incorporated with the modified separators exhibit improved electrochemical performance even under lean electrolyte conditions.This work provides a feasible strategy to improve the performance of lithium batteries through both fuoridized SEI formation and lithium ion fux manipulation.展开更多
Due to their low cost,environmental friendliness and high energy density,the lithium-sulfur batteries(LSB)have been regarded as a promising alternative for the next generation of rechargeable battery systems.However,t...Due to their low cost,environmental friendliness and high energy density,the lithium-sulfur batteries(LSB)have been regarded as a promising alternative for the next generation of rechargeable battery systems.However,the practical application of LSB is seriously hampered by its short cycle life and high self-charge owing to the apparent shuttle effect of soluble lithium polysulfides.Using MgSO_(4)@MgO composite as both template and dopant,template-guided S-doped mesoporous graphene(SMG)is prepared via the fluidized-bed chemical vapor deposition method.As the polypropylene(PP)modifier,SMG with high specific surface area,abundant mesoporous structures and moderate S doping content offers a wealth of physical and chemical adsorptive sites and reduced interfacial contact resistance,thereby restraining the serious shuttle effects of lithium polysulfides.Consequently,the LSB configured with mesoporous graphene(MG)as S host material and SMG as a separator modifier exhibits an enhanced electrochemical performance with a high average capacity of 955.64 mA h g^(-1) at 1C and a small capacity decay rate of 0.109%per cycle.Additionally,the density functional theory(DFT)calculation models have been rationally constructed and demonstrated that the doped S atoms in SMG possess higher binding energy to lithium polysulfides than that in MG,indicating that the SMG/PP separator can effectively capture soluble lithium polysulfides via chemical binding forces.This work would provide valuable insight into developing a versatile carbon-based separator modifier for LSB.展开更多
Aqueous zinc-ion batteries(AZIBs) hold great promise as a viable alternative to lithium-ion batteries owing to their high energy density and environmental friendliness.However,AZIBs are consistently plagued by the for...Aqueous zinc-ion batteries(AZIBs) hold great promise as a viable alternative to lithium-ion batteries owing to their high energy density and environmental friendliness.However,AZIBs are consistently plagued by the formation of zinc dendrites and concurrent side reactions,which significantly diminish their overall service life,In this study,the glass fiber separator(GF) is modified using zeolite imidazole salt framework-8(ZIF-8),enabling the development of efficient AZIBs.ZIF-8,which is abundant in nitrogen content,efficiently regulates the desolvation of [Zn(H_(2)O)_(6)]^(2+) to inhibit hydrogen production.Moreover,it possesses abundant nanochannels that facilitate the uniform deposition of Zn~(2+) via a localized action,thereby hindering the formation of dendrites.The insulating properties of ZIF-8 help prevent Zn^(2+) and water from trapping electron reduction at the layer surface,which reduces corrosion of the zinc anode.Consequently,ZIF-8-GF achieves the even transport of Zn^(2+) and regulates the homogeneous deposition along the Zn(002) crystal surface,thus significantly enhancing the electrochemical performance of the AZIBs,In particular,the Zn|Zn symmetric cell with the ZIF-8-GF separator delivers a stable cycle life at0.5 mA cm^(-2) of 2300 h.The Zn|ZIF-8-GF|MnO_(2) cell exhibits reduced voltage polarization while maintaining a capacity retention rate(93.4%) after 1200 cycles at 1.2 A g^(-1) The unique design of the modified diaphragm provides a new approach to realizing high-performance AZIBs.展开更多
Lithium metal batteries(LMBs)with high energy density are impeded by the instability of solid electrolyte interface(SEI)and the uncontrolled growth of lithium(Li)dendrite.To mitigate these challenges,optimizing the SE...Lithium metal batteries(LMBs)with high energy density are impeded by the instability of solid electrolyte interface(SEI)and the uncontrolled growth of lithium(Li)dendrite.To mitigate these challenges,optimizing the SEI structure and Li deposition behavior is the key to stable LMBs.This study novelty proposes a facile synthesis of MgF_(2)/carbon(C)nanocomposite through the mechanochemical reaction between metallic Mg and polytetrafluoroethylene(PTFE)powders,and its modified polypropylene(PP)separator enhances LMB performance.The in-situ formed highly conductive fluorine-doped C species play a crucial role in facilitating ion/electron transport,thereby accelerating electrochemical kinetics and altering Li deposition direction.During cycling,the in-situ reaction between MgF_(2)and Li leads to the formation of LiMg alloy,along with a LiF-rich SEI layer,which reduces the nucleation overpotential and reinforces the interphase strength,leading to homogeneous Li deposition with dendrite-free feature.Benefiting from these merits,the Li metal is densely and uniformly deposited on the MgF_(2)/C@PP separator side rather than on the current collector side.Furthermore,the symmetric cell with MgF_(2)/C@PP exhibits superb Li plating/stripping performance over 2800 h at 1 mA cm^(-2)and 2 mA h cm^(-2).More importantly,the assembled Li@MgF_(2)/C@PPILiFePO4full cell with a low negative/positive ratio of 3.6delivers an impressive cyclability with 82.7%capacity retention over 1400 cycles at 1 C.展开更多
The popularity of lithium–sulfur batteries has been increasing gradually due to their ultrahigh theoretical specific capacity and energy density. Nevertheless, they also have lots of drawbacks to be overcome, such as...The popularity of lithium–sulfur batteries has been increasing gradually due to their ultrahigh theoretical specific capacity and energy density. Nevertheless, they also have lots of drawbacks to be overcome, such as poor conductivity, severe volume expansion, and serious“shuttle effect”. In this work, reduced graphene oxide/molybdenum dioxide(rGO/MoO_(2)) composite is synthesized and applied to modify polypropylene separator. The modified polypropylene separator introduces synergistic tri-functions of physical adsorption, chemical interaction and catalytic effects, which can inhibit the“shuttle effect” and enhance the electrochemical performances of lithium-sulfur batteries. In the prepared r GO/MoO_(2) composite, the polar MoO_(2) chemically adsorbs the intermediate lithium polysulfide, while the rGO with good electrical conductivity not only acts as a physical barrier to prevent diffusion of polysulfide ions, but also improves the conversion efficiency of active material intercepted on the separator. As a consequence, the battery assembled with rGO/MoO_(2) modified polypropylene separator exhibits a reversible capacity of 757.5 mAh·g^(-1) after 200 cycles at0.2 C with a negligible capacity decay of 0.207% per cycle,which indicates a good long-period cycling stability. Furthermore, the rate performance and self-discharge suppression are also improved by introducing modified polypropylene separator. It shows that rGO/MoO_(2) composite is a promising material for separator modification in lithium-sulfur batteries.展开更多
The polysulfide shuttle limits the development of lithium-sulfur(Li-S) batteries with high energy density and long lifespan. Herein, nitrogen doped hollow carbon nanospheres(NHCS) derived from polymerization of dopami...The polysulfide shuttle limits the development of lithium-sulfur(Li-S) batteries with high energy density and long lifespan. Herein, nitrogen doped hollow carbon nanospheres(NHCS) derived from polymerization of dopamine on SiO_(2)nanospheres are employed to modify the commercial polypropylene/polyethylene/polypropylene tri-layer separators(PP/PE/PP@NHCS). The abundant nitrogen heteroatoms in NHCS exhibit strong chemical adsorption toward polysulfides, which can effectively suppress the lithium polysulfides shuttle and further enhance the utilization of active sulfur. Lithium-sulfur batteries employing the PP/PE/PP@NHCS deliver an initial discharge capacity of 1355 mAh/g and retain high capacity of 921 mAh/g after 100 cycles at 0.2 C. At a high rate of 2 C, the lithium-sulfur batteries exhibit capacity of 461 mAh/g after 1000 cycles with a capacity fading rate of 0.049% per cycle. This work demonstrates that the NHCS coated PP/PE/PP separator is promising for future commercial applications of lithium-sulfur batteries with improved electrochemical performances.展开更多
Magnesium-sulfur(Mg-S)batteries have attracted wide research attention in recent years,and are considered as one of the major candidates to replace lithium-ion batteries due to the high theoretical energy density,low ...Magnesium-sulfur(Mg-S)batteries have attracted wide research attention in recent years,and are considered as one of the major candidates to replace lithium-ion batteries due to the high theoretical energy density,low costs of active materials,and high safety.However,there are still significant challenges that need to be overcome before they can reach the large-scale practical applications.The key issue is the dissolution and shuttle effect of magnesium polysulfides(Mg-PSs),which leads to severe capacity degradation and shortens cycling life,greatly limiting the development of Mg-S batteries.In order to overcome these challenges,great efforts have been made in cathode materials,electrolytes,and separators.Herein,we review the investigations on suppressing the shuttle effect of Mg-PSs via the modification of separators,including schemes such as coating the functional materials that can hold Mg-PSs on the surface of polyolefin-based or glass fiber(GF)separators,forming gel polymer separators via cross-linking polymerization reactions,and developing gel polymer electrolytes coupled with GF separators.Furthermore,an outlook is proposed for the future design on separator exploitation to accelerate the development of Mg-S battery technology.展开更多
Regulating the catalyst electronic structure is critical for improving the adsorption and catalytic conversion of lithium polysulfides(LiPSs)in lithium-sulfur batteries(Li-S),yet which has been overlooked in current s...Regulating the catalyst electronic structure is critical for improving the adsorption and catalytic conversion of lithium polysulfides(LiPSs)in lithium-sulfur batteries(Li-S),yet which has been overlooked in current studies.In this work,structurally defined Ag_(30)Pd_(4)nanoclusters were loaded onto reduced graphene oxide(Ag_(30)Pd_(4)/rGO)as a modification material for polypropylene(PP)separators to elucidate the catalytic activity towards lithium polysulfides and the impact on the electrochemical properties to lithium sulfur batteries.This unique d-πcombination promotes charge transfer,influences overall charge states,and further enhances adsorption energies in potential reaction pathways with lithium polysulfides.Consequently,the Ag_(30)Pd_(4)/rGO/PP modified batteries exhibited an exceptionally low-capacity decay rate of 0.026%per cycle at 1.0C over 1000 stable cycles and 9.75 mAh cm^(-2)excellent performance even with lean electrolyte and high sulfur loading(9.7 mg cm^(-2)).This study paves a path for employing ultrasmall bimetallic nanoclusters to promote the polysulfides redox kinetics hence boosting the lithiumsulfur battery performance.展开更多
Lithium-sulfur(Li-S) batteries have received extensive attention due to their high theoretical specific energy density.However,the utilization of sulfur is seriously reduced by the shuttle effect of lithium polysulfid...Lithium-sulfur(Li-S) batteries have received extensive attention due to their high theoretical specific energy density.However,the utilization of sulfur is seriously reduced by the shuttle effect of lithium polysulfides and the low conductivity of sulfur and lithium sulfide(Li2S).Herein,we introduced bimetalorganic frameworks(Co/Zn-ZIF) derived cobalt and nitrogen-doped carbons(Co/N-C) into Li-S batteries through host design and sepa rator modification.The Co/N-C in Li-S batteries effectively limits the shuttle effect through simultaneously serving as polysulfide traps and chemical catalyst.As a result,the Li-S batteries deliver a high reversible capacity of 1614.5 mAh/g and superior long-term cycling stability with a negligible capacity decay of only 0.04% per cycle after 1000 cycles.Furthermore,they have a high area capacity of 5.5 mAh/cm2.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
Lithium-sulfur(Li-S)battery,as a promising next-generation high-energy-density battery,suffers from lithium polysulfides(LPSs)shuttle and Li dendrites issues.Porous crystalline framework-based membranes as separator c...Lithium-sulfur(Li-S)battery,as a promising next-generation high-energy-density battery,suffers from lithium polysulfides(LPSs)shuttle and Li dendrites issues.Porous crystalline framework-based membranes as separator can effectively absorb and restrain LPSs but without precise structural design principal exploration and mechanism studies.Herein,bio-inspired 1D oriented lithium-ion transport channels with molecular negatively charged PO_(3)(-1)have been developed in hybrid tetrazole frameworks for promoting the transmission of Li+ions.The theoretical calculations and in situ spectroscopy demonstrated the higher binding energy and inhibited diffusion of LPSs in PO_(3).The assembled PP@PO_(3)Janus separator in Li-S coin cell delivered a high initial capacity of 1410.9 mAhg^(-1)at 0.1 C and a low attenuation rate of 0.038%per cycle over 500 cycles at 5 C.Besides,the high capacities of 862,542 and 409 mAhg^(-1)based on high-sulfur-loading cathodes of 2.6,3.8 and 5.0 mg cm^(-2)at 0.5 C were achieved,respectively.Moreover,the punch battery of PO_(3)@PP separator with S-cathode of 1.2 mg cm^(-2)has been developed for demonstrating its potentials commercial application,which displays impressive capacity of 873.4 mAhg-1with the retention of~78.9%over 50 cycles.展开更多
The practical application of lithium(Li)metal batteries(LMBs)faces challenges due to the irreversible Li deposition/dissolution process,which promotes Li dendrite growth with severe parasitic reactions during cycling....The practical application of lithium(Li)metal batteries(LMBs)faces challenges due to the irreversible Li deposition/dissolution process,which promotes Li dendrite growth with severe parasitic reactions during cycling.To address these issues,achieving uniform Li‐ion flux and improving Li‐ion conductivity of the separator are the top priorities.Herein,a separator(PCELS)with enhanced Li‐ion conductivity,composed of polymer,ceramic,and electrically conductive carbon,is proposed to facilitate fast Li‐ion transport kinetics and increase Li deposition uniformity of the LMBs.The PCELS immobilizes PF6–anions with high adsorption energies,leading to a high Li‐ion transference number.Simultaneously,the PCELS shows excellent electrolyte wettability on both its sides,promoting rapid ion transport.Moreover,the electrically conductive carbon within the PCELS provides additional electron transport channels,enabling efficient charge transfer and uniform Li‐ion flux.With these advantages,the PCELS achieves rapid Li‐ion transport kinetics and uniform Li deposition,demonstrating excellent cycling stability over 100 cycles at a high current density of 12.0 mA cm–2.Furthermore,the PCELS shows stable cycling performances in Li–S cell tests and delivers an excellent capacity retention of 95.45%in the Li|LiFePO4 full‐cell test with a high areal capacity of over 5.5 mAh cm–2.展开更多
Lithium-sulfur(Li-S)batteries have great potential as the next generation of high-energy-density storage systems.However,the practical viability of Li-S batteries is largely hampered by undesirable shuttling behavior ...Lithium-sulfur(Li-S)batteries have great potential as the next generation of high-energy-density storage systems.However,the practical viability of Li-S batteries is largely hampered by undesirable shuttling behavior and sluggish conversion kinetics of polysulfides.Herein,a multifunctional separatormodified layer(In/Zr-BTB nanosheets)with the merits of robust structures and efficient catalytic metal sites has been presented.In/Zr-BTB nanosheets inherit the stable structure from Zr-BTB and strengthen the catalytic performance due to the introduction of highly catalytic species indium via metal-ion exchange.The thickness and areal mass loading of the modified layer are only 260 nm and 0.011 mg/cm2,respectively.Nevertheless,the ultrathin modification layers with efficient catalytic species,compact structures,and uniform pore channels can realize fast Li+transport,effective polysulfide interception,and rapid catalytic conversion.Therefore,the In/Zr-BTB@PP cell with a high sulfur content of 80 wt%could maintain high capacity retention of 85.6%with a low capacity fading rate of 0.048%per cycle after 300 cycles even at a high current rate of 2 C.This work opens a new door toward the design of versatile metal-organic framework(MOF)nanosheets and multifunctional separators for high-energy-density Li-S batteries.展开更多
Rechargeable aqueous zinc metal batteries(RAZMBs) have received extensive attention for large-scale energy storage systems due to the merits of Zn anodes, including moderate volumetric and gravimetric energy density, ...Rechargeable aqueous zinc metal batteries(RAZMBs) have received extensive attention for large-scale energy storage systems due to the merits of Zn anodes, including moderate volumetric and gravimetric energy density, low redox potential, abundant reserve, low cost and impressive intrinsic safety. However, Zn anodes suffer from a series of adverse reactions(dendrite growth,hydrogen evolution, and surface passivation) resulting in low Coulombic efficiency, large polarization, and unsatisfied cycling performance, which inevitably hinder the wide application of RAZMBs. To address the above issues, cellulose-based materials are widely used for Zn anode protection because of their unique physical and chemical properties and other advantages such as biocompatibility, non-toxicity, degradability and easy extraction. In order to better understand the current progress in cellulosebased materials for the Zn anode protection, we have classified and summarized the relevant literatures. In this review, we summarize and elaborate the causes of poor reversibility for Zn anodes, including dendrite formation, hydrogen evolution, and surface passivation. Subsequently, the effective strategies(anode interfacial engineering, gel electrolyte optimization, and separator modification) of cellulose-based materials toward stabilizing Zn anodes are overviewed. In the end, the existing challenges and prospects of cellulose-based materials in Zn anode protection are summarized to shed light on future work.展开更多
A simple method for the magnetic modification of various types of powdered agglomerate forming dia- magnetic materials was developed. Magnetic iron oxide particles were prepared from ferrous sulfate by microwave assis...A simple method for the magnetic modification of various types of powdered agglomerate forming dia- magnetic materials was developed. Magnetic iron oxide particles were prepared from ferrous sulfate by microwave assisted synthesis. A suspension of the magnetic particles in water soluble organic solvent （methanol, ethanol, propanol, isopropyl alcohol, or acetone） was mixed with the material to be modified and then completely dried at elevated temperature. The magnetically modified materials were found to be stable in water suspension at least for 2 months.展开更多
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).
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 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financially supported by the National Key Research and Development Program of China(No.2019YFA0708201)Suzhou Science and Technology Project-Prospective Application Research Program(No.SYG202038).
文摘Attention toward aqueous zinc-ion battery has soared recently due to its operation safety and environmental benignity.Nonetheless,dendrite formation and side reactions occurred at the anode side greatly hinder its practical application.Herein,we adopt direct plasma-enhanced chemical vapor deposition strategy to in situ grow N-doped carbon(NC)over commercial glass fiber separator targeting a highly stabilized Zn anode.The strong zincophilicity of such a new separator would reduce the nucleation overpotential of Zn and enhance the Zn-ion transference number,thereby alleviating side reactions.Symmetric cells equipped with NC-modified separator harvest a stable cycling for more than 1,100 h under 1 mA·cm^(−2)/1 mAh·cm^(−2).With the assistance of NC,the depth of discharge of Zn anode reaches as high as 42.7%.When assembled into full cells,the zinc-ion battery based on NC-modified separator could maintain 79%of its initial capacity(251 mAh·g^(−1))at 5 A·g^(−1) after 1,000 cycles.
基金financially supported by the National Natural Science Foundation of China(21931005,21871177,20172012002)the Natural Science Foundation of Shanghai(20ZR1427600)the Shanghai Science and Technology Committee(19JC1412600)。
文摘An unstable solid electrolyte interphase(SEI)and chaotic lithium ion fux are key impediments to commercial high-energy-density lithium batteries because of the uncontrolled growth of rigid lithium dendrites,which would pierce through the conventional polypropylene(PP)separator,causing short circuit and safety issues.Herein,the homogenization of lithium ion fux and the generation of stable SEI layers on lithium anodes were achieved via coating a fuorine-functionalized Ti_(3)C_(2)(F-Ti_(3)C_(2))nanosheets on PP separator(F-Ti_(3)C_(2)@PP).F-Ti_(3)C_(2)nanosheets provide abundant ions pathways to homogeneously manipulate lithium ion fux and increase the Young’s modulus and electrolyte wettability of the separators.In addition,F species derived from the F-Ti_(3)C_(2)nanosheets would promote the formation of Li F-rich SEI film.The synergistic effect contribute to the uniform lithium deposition.Symmetric Li|Li,asymmetric Li|Cu and full Li|Li Fe PO4cells incorporated with the modified separators exhibit improved electrochemical performance even under lean electrolyte conditions.This work provides a feasible strategy to improve the performance of lithium batteries through both fuoridized SEI formation and lithium ion fux manipulation.
基金supported by the Science Foundation of China University of Petroleum,Beijing(No.ZX20230047)Open Research Fund of State Key Laboratory of Coking Coal Exploitation and Comprehensive Utilization,China Pingmei Shenma Group(No.41040220201308).
文摘Due to their low cost,environmental friendliness and high energy density,the lithium-sulfur batteries(LSB)have been regarded as a promising alternative for the next generation of rechargeable battery systems.However,the practical application of LSB is seriously hampered by its short cycle life and high self-charge owing to the apparent shuttle effect of soluble lithium polysulfides.Using MgSO_(4)@MgO composite as both template and dopant,template-guided S-doped mesoporous graphene(SMG)is prepared via the fluidized-bed chemical vapor deposition method.As the polypropylene(PP)modifier,SMG with high specific surface area,abundant mesoporous structures and moderate S doping content offers a wealth of physical and chemical adsorptive sites and reduced interfacial contact resistance,thereby restraining the serious shuttle effects of lithium polysulfides.Consequently,the LSB configured with mesoporous graphene(MG)as S host material and SMG as a separator modifier exhibits an enhanced electrochemical performance with a high average capacity of 955.64 mA h g^(-1) at 1C and a small capacity decay rate of 0.109%per cycle.Additionally,the density functional theory(DFT)calculation models have been rationally constructed and demonstrated that the doped S atoms in SMG possess higher binding energy to lithium polysulfides than that in MG,indicating that the SMG/PP separator can effectively capture soluble lithium polysulfides via chemical binding forces.This work would provide valuable insight into developing a versatile carbon-based separator modifier for LSB.
基金financially supported by National Natural Science Foundation of China(No.51872090,51772097)Hebei Natural Science Fund for Distinguished Young Scholar(No.E2019209433)+2 种基金Youth Talent Program of Hebei Provincial Education Department(No.BJ2018020)Natural Science Foundation of Hebei Province(No.E2020209151)the financial support from Donghua University(101-08-0241022,23D210105,and 101-07-005759)。
文摘Aqueous zinc-ion batteries(AZIBs) hold great promise as a viable alternative to lithium-ion batteries owing to their high energy density and environmental friendliness.However,AZIBs are consistently plagued by the formation of zinc dendrites and concurrent side reactions,which significantly diminish their overall service life,In this study,the glass fiber separator(GF) is modified using zeolite imidazole salt framework-8(ZIF-8),enabling the development of efficient AZIBs.ZIF-8,which is abundant in nitrogen content,efficiently regulates the desolvation of [Zn(H_(2)O)_(6)]^(2+) to inhibit hydrogen production.Moreover,it possesses abundant nanochannels that facilitate the uniform deposition of Zn~(2+) via a localized action,thereby hindering the formation of dendrites.The insulating properties of ZIF-8 help prevent Zn^(2+) and water from trapping electron reduction at the layer surface,which reduces corrosion of the zinc anode.Consequently,ZIF-8-GF achieves the even transport of Zn^(2+) and regulates the homogeneous deposition along the Zn(002) crystal surface,thus significantly enhancing the electrochemical performance of the AZIBs,In particular,the Zn|Zn symmetric cell with the ZIF-8-GF separator delivers a stable cycle life at0.5 mA cm^(-2) of 2300 h.The Zn|ZIF-8-GF|MnO_(2) cell exhibits reduced voltage polarization while maintaining a capacity retention rate(93.4%) after 1200 cycles at 1.2 A g^(-1) The unique design of the modified diaphragm provides a new approach to realizing high-performance AZIBs.
基金financially supported by the Natural Science Foundation of China(52277218)the Hubei Provincial Natural Science Foundation of China(2024AFA094)+1 种基金the Excellent Discipline Cultivation Project by JHUN(2023XKZ009)the Graduate Student Innovation Fund of JHUN(KYCXJJ202422).
文摘Lithium metal batteries(LMBs)with high energy density are impeded by the instability of solid electrolyte interface(SEI)and the uncontrolled growth of lithium(Li)dendrite.To mitigate these challenges,optimizing the SEI structure and Li deposition behavior is the key to stable LMBs.This study novelty proposes a facile synthesis of MgF_(2)/carbon(C)nanocomposite through the mechanochemical reaction between metallic Mg and polytetrafluoroethylene(PTFE)powders,and its modified polypropylene(PP)separator enhances LMB performance.The in-situ formed highly conductive fluorine-doped C species play a crucial role in facilitating ion/electron transport,thereby accelerating electrochemical kinetics and altering Li deposition direction.During cycling,the in-situ reaction between MgF_(2)and Li leads to the formation of LiMg alloy,along with a LiF-rich SEI layer,which reduces the nucleation overpotential and reinforces the interphase strength,leading to homogeneous Li deposition with dendrite-free feature.Benefiting from these merits,the Li metal is densely and uniformly deposited on the MgF_(2)/C@PP separator side rather than on the current collector side.Furthermore,the symmetric cell with MgF_(2)/C@PP exhibits superb Li plating/stripping performance over 2800 h at 1 mA cm^(-2)and 2 mA h cm^(-2).More importantly,the assembled Li@MgF_(2)/C@PPILiFePO4full cell with a low negative/positive ratio of 3.6delivers an impressive cyclability with 82.7%capacity retention over 1400 cycles at 1 C.
基金financially supported by the National Natural Science Foundation of China (Nos.21606065 and 21676067)Anhui Provincial Natural Science Foundation (Nos.1708085QE98 and 1908085QE178)+1 种基金the Fundamental Research Funds for the Central Universities (Nos.JZ2017YYPY0253,JZ2017HGTB0198,JZ2018HGBZ0138 and PA2020GDGP0054)the Opening Project of CAS Key Laboratory of Materials for Energy Conversion (No.KF2018003)。
文摘The popularity of lithium–sulfur batteries has been increasing gradually due to their ultrahigh theoretical specific capacity and energy density. Nevertheless, they also have lots of drawbacks to be overcome, such as poor conductivity, severe volume expansion, and serious“shuttle effect”. In this work, reduced graphene oxide/molybdenum dioxide(rGO/MoO_(2)) composite is synthesized and applied to modify polypropylene separator. The modified polypropylene separator introduces synergistic tri-functions of physical adsorption, chemical interaction and catalytic effects, which can inhibit the“shuttle effect” and enhance the electrochemical performances of lithium-sulfur batteries. In the prepared r GO/MoO_(2) composite, the polar MoO_(2) chemically adsorbs the intermediate lithium polysulfide, while the rGO with good electrical conductivity not only acts as a physical barrier to prevent diffusion of polysulfide ions, but also improves the conversion efficiency of active material intercepted on the separator. As a consequence, the battery assembled with rGO/MoO_(2) modified polypropylene separator exhibits a reversible capacity of 757.5 mAh·g^(-1) after 200 cycles at0.2 C with a negligible capacity decay of 0.207% per cycle,which indicates a good long-period cycling stability. Furthermore, the rate performance and self-discharge suppression are also improved by introducing modified polypropylene separator. It shows that rGO/MoO_(2) composite is a promising material for separator modification in lithium-sulfur batteries.
基金supported by the National Natural Science Foundation of China (Nos. U1964205, 51872303, 52172253)Zhejiang Provincial Natural Science Foundation of China (No. LD18E020004)+3 种基金Ningbo S&T Innovation 2025 Major Special Programme (Nos. 2019B10044, 20211ZDYF020077)Zhejiang Provincial Key R&D Program of China (No. 2022C01072)Chongqing Research Program of Basic Research and Frontier Technology (No. cstc2019jcyjmsxm X0510)Youth Innovation Promotion Association CAS (No. 2017342)。
文摘The polysulfide shuttle limits the development of lithium-sulfur(Li-S) batteries with high energy density and long lifespan. Herein, nitrogen doped hollow carbon nanospheres(NHCS) derived from polymerization of dopamine on SiO_(2)nanospheres are employed to modify the commercial polypropylene/polyethylene/polypropylene tri-layer separators(PP/PE/PP@NHCS). The abundant nitrogen heteroatoms in NHCS exhibit strong chemical adsorption toward polysulfides, which can effectively suppress the lithium polysulfides shuttle and further enhance the utilization of active sulfur. Lithium-sulfur batteries employing the PP/PE/PP@NHCS deliver an initial discharge capacity of 1355 mAh/g and retain high capacity of 921 mAh/g after 100 cycles at 0.2 C. At a high rate of 2 C, the lithium-sulfur batteries exhibit capacity of 461 mAh/g after 1000 cycles with a capacity fading rate of 0.049% per cycle. This work demonstrates that the NHCS coated PP/PE/PP separator is promising for future commercial applications of lithium-sulfur batteries with improved electrochemical performances.
基金the financial support from the National Natural Science Foundation of China(No.21975159)Open Fund of Shanghai Jiao Tong University Shaoxing Institute of New Energy and Molecular Engineering(No,JDSX2022033)Oceanic Interdisciplinary Program of Shanghai Jiao Tong University(No.WH410260401/006)。
文摘Magnesium-sulfur(Mg-S)batteries have attracted wide research attention in recent years,and are considered as one of the major candidates to replace lithium-ion batteries due to the high theoretical energy density,low costs of active materials,and high safety.However,there are still significant challenges that need to be overcome before they can reach the large-scale practical applications.The key issue is the dissolution and shuttle effect of magnesium polysulfides(Mg-PSs),which leads to severe capacity degradation and shortens cycling life,greatly limiting the development of Mg-S batteries.In order to overcome these challenges,great efforts have been made in cathode materials,electrolytes,and separators.Herein,we review the investigations on suppressing the shuttle effect of Mg-PSs via the modification of separators,including schemes such as coating the functional materials that can hold Mg-PSs on the surface of polyolefin-based or glass fiber(GF)separators,forming gel polymer separators via cross-linking polymerization reactions,and developing gel polymer electrolytes coupled with GF separators.Furthermore,an outlook is proposed for the future design on separator exploitation to accelerate the development of Mg-S battery technology.
基金supported in part by the Institute for Advanced Study of Central South University and the High Performance Computing Center of Central South Universitythe funding from Guangdong Natural Science Funds(No.2023A0505050107)。
文摘Regulating the catalyst electronic structure is critical for improving the adsorption and catalytic conversion of lithium polysulfides(LiPSs)in lithium-sulfur batteries(Li-S),yet which has been overlooked in current studies.In this work,structurally defined Ag_(30)Pd_(4)nanoclusters were loaded onto reduced graphene oxide(Ag_(30)Pd_(4)/rGO)as a modification material for polypropylene(PP)separators to elucidate the catalytic activity towards lithium polysulfides and the impact on the electrochemical properties to lithium sulfur batteries.This unique d-πcombination promotes charge transfer,influences overall charge states,and further enhances adsorption energies in potential reaction pathways with lithium polysulfides.Consequently,the Ag_(30)Pd_(4)/rGO/PP modified batteries exhibited an exceptionally low-capacity decay rate of 0.026%per cycle at 1.0C over 1000 stable cycles and 9.75 mAh cm^(-2)excellent performance even with lean electrolyte and high sulfur loading(9.7 mg cm^(-2)).This study paves a path for employing ultrasmall bimetallic nanoclusters to promote the polysulfides redox kinetics hence boosting the lithiumsulfur battery performance.
基金supported by National Natural Science Foundation of China(Nos.51822205,21875121,51602218 and 51972231)Ministry of Science and Technology of China(No.2017YFA0206700)+2 种基金Ministry of Education of China(No.B12015)Natural Science Foundation of Tianjin Municipal Science and Technology Commission(No.18JCQNJC02400)the Science&Technology Development Fund of Tianjin Education Commission for Higher Education(No.2017KJ248)。
文摘Lithium-sulfur(Li-S) batteries have received extensive attention due to their high theoretical specific energy density.However,the utilization of sulfur is seriously reduced by the shuttle effect of lithium polysulfides and the low conductivity of sulfur and lithium sulfide(Li2S).Herein,we introduced bimetalorganic frameworks(Co/Zn-ZIF) derived cobalt and nitrogen-doped carbons(Co/N-C) into Li-S batteries through host design and sepa rator modification.The Co/N-C in Li-S batteries effectively limits the shuttle effect through simultaneously serving as polysulfide traps and chemical catalyst.As a result,the Li-S batteries deliver a high reversible capacity of 1614.5 mAh/g and superior long-term cycling stability with a negligible capacity decay of only 0.04% per cycle after 1000 cycles.Furthermore,they have a high area capacity of 5.5 mAh/cm2.
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(22271178)the International Cooperation Key Project of Science and Technology Department of Shaanxi,China(2022KWZ-06)+4 种基金the Youth Talent Promotion Project of Science and Technology Association of Universities of Shaanxi Province(20210602)the Research Project of Xi’an Science and Technology Bureau(2022GXFW0011)the Science and Technology New Star in Shaanxi Province(2023KJXX-045)the Shaanxi Provincial Department of Education Service Local Special Projectthe Industrialization Cultivation Project(23JC007)。
文摘Lithium-sulfur(Li-S)battery,as a promising next-generation high-energy-density battery,suffers from lithium polysulfides(LPSs)shuttle and Li dendrites issues.Porous crystalline framework-based membranes as separator can effectively absorb and restrain LPSs but without precise structural design principal exploration and mechanism studies.Herein,bio-inspired 1D oriented lithium-ion transport channels with molecular negatively charged PO_(3)(-1)have been developed in hybrid tetrazole frameworks for promoting the transmission of Li+ions.The theoretical calculations and in situ spectroscopy demonstrated the higher binding energy and inhibited diffusion of LPSs in PO_(3).The assembled PP@PO_(3)Janus separator in Li-S coin cell delivered a high initial capacity of 1410.9 mAhg^(-1)at 0.1 C and a low attenuation rate of 0.038%per cycle over 500 cycles at 5 C.Besides,the high capacities of 862,542 and 409 mAhg^(-1)based on high-sulfur-loading cathodes of 2.6,3.8 and 5.0 mg cm^(-2)at 0.5 C were achieved,respectively.Moreover,the punch battery of PO_(3)@PP separator with S-cathode of 1.2 mg cm^(-2)has been developed for demonstrating its potentials commercial application,which displays impressive capacity of 873.4 mAhg-1with the retention of~78.9%over 50 cycles.
基金supported by Ministry of Science and ICT,South Korea(RS‐2024‐00407282)National Research Foundation of Korea(RS‐2024‐00408156).
文摘The practical application of lithium(Li)metal batteries(LMBs)faces challenges due to the irreversible Li deposition/dissolution process,which promotes Li dendrite growth with severe parasitic reactions during cycling.To address these issues,achieving uniform Li‐ion flux and improving Li‐ion conductivity of the separator are the top priorities.Herein,a separator(PCELS)with enhanced Li‐ion conductivity,composed of polymer,ceramic,and electrically conductive carbon,is proposed to facilitate fast Li‐ion transport kinetics and increase Li deposition uniformity of the LMBs.The PCELS immobilizes PF6–anions with high adsorption energies,leading to a high Li‐ion transference number.Simultaneously,the PCELS shows excellent electrolyte wettability on both its sides,promoting rapid ion transport.Moreover,the electrically conductive carbon within the PCELS provides additional electron transport channels,enabling efficient charge transfer and uniform Li‐ion flux.With these advantages,the PCELS achieves rapid Li‐ion transport kinetics and uniform Li deposition,demonstrating excellent cycling stability over 100 cycles at a high current density of 12.0 mA cm–2.Furthermore,the PCELS shows stable cycling performances in Li–S cell tests and delivers an excellent capacity retention of 95.45%in the Li|LiFePO4 full‐cell test with a high areal capacity of over 5.5 mAh cm–2.
基金support by the National Natural Science Foundation of China(grant nos.22005054,22101048,21805039,21971038,and 21975044)Natural Science Foundation of Fujian Province(grant no.2021J01149)State Key Laboratory of Structural Chemistry(grant no.20200007).
文摘Lithium-sulfur(Li-S)batteries have great potential as the next generation of high-energy-density storage systems.However,the practical viability of Li-S batteries is largely hampered by undesirable shuttling behavior and sluggish conversion kinetics of polysulfides.Herein,a multifunctional separatormodified layer(In/Zr-BTB nanosheets)with the merits of robust structures and efficient catalytic metal sites has been presented.In/Zr-BTB nanosheets inherit the stable structure from Zr-BTB and strengthen the catalytic performance due to the introduction of highly catalytic species indium via metal-ion exchange.The thickness and areal mass loading of the modified layer are only 260 nm and 0.011 mg/cm2,respectively.Nevertheless,the ultrathin modification layers with efficient catalytic species,compact structures,and uniform pore channels can realize fast Li+transport,effective polysulfide interception,and rapid catalytic conversion.Therefore,the In/Zr-BTB@PP cell with a high sulfur content of 80 wt%could maintain high capacity retention of 85.6%with a low capacity fading rate of 0.048%per cycle after 300 cycles even at a high current rate of 2 C.This work opens a new door toward the design of versatile metal-organic framework(MOF)nanosheets and multifunctional separators for high-energy-density Li-S batteries.
基金supported by National Natural Science Foundation of China (52273095, 22209140, 52202286)Zhejiang Provincial Natural Science Foundation of China (LGG23B030011,LY24B030006)+7 种基金Zhejiang Provincial Natural Science Key Foundation of China (LZ20E030003LGG22E030005)Natural Science Foundation of Shandong Province (ZR2022QE059)the Outstanding Youth Project of Zhejiang Provincial Natural Science Foundation (LR22E030002)the State Key Laboratory for Modification of Chemical Fibers and Polymer Materials(KF2314)a Project Supported by Scientific Research Fund of Zhejiang Provincial Education Department (Y202148249)Science Foundation of Zhejiang Sci-Tech University (ZSTU) under Grant No. 21202086-YShandong Laboratory of Advanced Materials and Green Manufacturing at Yantai (Yantai)(AMGM2023A08)。
文摘Rechargeable aqueous zinc metal batteries(RAZMBs) have received extensive attention for large-scale energy storage systems due to the merits of Zn anodes, including moderate volumetric and gravimetric energy density, low redox potential, abundant reserve, low cost and impressive intrinsic safety. However, Zn anodes suffer from a series of adverse reactions(dendrite growth,hydrogen evolution, and surface passivation) resulting in low Coulombic efficiency, large polarization, and unsatisfied cycling performance, which inevitably hinder the wide application of RAZMBs. To address the above issues, cellulose-based materials are widely used for Zn anode protection because of their unique physical and chemical properties and other advantages such as biocompatibility, non-toxicity, degradability and easy extraction. In order to better understand the current progress in cellulosebased materials for the Zn anode protection, we have classified and summarized the relevant literatures. In this review, we summarize and elaborate the causes of poor reversibility for Zn anodes, including dendrite formation, hydrogen evolution, and surface passivation. Subsequently, the effective strategies(anode interfacial engineering, gel electrolyte optimization, and separator modification) of cellulose-based materials toward stabilizing Zn anodes are overviewed. In the end, the existing challenges and prospects of cellulose-based materials in Zn anode protection are summarized to shed light on future work.
文摘A simple method for the magnetic modification of various types of powdered agglomerate forming dia- magnetic materials was developed. Magnetic iron oxide particles were prepared from ferrous sulfate by microwave assisted synthesis. A suspension of the magnetic particles in water soluble organic solvent （methanol, ethanol, propanol, isopropyl alcohol, or acetone） was mixed with the material to be modified and then completely dried at elevated temperature. The magnetically modified materials were found to be stable in water suspension at least for 2 months.
